NanoSpain 2016 abstracts book

Abstracts Book

10 μm

Sample: Thermally aged stainless steel. (Left) Helios PFIB, slice thickness 46.6 μm. (Right) Ga PFIB, slice thickness 7.6 μm.

Helios PFIB DualBeam Large 3D volumes with unprecedented surface resolution The Helios PFIB DualBeam provides serial sectioning volumes of 97 x 79 x 47 um after cropping, compared to typical volumes of 19 x 18 x 8 um for Ga FIB. And Helios is optimized for large cross-sections and high-throughput processing—20 to 100 times faster than traditional FIB—without causing the mechanical damage typical during polishing.

Obtaining larger, high-resolution volumes faster enables: • Better statistical accuracy when processing data • Imaging and analysis of large-grained materials/metals in 3D • Biopsies or chunking of large regions of interest for further investigation with other techniques while keeping the bulk sample intact

FEI.com | Explore. Discover. Resolve.

Index

Foreword Organisers & Sponsors Committees Exhibitors Contributions Abstracts

02 03 03 04 08 17

Consolidated as a reference meeting of Nanoscience and Nanotechnology (N&N) in Spain, the NanoSpain2016 conference is not limited to a conventional presentation of ideas or results, but seeks to deepen the common themes among the participants, also serving as a link between industry and researchers.

Since 2004, year the event was launched, NanoSpain conference series is now an established and wellknown meeting in Spain, aiming to agglutinate and coordinate the efforts made in the field of the Nanotechnology by Spanish groups from universities, research institutes and companies.

NanoSpain events facilitate the dissemination of knowledge and promote interdisciplinary discussions not only in Spain but among the different groups from Southern Europe.

Over the past years, NanoSpain conference became more and more multidisciplinary and 2016 won’t be an exception. NanoSpain2016 will cover a broad range of current research in Nanoscience and Nanotechnology.

2

The NanoSpain2016 edition will take place in the RiojaForum - Logroño (Spain).

NanoSpain2016 will offer a multitude of renowned international Keynote and Invited speakers, contributed talks, posters and a commercial exhibition. In addition thematic parallel sessions will also be organised to enhance information flow between participants and in particular:    

Exchange information of current work in specific research areas Solve particular technological problems Look for areas of common ground between different technologies Provide contributions to specific reports

The following Thematic Sessions will be organised: 1.

2.

3.

Graphene Nanobiotechnology / Nanomedicine Nanochemistry

We would like to thank all participants, speakers, sponsors and exhibitors that joined us this year.

Finally, thanks must be directed to the staff of all organising institutions whose hard work has helped the smooth organisation and planning of this conference.

THE ORGANISING COMMITTEE

Organisers

Sponsors

Organising Committee Jean-Pierre Aime Xavier Bouju Fernando Briones Antonio Correia Pedro Miguel Echenique Lars Montelius José Manuel Perlado Martín Emilio Prieto Juan José Sáenz Josep Samitier Daniel Sánchez Portal

Universite Bordeaux I & C'Nano Grand Sud-Ouest (France) CEMES-CNRS & C'Nano Grand Sud-Ouest (France) CNM/IMM-CSIC (Spain) Conference Chairman - Fundación Phantoms (Spain) UPV/EHU – DIPC - CFM (Spain) INL (Portugal) IFN-ETSII / UPM (Spain) Centro Español de Metrología - CEM (Spain) Donostia International Physics Center (Spain) IBEC/Universidad de Barcelona (Spain) CSIC - UPV/EHU - DIPC (Spain)

Advisory Board Sabino Azcarate Jaime Colchero Jesús M. de la Fuente Pedro Miguel Echenique Javier Méndez Rodolfo Miranda Enrique Navarro Pablo Ordejón Fernando Palacio José Mª Pitarke Emilio Prieto José Rivas Juan Jose Saenz Josep Samitier Conchita Solans Jaume Veciana José Luis Viviente

Tekniker - IK4 (Spain) Universidad de Murcia (Spain) ICMA / CSIC / Universidad de Zaragoza (Spain) UPV/EHU – DIPC - CFM (Spain) ICMM - CSIC (Spain) Universidad Autónoma de Madrid (Spain) Instituto Pirenaico de Ecología-CSIC (Spain) ICN2 (Spain) ICMA / CSIC / Universidad de Zaragoza (Spain) CIC nanoGUNE Consolider (Spain) Centro Español de Metrología - CEM (Spain) Universidad Santiago de Compostela (Spain) Donostia International Physics Center (Spain) IBEC/Universidad de Barcelona (Spain) Instituto de Investigaciones Químicas y Ambientales de Barcelona (Spain) Instituto de Ciencia de Materiales de Barcelona - CSIC (Spain) Tecnalia (Spain)

3

Exhibitors

4

Raith offers innovative solutions for sub-10nm focused ion beam (FIB) nanofabrication, SEM-based electron beam lithography (EBL), large area SEM image capture, gas-assisted nanolithography, in situ nanomanipluation and nanoprofilometry. Raith’s proprietary FIB technology offers a wide range of ion species and elevates FIB based nanofabrication to a new level with highest selectivity and unsurpassed stability for automated wafer-scale patterning. www.raith.com sales@raith.com

ScienTec, specialized in the distribution of rigorously selected scientific equipments (AFM microscope, Vacuum technology, NanoIndentation systems, Profilometers), has for mission to serve and assist French, Iberian and Nordic markets.

With more than 15 years experience in Nanotechnology, our sales engineers will help you to define the right tool and configuration, our application group will teach and help you run the machines and our after sales team will preventively maintain or repair your systems.

Your investment will be back up with a perfect combination of top level instruments with the know-how and tool expertise in the distribution. info@scientec.fr www.scientec.fr

SPECS Surface Nano Analysis GmbH - A Story of Constant Innovation SPECS has more than 150 employees at its headquarters in Berlin and its subsidiaries in the USA and Switzerland. The company also has sales offices and international sales channels in more than sixteen countries. A team of scientists and engineers are involved in developing and producing scientific instruments for surface analysis, material science and nanotechnology. By constant innovation new techniques, components or system concepts are launched every year since more than 30 years, revolutionizing the field of surface analysis. www.specs.com

Lasing, S.A. is, since 1980, a company dedicated to the distribution in Spain of the highest technology in instrumentation and photonics products. We are pioneers of introducing new technologies in Spain, with excellent technical support.Lasing facility is based in Madrid, which is a multi purpose-built 1000 m2 premises. The premises include optical, electronic and mechanical workshops for system integration and equipment testing.

Lasing consists of highly qualified, professional staff members. Our teamwork possess superb educational backgrounds, many with advanced degrees in science (physics and chemistry), electronics engineering and marketing/business management. Lasing has a large number of installations in Research Centers, Universities, Hospitals and main Industries. Reliability and customer satisfaction have the priority at Lasing to establish long term relationship with our customers and principals. www.lasing.com info@lasing.com

5 Nanovex Biotechnologies SL is an innovative technology-based spin-off founded in 2014 that provides a wide range of services and products in the nanobiotechnology field.

Our specialized team has great experience in the design, development, modification, functionalization and characterization of nanovesicles and metallic nanoparticles for multiple applications.

Nanovex Biotechnologies SL provides services linked to the design and development of several nanomaterials such as nanovesicles and metallic nanoparticles, as well as their surface modification or functionalization with biomaterials (e. g. antibodies, biotin, avidin).

Furthermore, our company offers several products based in different nanomaterials by appling our technology of design, development and modification of nanovesicles and metallic nanoparticles to assist in the development of applications and products in the field of medicine, pharmacy or food industry. www.nanovexbiotech.com info@nanovexbiotech.com

6

CEMITEC ADItech (www.cemitec.com), the Multidisciplinary Centre of Technologies for Industry – being FUNDACION CETENA as legal entity – is part of the Industry area of ADItech. ADItech (Advanced Innovation and Technology Corporation/ www.aditechcorp.com) is a private entity with more than 800 researchers that brings together technology centres located in Navarra in the fields of: Energy, Industry, Agro-food, and Biomedicine, and it has a clear international objective.

CEMITEC'S goal is to develop technology that can be transferred to industry. CEMITEC ADItech has a team of high qualified people specialised in four technological areas: Electronics, Mechanics, Materials, and Material Deposition Technologies.

This multidisciplinary team is composed of people with varied but complimentary experience, qualifications, and skills, working together to give solution to very different situations. CEMITEC ADItech works with over 350 industrial partners every year, participates in many FP7 and H2020 European consortiums (e.g.: NanoSelect, SusFoFlex, PowGeTec, Seed Capital, Net Market Fluids, EnviGuard…), and in national and regional research projects. Its facilities include: materials testing laboratories, chemical laboratories, nanomaterials handling clean rooms, electronical laboratories, climatic chambers, FE-SEM, printing pilot lines, nanolitography equipment, sensing lab … www.cemitec.com

The Institut Català de Nanociència i Nanotecnologia (ICN2 – Catalan Institute of Nanoscience and Nanotechnology) is a non-profit international research institute close to Barcelona (Spain). Its research lines focus on the newly discovered physical and chemical properties that arise from the fascinating behaviour of matter at the nanoscale.

Its mission is to become an international centre of reference in Nanoscience and Nanotechnology.

ICN2 interacts with universities, research centres, technology centres, private sector R&D, the scientific community and society in general. It is among the initial promoters of the Graphene Flagship and part of the Barcelona Institute of Science and Technology (www.bist.eu). www.icn.cat

From cutting edge scientific research to routine surface investigations, NT-MDT has a unique and unrivalled portfolio of scanning probe microscopes.

Our application-focused instruments provide you with a full range of capabilities in AFM-Raman, high-resolution, multi-frequency measurements, and AFM based nanomechanics. As an innovator in SPM for over 20 years, NT-MDT has a specialized high-performance solution for your research needs.

Key Products: SPM/AFM/STM; Raman TERS; Spectroscopy www.ntmdt.com info@ntmdt.ie

Alava Ingenieros Group is an entirely privately owned group which has been providing high technology solutions in the Testing, Measurement, Communications, Security, Defence and Preventive Maintenance fields since it was first founded in 1973 and recently in Nanotechnology.

The group not only offers high technology distribution but also consultancy, engineering, training and technical services, providing turn-key projects. Alava Ingenieros excels in its ability to adapt to the specific needs of its customers and its responsible attitude towards supplies and services carried out, all of which is backed by solid international partnerships and in house resources for integration, installation and after-sales technical service. www.alava-ing.es

Microtest distributes, since more than 20 years, in Europe, High Quality equipment for Physics and Chemistry, materials, microelectronics and nanotechnologies universities and labs.

Microtest Sales and Technical Engineers will bring you their knowledge and support along your project, from the configuration choice to the install of your equipment and will provide the After-Sale Service adapted to your need. microtest@microtest-semi.com www.microtest-semi.com

The Centre for the Development of Industrial Technology (CDTI) is a Public Business Entity, answering to the Ministry of Economy and Competitiveness, which fosters the technological development and innovation of Spanish companies.

It is the entity that channels the funding and support applications for national and international R&D&i projects of Spanish companies. The CDTI thus seeks to contribute to improving the technological level of the Spanish companies. www.cdti.es info@cdti.es

ITENE is a Technological Center offering specialized services in the fields of occupational and environmental health, hygiene and safety. Within our safety and emerging risks unit, we help our clients to successfully implement environmental, health and safety (EHS) regulations, as well as to deal with emerging risks from new technologies such as nanotechnology. We bring together multidisciplinary expertise in hazard assessment, exposure, occupational hygiene and risk assessment of engineering nanomaterials (ENMs). Our facilities cover the needs of the industry including laboratory services to support either hazard and exposure assessment, personal protective equipment testing, simulation of common operative conditions, dustiness testing and morphological and elemental sample analysis. For further info visit: www.itene.com info@itene.com

Graphene-Tech is a technology-based company dedicated to the development of new materials, based on the multilayered graphene manufactured by the company, to be used in the technical industry and other specialized markets. The company also works in the efficient use of resources and environmental care, holding a spirit of both ecological and economical sustainability. www.graphene-tech.net info@graphene-tech.net

The Footwear Technology Centre of La Rioja (CTCR), a non-profit organization, first opened in January 16th 2007 with the clear vocation to provide technology solutions and meet the demands of businesses within the footwear sector.

Whilst adapting and evolving in a constantly changing market, the CTCR demonstrates a clear commitment to promoting Research, Development and Innovation (R&D&i) as a process for sustainable growth and enhancing competitiveness among companies within the footwear sector. www.ctcr.es info@ctcr.es

AVANZARE is a supplier of high-performance nanomaterials and nanotechnology based solutions used in a wide range of products for everyday life.

AVANZARE nanomaterials and nanocomposites create added values and competitive advantages for our customers. In many applications, our nanomaterials allow the reduction of costs compared to traditional materials. www.avanzare.es info@avanzare.es

The Universidad de la Rioja is the only Higher Education institution in the Autonomous Region of La Rioja devoted to the multiple tasks of teaching, research, dissemination of culture and innovation.

Located in the North of Spain, La Rioja is a modern, hospitable region with a very high quality of life, best known for its famous wine and as being regarded as the cradle of the Spanish language. www.unirioja.es info@unirioja.es

The association, Institute of Chemical Technologies Emerging Rioja emerges as a nonprofit organization that aims to fill the gap between the production company and the university as being able to develop technology for direct application technology in the industry. www.interquimica.org mperez@interquimica.org

7

Contributions

INDEX- Alphabetical Order Page Lorenzo Albertazzi (Institute for Bioengineering of Catalonia (IBEC), Spain)

INVITED Parallel Session

18

Nanoscopy for Nanomedicine: looking at nanomaterials one molecule at a time Julio A. Alonso (Universidad de Valladolid, Spain)

INVITED Parallel Session

Adsorption and storage of hydrogen in porous and layered materials Antonio Ardizzone (Institut de Ciència de Materials de Barcelona (ICMABCSIC), Spain) Quatsomes: Promising Highly Stable Nanovesicles for Drug Delivery

ORAL Parallel Session

Enrique Barrigón (Division of Solid State Physics / Nanolund, Sweden)

ORAL Plenary Session

Shell material assessment for GaAs-based nanowire solar cells Fabienne Barroso-Bujans (Donostia International Physics Center, Spain)

INVITED Parallel Session

Extreme 2D-confinement of polymers in graphene-based materials Massimiliano Bartolomei (Institute of Fundamental Physics, IFF-CSIC, Spain)

ORAL Parallel Session

Hydrogen physisorption and intercalation in novel nano-porous graphites Ofra Benny (The Hebrew University of Jerusalem, Israel)

KEYNOTE Plenary Session

Targeting Tumors with Solidified Polymer Micelles Dario Bercioux (Donostia International Physics Center, Spain)

INVITED Parallel Session

Mode splitting in zigzag carbon nanotubes Jesús R. Berenguer (Universidad de La Rioja, Spain)

ORAL Plenary Session

Design of mesoporous hybrid titania for solar light harvesting using coordination transition metal complexes as building blocks Luca Bergamini (CFM, CSIC-UPV/EHU and DIPC, Spain)

ORAL Plenary Session

Ultrafast control of plasmonic nanoantennas driven by hot-spot induced phase-transitions transitions in VO2 POSTER Luca Bergamini (CFM, CSIC-UPV/EHU and DIPC, Spain) Enhanced and Tunable Magneto-Optcs Optcs via Fano Lattice Surface Modes in Arrays of Anisotropic Magnetic Nanoantennas

Francesco Bonaccorso (IIT, Graphene Labs, Italy)

KEYNOTE Plenary Session

Graphene, other 2D crystals and hybrid superstructures ures for energy and (opto)electronic applications Alex Bondarchuk (CIC energiGUNE, Spain)

ORAL Parallel Session

Vanadium nitride thin films and nanoclusters: combined XPS and electrochemical characterization Paolo Bondavalli (THALES Research and Technology, France) Nanomaterials for different applications: sensing, energy storage and memories

KEYNOTE Plenary Session

19 20 21 23 24 26 27

28

29 31

33

34

36

9

Page ORAL Enrique Burzurí (Kavli Institute of Nanoscience. Delft University of Plenary Session Technology, The Netherlands) Kondo effect and magnetic exchange inversion in neutral and stable organic radical single molecule break junctions

Izaskun Bustero (TECNALIA, Spain)

ORAL Parallel Session

Graphene-based composites for thermal management applications Laura Cabeza Montilla (SAS-Universidad de Granada, Spain) PLGA nanoparticles as paclitaxel delivery system for the treatment of breast cancer Inmaculada Cabrera Hinojosa (CDTI, Spain)

POSTER

ORAL Parallel Session

EUREKA Cluster "Graphene & 2D Materials" Nuria Campos Alfaraz (Graphene Square Europe, Spain)

ORAL Parallel Session

Advanced CVD systems for the synthesis of two-dimensional dimensional materials beyond graphene Alba Centeno (Graphenea, Spain)

INVITED Parallel Session

Graphene status and needs for industry integration Jean-Christophe Charlier (University of Louvain, Belgium)

KEYNOTE Plenary Session

Electronic transport in 1D atomic carbon chains and in 2D conjugated polymer networks Patrick Chaskiel (Université Paul Sabatier, France)

10

KEYNOTE Plenary Session

From “beneficial properties” to the “benefits” of nanos: a social process Javier Conesa-Egea (Universidad Autónoma de Madrid, Spain) Luminescent nanoribbons based on 1D coordination polymers with Cu-I chains

POSTER

Elena Contreras-García (Universidad de La Rioja, Spain) Photocontrol of antibacterial capacity based on Z/E isomerism

POSTER

Juan Carlos Cuevas (Universidad Autónoma de Madrid, Spain)

INVITED Plenary Session

Near-field radiative heat transfer at the nanoscale POSTER Inmaculada De la Calle Gonzalez (Ultra Trace Analyses Aquitaine UT2A/ADERA, France and Universidad de Vigo, Spain) Particle size determination of metal oxides and metallic (nano-)particles )particles in consumer products

by DLS, AF4-MALLS-ICP-MS and SP-ICP-MS

Pilar de Miguel (CDTI, Spain)

ORAL Parallel Session

CDTI: Funding Opportunities for Graphene Pablo Díaz Núñez (Instituto de Fusión Nuclear, UPM, Spain)

ORAL Plenary Session

Effect of organic stabilizers rs over silver nanoparticles fabricated by femtosecond pulsed laser ablation POSTER Pablo Díaz Núñez (Instituto de Fusión Nuclear, UPM, Spain) Embedded silver nanoparticle multilayers fabricated by femtosecond pulsed laser deposi deposition

Álvaro Díez (Footwear Technology Center of La Rioja (CTCR), Spain) Towards the nanotechnology in the footwear sector

ORAL Plenary Session

37

38 40 42 44 45 46 47 48 49

50

52 53 54

Page Gema M. Durán (University of Castilla-La Mancha, Spain)

ORAL Parallel Session

CdSe/ZnS Quantum Dots for Improving ving Detection Capabilities in Analytical Processes Jean-Olivier Durand (Institut Charles Gerhardt Montpellier - CNRS, France)

KEYNOTE Plenary Session

Mesoporous silica, periodic mesoporous organosilica, and mesoporous silicon nanoparticles for drug delivery and two-photon Photodynamic Therapy Pedro Miguel Echenique (UPV-EHU, DIPC, CFM, Spain)

PLENARY LECTURE Plenary Session

Surface Attophysics POSTER

Adela Eguizábal (Centro Tecnológico del Calzado de La Rioja, Spain) Approaching Nanoscience to the Footwear Sector Klaus Ensslin (ETH Zurich, Switzerland)

KEYNOTE Plenary Session

Mesoscopic thermodynamics in nanostructures Nerea Epelde-Elezcano (University of the Basque Country, Spain)

ORAL Parallel Session

Photosensitizer-Silica Nanoparticle as Platform for Photodynamic Therapy POSTER

Cintia Ezquerro (Universidad de La Rioja, Spain) Synthesis of luminescent hybrid silica-based materials Jordi Faraudo (ICMAB-CSIC, Spain)

INVITED Parallel Session

Self-assembly of organic molecules onto surfaces: computer simulations Gianluca M. Farinola (Università degli Studi di Bari “Aldo Moro”, Italy)

KEYNOTE Plenary Session

Smart nanomaterials built up from functional organic molecules and photosynthetic microorganisms Matthias A. Fenner (Keysight Technologies, Germany)

ORAL Plenary Session

Improved Method for Probing Resistivity and Doping Concentration of Semiconductors at the Nanoscale Using Scanning Microwave Microscopy (SMM) Paulo J. Ferreira (The University of Texas at Austin, USA)

KEYNOTE Plenary Session

The Science of the Small: Understanding the Coalescence of Nanoparticles by Advanced Transmission Electron Microscopy Carlos Fito (ITENE, Spain)

ORAL Plenary Session

Lessons from case studies: exposure to engineered nanomaterials and effectiveness of workplace controls in the polymer nanocomposites industry Mar García Hernández (Instituto de Ciencia de Materiales de Madrid -CSIC, Spain) GRAPHENET: The Spanish Graphene Network Antonio Garcia-Martin (IMM-(CNM-CSIC), Spain)

ORAL PParallel Sessions

INVITED Plenary Session

Sensing Performance of Hybrid Magnetoplasmonic Nanohole Arrays POSTER Alba García Rodríguez (Universitat Autònoma de Barcelona (UAB), Spain) Genotoxicity Assessment of Air-Borne Engineered Nanomaterials using the BEAS-2B 2B and A549 in vitro System

56

57

58 59 60 61 62 63

11 64

65

66

-

67 68 70

Page Julio Gómez Cordón (Avanzare, Spain)

INVITED Parallel Session

Bulk graphene preparation for energy and composites applications Julio Gómez-Herrero (UAM, Spain)

INVITED Parallel Session

Mechanical properties of fluctuating graphene Consuelo Gómez de Castro (Universidad Complutense de Madrid, Spain) Study of the grain thermal stability in the nanostructured tungsten coatings

POSTER

73 75

POSTER Sara Gómez Miralles (ICMol (Instituto de Ciencia Molecular), Spain) Interface-assisted assisted Sign Inversion of Magnetoresistance in Spin Valves based on Novel Lanthanide Quinoline Molecules

76

INVITED Pedro Gómez-Romero (Catalan Institut of Nanoscience and Nanotechnology, Parallel Session ICN2 (CSIC-CERCA), Spain) Spicing Graphene with electroactive inorganic compounds: Graphene hybrid nanocomposites for energy storage

77

ORAL César González (Universidad de Granada, Spain and Service de Physique de Plenary Session l'Etat Condensé, CEA/Saclay, France) Detection of Inorganic Molecules on reactive MoS2 defects by ab-initio initio Atomic Force Microscopy Simulations

79

Lucía González Bermúdez (GrapheneTech, Spain)

ORAL Parallel Session

Industrial Graphene nanoplatelets possibilities

12

72

POSTER Daniel González Mancebo (Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Spain) Tunable size Ln:BaGdF5 (Ln= Eu3+ and Nd3+) nanoparticles. Luminescence,, magnetic properties, and biocompatibility

Natascia Grimaldi (Nanomol Technologies SA, Spain)

ORAL Parallel Session

CO2-based-surfactant-free microemulsions-like like system as futurist universal green medium for chemical processes Ruta Grinyte (CIC biomaGUNE, Spain)

ORAL Parallel Session

Facile and inexpensive biocatalytic method for resizing of semiconductor cadmium sulfide nanoparticles Gonzalo Guerrica-Echevarría (University of the Basque Country (UPV/EHU), Spain) Bio-based polyamide/carbon nanotube nanocomposites

POSTER

Victor Herrero-Solana (Universidad de Granada, Spain) Patentometric Study of Nanotechnology in Spain

POSTER

Rainer Hillenbrand (CIC nanoGUNE and IKERBASQUE, Spain)

INVITED Plenary Session

ORAL Parallel Session

Nanomedicine, from PoC to reality: the importance of an industrial perspective and GMP scale up David Jiménez (Universitat Autònoma de Barcelona, Spain) Scalability of the graphene/semiconductor barristor targeting digital applications

83

85

86

87

Nanoimaging and manipulation of polaritons in graphene and boron nitride Oihane Ibarrola (Biopraxis Research AIE (Praxis Pharmaceutical) Spain)

81

POSTER

90 92 93 95

Page POSTER Julia Jiménez López (Universidad de Granada, Spain) Enhanced delivery of Paclitaxel aclitaxel using PLGA nanoparticles: therapeutic effect in lung cancer cell cultures

96

POSTER Marlene Klein (Ultra Traces Analyses Aquitaine (ADERA-UT2A), France) Characterization of polymer based nanopharmaceuticals by Asymmetrical Flow Field Flow Fractionation

98

Frank Koppens (ICREA/ICFO, Spain)

INVITED Parallel Session

Photons, Plasmons and Electrons meet in 2d materials Lise-Marie Lacroix (LPCNO, UMR 5215 INSA-CNRS-UPS, France)

KEYNOTE Plenary Session

Nanoparticles with optimized properties:: from chemical synthesis to assembly A bottom bottom-up approach for nanostructured materials Rebeca Lara (Universidad de La Rioja, Spain) Luminescent platinum systems based on the chromophore 2-phenylbenzothiazole phenylbenzothiazole

POSTER

Fernando Ignacio López-Bara (Autonomous Barcelona University, Spain) Dynamics of the spin-ice states with magnetic charges

POSTER

Manuel López-López (Universidad de Huelva, Spain)

ORAL Plenary Session

Do strong surfactant/swcnt-cooh interactions assure good dispersion quality?

100

102 104 105 106

POSTER Manuel López-López (Universidad de Huelva, Spain) A thorough spectroscopic study about the interaction of surfactants with carboxylated singlewalled carbon nanotubes

107

POSTER Diego López-Torres (Public University of Navarre, Spain) SnO2 humidity interferometric sensor based on photonic crystal optical fiber and Fast Fourier Transform

108

Samuel Mañas-Valero (University of Valencia - ICMol, Spain)

ORAL Plenary Session

Transition metal chalcogenides in the 2D limit: superconductivity in 2H-TaS2 José Miguel Martín Martínez (University of Alicante, Spain)

ORAL Parallel Session

Improvement of the toughness of PMMA-based based acrylic resin for dental application by adding small amounts of graphene nanoparticles Nicolas F. Martinez (ScienTec Iberica, Spain)

ORAL Plenary Session & Poster

Bimodal HD-KFM KFM and Resiscope Atomic Force Microcopy characterization of bidimensional materials and solar cells Johann G. Meier (ITAINNOVA, Spain)

13

110

111

113

ORAL Plenary Session

On the peculiar mechanical and tribological behavior of polymer nanocomposites with nanotubes of WS2 and nanowires of Mo6S2I8 ORAL Roderick Melnik (MS2Discovery Interdisciplinary Research Institute, Canada Plenary Session and BCAM, Spain) Coupling, geometric phases, and properties of quantum dots: analytics and numerics for the Berry phase case

114

115

Page Arben Merkoçi (ICREA/ICN2, Spain)

INVITED Plenary Session

Diagnostic devices using graphene and other nanomaterials César Merino (Grupo Antolin, Spain)

INVITED Parallel Session

Nestor Merino-Díez (CIC nanoGUNE, DIPC and CSIC/UPV-EHU, Spain) Structure-property relation in atomically omically precise graphene nanoribbons on Au(111) Angel Millán (ICMA, CSIC–Universidad de Zaragoza, Spain)

POSTER

ORAL Parallel Session

High time resolution thermometry on a magnetic nanoheater. A new tool for hyperthermia Miguel Monge (Universidad de la Rioja, Spain)

ORAL Plenary Session

116 117 119 121

Ultrathin Gold-Silver Silver Nanorods and Nanowires Stabilized with Long Alkyl Chain Carboxylic Acids: Synthesis and Plasmonic Properties

14

ORAL Juan Francisco Muñoz-Martínez (Universidad Autónoma de Madrid and Plenary Session UPM, Spain) Electrophoretic vs. dielectrophoretic forces in 2D optoeletric nanoparticle patterning

122

POSTER Mª del Pilar Muñoz Muñoz (Technical Research Centre of Furniture and Wood of Region of Murcia (CETEM), Spain) Methods of the incorporation of nanoparticles of SIO2 in synthesis of aqueous polyurethane dispersion; evaluation of mechanical properties

124

INVITED José María Navas Antón (INIA (National Institute for Agricultural and Food Parallel Session Research and Technology, Spain) Graphene interaction with cellular structures and potentiating action on environmental pollutants effects

125

Juan José Ortega Gras (Technical Research Centre of Furniture and Wood of POSTER Region of Murcia (CETEM), Spain) - NanoMaterials Effect of adding oxide ceramic nanoparticles into free-formaldehyde formaldehyde wood adhesive for preparing particleboards Alfredo Pacheco Tanaka (TECNALIA, Spain)

POSTER

127

128

Innovative graphene applications José Ignacio Pascual (CIC nanoGUNE, Spain)

INVITED Plenary Session

Single-molecule molecule spintrometry: measuring and tuning the spin states of a molecule with STM Valery Pavlov (CIC BiomaGUNE, Spain)

ORAL Plenary Session

Enzymatic etching of nonoparticles in biosensing Alain Pénicaud (Université Bordeaux, France)

KEYNOTE Plenary Session

Additive Free, Single Layer Graphene in Water Uxua Pérez de Larraya (CEMITEC, Spain)

ORAL Plenary Session

Synthesis of iron based nanoparticles in presence of nanocellulose for contaminant removal removaly" POSTER Jaime Andrés Pérez Taborda (IMM-CSIC, Spain) Silver and copper selenide: New approach in manufacture of highly efficient thermoelectric

129

130 132 133 135

Page Andrew J. Pollard (National Physical Laboratory, UK)

KEYNOTE Plenary Session

Metrology for Graphene and 2-D D Materials: Characterisation and Standardisation for an Emerging Industry Danny Porath (The Hebrew University of Jerusalem, Israel)

KEYNOTE Plenary Session

The Quest for Charge Transport in single Adsorbed Long DNA-Based Molecules Recio, Imanol (AVANZARE, Spain) Electrical Characterization of polymer matrix graphene composites Javier Reguera Gomez (CIC biomaGUNE, Spain)

POSTER

ORAL Plenary Session

Patchy nanoparticles at the air-liquid liquid interface: contact angles and adsorption energies measured by neutron reflectivity Miguel Ángel Ruiz Fresneda (University of Granada, Spain)

ORAL Parallel Session

Fabrication and molecular scale characterization of selenium nanoparticles produced by Stenotrophomonas sp. BII-R7 Enrico Sabbioni (CeSI- Aging Research Center, “G. d’Annunzio” University Foundation, Italy) Nanotoxicology for safe development of nanomaterials: light and shadows

KEYNOTE Plenary Session

Ghoutia Naima Sabri (University of Tahri Mohamed, Algeria) Modeling of an optical microwave isolator

POSTER

Nawal Sabri (University of Abou Bakr Belkaid, Algeria) The Application of Permanent Magnets Materials in Electrical motors

POSTER

Sascha Sadewasser (INL - Inter. Iberian Nanotechnology Lab., Portugal)

KEYNOTE Plenary Session

INL next decade - a general perspective and a specific look at INL’s energy research Lars Samuelson (Lund University, Sweden)

KEYNOTE Plenary Session

From basic Nanowire research to real-world applications Eduardo Santamaría-Aranda (Universidad de La Rioja, Spain) Molecular photoswitches as solar energy storage devices

POSTER

137

138 140 141

142

143 144 145 146 147

Sábel Santibáñez (Universidad de La Rioja and Centro Tecnológico del POSTER Calzado de La Rioja (CTCR), Spain) Hollow Mesoporous Silica Nanostructures: Synthesis and inclusion in rubber compounds

148

Neelotpol Sarkar (Amity Institute of Nanotechnology, India) Synthesis and characterization of alloy nanoparticles

149

Aleksei Savenko (FEI Company, The Netherlands)

POSTER

ORAL Plenary Session

Broadening of FIB applications using Xe plasma FIB Isabelle Sicé (MICROTEST, France)

ORAL Parallel Session

ALD deposition of AlN for AlN/NbN multilayers Mattin Urbieta (CFM-MPC, CSIC-UPV/EHU, Spain) Optical spectroscopy of metallic icosahedral nanoparticles: classical versus atomistic description

151 -

POSTER

153

15

Page María Varela (Universidad Complutense de Madrid, Spain)

INVITED Plenary Session

Aberration corrected views into the nano-world Mercedes Vila Juárez (CTECHnano, Spain)

INVITED Parallel Session

Atomic layer deposition in biomedical applications

156

POSTER Laura Vila (Universitat Autònoma de Barcelona, Spain) Caco-2 cells as an in vitro model to determine detrimental effects on the intestinal barrier.

Studies with SiO2- and ZnO-NPs at sub-toxic doses

157

Elvira Villaro Ábalos (Instituto de Tecnologías Químicas Emergentes de La ORAL Parallel Session Rioja and UNED, Spain) Manufacturing and characterization of high electrical ical conductivity structural epoxy graphene composites

159

Elvira Villaro Ábalos (Instituto de Tecnologías Químicas Emergentes de La Rioja and UNED, Spain) “iGCAuto: Innovative Graphene-Based Based Polymer Composite Materials for Automotive Applications

160

Pablo Villarreal (Instituto de Física Fundamental-CSIC, Spain)

POSTER

ORAL Parallel Session

Structure and Spectroscopy of Helium Nanodroplets Doped with Molecular Impurities at Low Temperatures Helge Weman (CrayoNano AS, Norway)

16

155

KEYNOTE Plenary Session

Epitaxial growth of semiconductor nanostructures on graphene: Generic model and a potential first device application Felix Zamora (Universidad Autónoma de Madrid and IMDEA-Nanoscience, Spain) Conductive Coordination Polymers at the Nanoscale

INVITED Parallel Session

161

163

165

Abstracts

Nanoscopy for Nanomedicine: looking at nanomaterials one molecule at a time Lorenzo Albertazz Nanoscopy for Nanomedicine Group, Institute for Bioengineering of Catalonia (IBEC) C\ Baldiri Reixac 15-21, Helix Building, 08028 Barcelona

The use of nanocarriers for intracellular delivery of therapeutic moieties is a great challenge for synthetic chemistry and nanotechnology. In this framework, supramolecular materials such as micelles, liposomes self-assembled nanoparticles and nanofibers plays a pivotal role. A crucial factor limiting the design of effective materials is the lack of understanding about material-cell interactions that hampers the rational design of nanosized carriers. This is particularly relevant for supramolecular materials as their complex structure poses several unanswered questions.

Here we discuss the use of super resolution microscopy to image materials in vitro and in mammalian cells. This novel technique, allowing to obtain a resolution down to 20nm, had a dramatic impact in the field of cell biology, however its use in the field of chemistry and nanotechnology is poorly explored. Super resolution microscopy offers nanometric resolution and multicolor ability, therefore it is an ideal tool to study nano-sized supramolecular assemblies of multiple components in vitro and in cells.

We employed Stochastic Optical Reconstruction Microscopy (STORM) to image biomaterials in vitro, with special emphasis on supramolecular polymers and nanoparticles, unveiling novel information on materials structure and dynamics, a key issue of supramolecular materials.

18

Moreover we propose a methodology to image nano-sized materials in cells, tracking them during their membrane targeting, cell uptake and intracellular targeting. We show how 2-color STORM can be used to perform nanometric-accurate colocalization unveiling at the molecular level materials-cell interactions.

This allow to look at nanomaterials in action with new eyes and use the information obtained for the “STORM-guided� design of novel nanomaterials for drug delivery and other targeted therapies.

Adsorption and storage of hydrogen in porous and layered materials

Julio A. Alonso Departamento de Física Teórica, Atómica y Optica, University of Valladolid, 47011 Valladolid, Spain jaalonso@fta.uva.es

Hydrogen adsorption on porous materials is a promising technology for hydrogen storage. Pure carbon materials do not reach the technological targets, but experimental work has shown that doping the porous carbons with palladium nanoparticles enhances the storage capacity of those materials [1]. We have investigated the role of the Pd dopant on the adsorption and storage mechanisms. Density functional calculations indicate that H2 molecules adsorb on the Pd clusters following two channels: molecular adsorption and dissociative chemisorption [2]. The competition between those two channels on Pd clusters, free and anchored on a vacancy in graphene, has been studied, and the effects of the carbon substrate have been identified. The hypothesis normally used to justify the enhancement of the storage capacity is that the hydrogen molecules dissociate on the Pd particles and then the hydrogen atoms spill over the carbon substrate. To test this hypothesis we have performed ab initio molecular dynamics simulations of the deposition of molecular hydrogen on Pd clusters supported on graphene [3]. The results of the simulations cast doubts on the validity of the spillover mechanism for explaining the enhancement of hydrogen storage in Pd-doped porous carbons.

Layered inorganic materials, like nanotubes and fullerene-like nanoparticles of WS2 are also investigated as media for hydrogen storage [4]. Using hydrogen activated by radiofrequency plasma increased the efficiency of its absorption on the nanoparticles as compared to hydrogenation by high pressure molecular unactivated hydrogen. The chemical configuration of the absorbed hydrogen is of primary importance, as it affects its absorption stability and possibility of release. Micro-Raman spectroscopy was applied to elucidate the chemical bonding of hydrogen and to distinguish between chemi- and physisorption. A model based on density functional theory was used to simulate the adsorption of hydrogen on the WS2 nanoparticles, demonstrating good agreement between theory and experiment [5]. .

References [1] [2] [3] [4] [5]

C. I. Contescu et al., Carbon 49, 4050 (2011).

A. Granja, J. A. Alonso, I. Cabria and M. J. López, RSC Advances 5, 47945 (2015).

M. Blanco-Rey, J. I. Juaristi, M. Alducin, M. J. López and J. A. Alonso (submitted for publication).

A. Laikhtman et al., Int. J. Hydrogen Energy, 39, 9837 (2014).

A. Laikhtman, G. Makrinich, M. Sezen, M. M. Yildizhan, J. I. Martinez, D. Dinescu, M. Prodana, M. Enachescu, J. A. Alonso and A. Zak (submitted for publication).

19

Quatsomes: Promising Highly Stable Nanovesicles for Drug Delivery A. Ardizzone1,2, L. Ferrer-Tasies1,2, E. Moreno-Calvo1,2, I. Cabrera1,2, N. Grimaldi3, N. Segovia1,2, S. Sala2,1, J. Faraudo1, J. Veciana1,2 *and N. Ventosa1,2* 1

Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Esfera UAB; Campus UAB s/n, E-08193 Cerdanyola del Vallés, Spain 2 CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Bellaterra, 08193, Spain vecianaj@icmab.es, ventosa@icmab.es

There is a large interest in finding non-lipid building-blocks or tectons, which self-assemble into stable vesicles, and which satisfy the quality standards required in pharmaceutical formulations [1].

20

Here we show the ability of quaternary ammonium surfactants and sterols to self-assemble forming stable amphiphilic bimolecular building-blocks with the appropriate structural characteristics to form, in aqueous phases, closed bilayers, which we named quatsomes. Phase behavior analysis of different aqueous mixtures of the quaternary ammonium surfactant CTAB and cholesterol (Chol) have shown that a pure vesicular phase is only formed at equimolar proportions of both components [4]. Molecular dynamic simulations revealed that the cholesterol and CTAB pair works as a unique supramolecular architecture for the formation of more complex colloidal phases such as vesicles. Many functionalities can be implemented simultaneously in quatsomes, either by covalent attachment to sterol like molecules, by electrostatic interaction with the cationic ammonium head of surfactant units or by hydrophobic interaction with the bilayer. These possibilities open a broad range of applications in pharmacy [5], cosmetics and materials synthesis.

When prepared by using compressed fluids (DELOS-SUSP method) [2] , these colloidal structures are stable for periods as long as several years, their morphology do not change upon rising temperature or dilution, and show outstanding vesicle to vesicle homogeneity regarding size, lamelarity and membrane supramolecular organization. [3] It is worth to say, that all these structural attributes are relevant quality data, fulfilling requests of EMA and FDA to support a marketing authorization of any new nanomedicine candidate. Quatsomes have the appropriate physico-chemical and biological characteristics to be used as topical drug delivery systems [3,4].

References [1] [2] [3] [4] [5]

M. Antonietti et al., Adv. Mater. 2003, 15, 1323.

I.Cabrera et al. Nano Lett. 2013, 13, 3766−3774.

E. Elizondo et al., J.Am.Chem. Soc. 2012, 134, 1918.

L. Ferrer-Tasies et al, Langmuir 2013, 29, 6519−6528.

N. Ventosa et al., Patent Appl. WO2014/019555.

Shell material assessment for GaAs-based nanowire solar cells Enrique Barrigón, Vilgailė Dagytė, Magnus Heurlin, Gaute Otnes, Lars Samuelson, Magnus Borgström Division of Solid State Physics / Nanolund, Lund University, Box 118, SE-221 00 Lund, Sweden enrique.barrigon@ftf.lth.se

Nanowire (NW) solar cells are an innovative and promising way to further reduce the cost of photovoltaic electricity for terrestrial applications, due to their efficient light absorption and significant cost reduction [1], [2]. A record NW solar cell efficiency value of 15.3% has been recently published for a GaAs-based NW device, with a volume of GaAs equivalent to a 370-nm thick planar layer [3].

So far, all high performance NW solar cells have been grown axially with Au-mediated vapour-liquidsolid (VLS) method in MOVPE [3], [4]. However, due to the high density of surface states in GaAs, an additional growth of a radial shell material must be included after NW growth to passivate its surface, as in any GaAsbased NW electronic device. In particular for GaAs-based NW solar cells, the shell material should be transparent to the incident light (i.e., higher energy bandgap than GaAs) and should not introduce any strain (i.e., lattice-matched composition to GaAs) to avoid optical and electrical losses, respectively.

In this work, several candidate materials to be employed as shells for GaAs NW solar cells are assessed, namely AlGaAs, GaInP and AlInP. Intrinsic GaAs core NWs were firstly grown by the VLSMOVPE method on GaAs(111)B substrates with a Au pattern defined by nano imprint lithography. Subsequently, the shell material was grown in the same reactor without removal of the Au particle. Shell materials were grown at different temperatures, growth rates and lattice-matching composition. Fig.1 (a) shows as an example a cross section SEM image of GaAs NWs with a 35 nm thickness GaInP shell. Fig.1(b) shows the PL measurement at RT of GaAs NWs with and without a lattice-matched 15 nm thickness AlInP shell, where a 60 fold increase in the room temperature ensamble PL signal can be observed. The full morphological, structural and optoelectronical characterization will be presented in the final contribution to the conference.

Figure 1: (a) SEM image of GaAs NWs with GaInP shell (b) RT PL ensemble of GaAs NWs with and without AlInP shell.

21

References [1] [2] [3] [4]

22

] M. T. Borgström, J. Wallentin, M. Heurlin, S. Fält, P. Wickert, J. Leene, M. H. Magnusson, K. Deppert, and L. Samuelson, IEEE J. Sel. Top. Quantum Electron, 17, (2011), pp. 1050–1061.

R. R. LaPierre, A. C. E. Chia, S. J. Gibson, C. M. Haapamaki, J. Boulanger, R. Yee, P. Kuyanov, J. Zhang, N. Tajik, N. Jewell, and K. M. A. Rahman, Phys. Status Solidi RRL, 7, (2013), pp. 815–830.

I. Aberg, G. Vescovi, D. Asoli, U. Naseem, J. P. Gilboy, C. Sundvall, A. Dahlgren, K. E. Svensson, N. Anttu, M. T. Bjork, and L. Samuelson, IEEE J. Photovolt., PP, no. 99 (2015), pp. 1–6.

J. Wallentin, N. Anttu, D. Asoli, M. Huffman, I. Åberg, M. H. Magnusson, G. Siefer, P. FussKailuweit, F. Dimroth, B. Witzigmann, H. Q. Xu, L. Samuelson, K. Deppert, and M. T. Borgström, Science, 339, no. 6123, (2013), pp. 1057–1060.

Extreme 2D-confinement of polymers in graphene-based materials Fabienne Barroso-Bujans Donostia International Physics Center (DIPC), 20018 San Sebastian, Spain IKERBASQUE-Basque Foundation for Science, María Díaz de Haro 3, Bilbao 48013, Spain fbarroso@ehu.eus

Confined macromolecules at a nanometer scale exhibit a fascinating and unexpected dynamic behavior.

Upon a decrease of confining dimensions down to the nanoscale, properties such as glass transition and crystallization are often observed to deviate quite significantly from those of the bulk material. Graphenebased materials are exceptional hosts to study confined polymers at the sub-nanometric scale due to the ability to control and tune their degree of oxidation and exfoliation and, therefore, to control the strength of the interaction between host and macromolecules. In this study, we report on the extreme twodimensional (2D) confinement of poly(ethylene oxide) (PEO) in the interlayer space of graphite oxide (GO) and in the surface of thermallyreduced graphene sheets by using a combination of diffraction, calorimetric, and spectroscopic methods, including high-resolution inelastic neutron scattering (INS) [1-4].

Careful control over the degree of graphite oxide oxidation and exfoliation reveals three distinct cases of spatial confinement: (i) subnanometer 2D-confinement; (ii) frustrated absorption; and (iii) surface immobilization. Case (i) results in drastic changes to PEO conformational and collective vibrational modes as a consequence of a preferentially planar zigzag (trans–trans–trans) chain conformation in the confined polymer phase, which is accommodated in a layer of thickness 3.4 Å within the GO substrate. In case (ii), GO is thermally reduced resulting in a disordered pseudo-graphitic structure. As a result, we observe minimal PEO absorption owing to a dramatic reduction in the abundance of hydrophilic groups inside the distorted graphitic galleries. In case (iii), the INS data unequivocally show that PEO chains adsorb firmly onto graphene sheets, with a substantial increase in the population of gauche conformers. Well-defined glass and melting transitions associated with the confined polymer phase are recovered in case (iii), albeit at significantly lower temperatures than those of the bulk.

References [1] [2] [3] [4]

F. Barroso-Bujans, F. Fernandez-Alonso, J.A. Pomposo, E. Enciso, J.L.G. Fierro, J. Colmenero.

Carbon 50, 5232-5241 (2012).

F. Barroso-Bujans, F. Fernandez-Alonso, S. Cerveny, S. Arrese-Igor, A. Alegría, J. Colmenero.

Macromolecules 45, 3137-3144 (2012).

F. Barroso-Bujans, F. Fernandez-Alonso, J.A. Pomposo, S. Cerveny, A. Alegría, J. Colmenero. ACS Macro Lett. 1, 550-554 (2012).

F. Barroso-Bujans, F. Fernandez-Alonso, J. Colmenero. J. Phys: Conf. Ser. 549, 012009 (2014).

23

Hydrogen physisorption and intercalation in novel nano-porous graphites Massimiliano Bartolomei1, Estela Carmona-Novillo1, Giacomo Giorgi2 1

Institute of Fundamental Physics, IFF-CSIC, Serrano 123, 28006 Madrid, Spain Department of Chemical System Engineering, School of Engineering, University of Tokyo, Japan maxbart@iff.csic.es

2

Pristine graphene is in principle an ideal adsorbing material due to its large specific area, stability, mechanical properties and low weight. Nevertheless, it has been theoretically demonstrated that molecular hydrogen (H2) physisorption on graphene is not particularly favourable, being tha adsorption energy, mainly determined by van der Waals interactions, around 0.05 eV. Intercalation between graphene layers could lead to more encouraging adsorption energies but, unfortunately, in pure graphite there is no room for any atomic or molecular species to be hosted.

A possible solution to this problem is the use of porous derivative of graphene as “building blocks� to construct a new class of porous graphites characterized by a larger interlayer volume available for gas storage. To this regard graphynes, which are novel two-dimensional (2D) carbon-based materials, represent promising candidates since they naturally exhibit a nanoweb-like structure characterized by triangular and regularly distributed subnanometer pores [1]. These intriguing features make them appealing for molecular filtering as shown by recent theoretical predictions [2].

24

The possibility to exploit graphynes as ideal media for the H2 reversible storage is here theoretically studied. First principles adsorption energies of H2 on graphene, graphdiyne and graphtriyne molecular prototypes are obtained at the MP2C [3] level of theory. First, the case of a single layer is investigated and it is found that graphynes are more suited than graphene for H2 physical adsorption since they provide larger binding energies at equilibrium distances much closer to the 2D plane. In particular, for graphtriyne a flat minimum located right in the geometric center of the pore is identified.

A novel graphite composed of graphtriyne stacked sheets is then proposed [4] and an estimation of its 3D arrangement is obtained at the DFT level of theory by considering a periodic model of the involved bilayers. In contrast to pristine graphite this new carbon material allow both H2 intercalation and outofplane diffusion by exploiting the larger volume provided by its nanopores. Related H2 binding energies for intercalation and in-pore adsorption are around 0.1 eV (see Figure) and they could lead to high storage capacities exceeding those found to date for carbon nanostructures of different nature. The proposed layered carbon allotrope should be considered as a promising material for a safer and potentially cheaper alternative for hydrogen on-board storage than conventional solutions based on cryogenic liquefaction and/or high compression.

References [1] [2] [3] [4]

G. Li et al., Chem. Commun., 46, 3256-3258 (2010).

M. Bartolomei et al., J. Phys. Chem. Lett., 5, 751-755 (2014); J. Phys. Chem. C, 118, 29966-29972 (2014).

M. PitonĂĄk and A. Hesselmann, J. Chem. Theory Comput. Chem., 6, 168-178 (2010).

M. Bartolomei et al., Carbon, 95, 1076-1081 (2015).

Figures

Figure 1: Adsorption energy evolution of one H2 molecule crossing a porous graphite composed of stacked graphtriyne layers. A prototype consisting of three parallel graphtriyne pores in a Bernal-like 3D arrangement is used.

25

Targeting Tumors with Solidified Polymer Micelles Ofra Benny, PhD Institute for Drug Research, Faculty of Medicine, The Hebrew University of Jerusalem, Jerusalem, Israel ofrab@ekmd.huji.ac.il

Nanomedicine is an emerging field in cancer therapy that has the potential of revolutionizing the way drugs are introduced to patients today. Many drugs have critical limitations such as low solubility, stability, and specificity – leading to inefficient treatment and to adverse side effects.

Among the different types of drug-delivery systems, polymer micelles represent an appealing technology for delivering drugs to tumors because of their relatively simple formulation and their small size, enabling efficient tumor extravasation from leaky tumor blood vessels.

26

We found that self-assembled di-block polymers can be used successfully to deliver small molecule drugs by encapsulation or by chemical conjugation of the drug, and that these nanomicelles can be further stabilized by a secondary solidification step. The formation of stable solidified nano-micelles enables efficient cellular internalization, and improve drugs’ bioavailability half-time, enhances blood circulation time, increases tumor uptake, and reduces side effects as demonstrated in-vivo. Moreover, our studies also revealed that the endocytosis of stabilized particles occur via clathrin pathway, unlike the reported mechanism for nonsolidified polymer micelles. Because of the high stability of this particles our data suggest that the nanoparticles can be transported by transcytosis and thereby they can also be efficient in tumors that are not vascularize.

Figures

Mode splitting in zigzag carbon nanotubes Jhon González1, Gilles Buchs2, Dario Bercioux3,4, Andres Ayuela1,3 1 Centro de Física de Materiales (CFM-MPC) Centro Mixto CSIC-UPV/EHU, E-20018 Donostia-San Sebastián, Spain Centre Suisse d’Electronique et de Microtechnique (CSEM) SA, Rue de l’Observatoire 58, CH-2002 Neuchâtel, Switzerland 3 Donostia International Physics Center, E-20018 Donostia-San Sebastian, Spain 4 IKERBASQUE, Basque Foundation of Science, E-48011 Bilbao, Spain dario.bercioux@dipc.org

2

We investigate theoretically the electron scattering properties of defected and freestanding zigzag singlewalled carbon nanotubes. The variation of the chemical potential, realized in the suspended region, produces quasi-bound states, which compete with the ones created by multiple defects [1,2]. We show that a particular configuration of the tube defects produces a degeneracy lifting in the metallic branches of a zigzag nanotube. As a consequence we observe a doubling or splitting of the quasibound states. We also observe a particle-hole symmetry breaking due to selection rules associated to the interplay of tube and defects [3]. Our predictions are supported by an experimental case where a partially suspended zigzag tube that shows split quasi-bound states between defects induced by Ar+ ions [1,2]. We propose that our results can find applications in angular momentum filtering as well as in THz optics [4].

References [1] [2] [3] [4]

G. Buchs et al., Phys. Rev. Lett. 102, 245505 (2009).

D. Bercioux et al., Phys. Rev. B 83, 165439 (2011).

L. Mayrhofer and D. Bercioux, Phys. Rev. B 84, 115126 (2011).

J. González et al., submitted.

Figures

Figure 1: Sketch of the zigzag carbon nanotube suspended between a terrace of Au(111), on the right, and a rope of other tubes, on the left. It is also represented the tip of an STM that is employed for visualizing the local density of states.

27

Design of mesoporous hybrid titania for solar light harvesting using coordination transition metal complexes as building blocks J. R. Berenguer1, A. Sepulveda1, M. Rico2, C. Ezquerro1, E. Serrano2, E. Lalinde1, J. Garcia Garcia-Martinez2 1

Organometallics Molecular Materials, Departamento de Química-Centro Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, C/ Madre de Dios 54, Logroño, La Rioja, Spain.

Molecular Nanotechnology Lab, Univ. de Alicante, Ctra. Alicante-S. Vicente s/n, Alicante, Spain. www.nanomol.es jesus.berenguer@unirioja.es

2

The quest for materials able to efficiently harvest solar light has become one of the biggest challenges of our time. Titania (TiO2) is one of the most widely used materials in light harvesting systems, despite having a large band-gap gap (of about 3.0 eV), which only uses ca. 5% of the solar radiation (U.V.). Based on a versatile approach that we have recently developed, namely “Sol-Gel Gel Coordination Chemistry”, [1] we have prepared the first hybrid organo-titanias, with efficient incorporation of organic moieties into the structure of the titania. [2] These materials showed a very significant reduction of its band gap (up to 2.74 eV) and revealed highly active and remarkably stable photocatalytic properties.

28

Building on this strategy, herein we communicate the one-pot co-condensation condensation of tetrabutyl orthotitanate (TBOT) and the neutral Ru(II) N3 dye or the new cationic Ir(III) complex [Ir(ppy)2(3,3’ [Ir(ppy)2(3,3’-H2dcbpy)]PF6, which yields titanias containing the coordination chromophores not only on the surface but also within the network (Figure 1). These complexes act both as defects (or disruptors) of the crystalline structure of the anatase (narrowing its band gap) and as dyes (molecular antenna). The novel hybrid metal ccomplex-titania materials have been tested for the degradation of rhodamine 6G under UV or visible light and have bee also used as part of the anode architecture of new low temperature sintered dye--sensitized solar cells (ltDSSCs). In both cases, the new materials aterials show a superior activity and stability when compared to related conventional dye-sensitized sensitized titania prepared by grafting. The incorporation of dyes the crystalline structure is a promising alternative route to prepare dye-sensitized materials.

References [1] [2]

E. Serrano, N. Linares, J.R. Berenguer, J. García-Martínez, rtínez, ChemCatChem (2013), 844. a) M. Rico-Santacruz, Santacruz, A.E. Sepúlveda, E. Serrano, J.R. Berenguer, E. Lalinde, J. Garcia Garcia-Martinez Spanish Patent 201300536 (2013); b) M. Rico-Santacruz, A.E. Sepúlveda, púlveda, E. Serrano, E. Lalinde, J.R. Berenguer, J. Garcia-Martinez, Martinez, Journal, J. Mater. Chem. C (2014) 9497 9497.

Figures

Figure 1: Scheme of the procedure that has been used to incorporate different metal complexes into the structure of titania. This methodology is based on a strategy previously described for the preparation of hybrid silica materials. [1].

Ultrafast control of plasmonic nanoantennas driven by hot-spot induced phase-transitions in VO2 Luca Bergamini1,2, Yudong Wang3, Jeffrey M. Gaskell4, Nerea Zabala1,2, C. H. de Grootc, David W. Sheeld, Javier Aizpurua2, and Otto L. Muskens3 1

Department of Electricity and Electronics, UPV/EHU, 48080, Bilbao, Spain 2 CFM, CSIC-UPV/EHU and DIPC, 20018, San Sebastian, Spain Faculty of Physical Sciences and Engineering, University of Southampton, SO17 1BJ, Southampton, UK 4 Materials and Physics Research Centre, University of Salford, M5 4WT, Manchester, UK luca.bergamini@ehu.eus; O.Muskens@soton.ac.uk

3

Efficient and reversible switching of plasmonic modes at visible and near-infrared wavelengths is one of the key desirable properties for tunable devices [1]. Phase-change materials offer technologically relevant opportunities as they can provide very large changes in the dielectric response [2]. So far most studies have reported the effects of a global phase transition of these materials on the plasmonic response of nanoparticles and metamaterials. Compared to chalcogenide phase-change materials which offer slow, rewritable memory functionality at relatively high temperatures, vanadium oxide (VO2) provides an ultrafast, reversible phase transition at only modestly elevated temperatures around 68°C [3].

Here, we exploit for the first time resonant pumping and nanometer-scale plasmonic hot-spots to induce an optical change of the nanoantenna response through highly localized phase-changes in the underlying substrate. Multifrequency crossed gold antenna arrays were fabricated on top of high-quality VO2 films (nanoantenna-VO2 hybrids). Optical experiments show that fully reversible switching of antenna resonances at the picosecond timescale are possible using resonant pumping schemes. Simulations revealed that the change in optical response of the antennas stems from the change in dielectric properties of VO2 regions neighboring the nanoantennas. Moreover, it is demonstrated that the phase transition mediated by local pumping of a plasmon resonance does not influence the resonance of a perpendicular nanoantenna positioned less than 100 nm away from the modulated antenna.

The nanoantenna-VO2 hybrids enable new directions in all-optical ultrafast switching at picoJoule energy levels, and open up the possibility for plasmonic memristor-type devices exploiting nanoscale thermal memory.

References [1] [2] [3]

J. A. Schuller, et al., Nature Mater., 9 (2010) 193-204.

Z. Yang, and S. Ramanathan, IEEE Phot. J., 7 (2015) 0700305.

M. M. Qazilbash, et al., Science, 318 (2007) 1750–1753.

29

Figures

Figure 1: (a) Example of a fabricated antenna-VO2 hybrid. (b) Simulated 68°C isosurfaces showing the phase phase-changed hotspots around the nanoantennas generated by resonant pumping. (c) Change in the optical response of the nanoantenna array as a consequence of the picoJoule pumping.

30

Enhanced and Tunable Magneto-Optcs via Fano Lattice Surface Modes in Arrays of Anisotropic Magnetic Nanoantennas Luca Bergamini1,2, Nicolò Maccaferri3, Matteo Pancaldi3, Mikolaj K. Schmidt2, Mikko Kataja4, Sebastiaan van Dijken4, Nerea Zabala1,2, Javier Aizpurua2 and Paolo Vavassori3,5 1

Department of Electricity and Electronics, UPV/EHU, 48080 Bilbao, Spain 2 CFM, CSIC-UPV/EHU and DIPC, 20018, San Sebastián, Spain 3 CIC nanoGUNE, 20018, San Sebastián, Spain 4 Department of Applied Physics, Aalto University School of Science, 00076, Aalto, Finland 5 Ikerbasque, Basque Foundation for Science, 48011, Bilbao, Spain luca.bergamini@ehu.eus; n.maccaferri@nanogune.eu, p.vavassori@nanogune.eu

Recently it has been demonstrated that randomly distributed ferromagnetic nanoantennas (NAs) can jointly support Localized Surface Plasmons (LSPs) and Magneto-Optical Activity (MOA) when magnetized by an external static magnetic field [1]. Moreover, the dependence of the optical and MO responses on the antenna shape/size is further enriched when shape anisotropy of the NAs is exploited, which introduces resonance modes dependent on the incident light polarization [2]. Furthermore, ordered arrays of metal nanoparticles have been found to exhibit Fano-like resonances (called Lattice Surface Modes LSMs), due to the interference between the inherent LSP resonances of the antennas and the narrow diffraction orders of the array [3].

In this work, we combine both the NA-shape anisotropy and the array arrangement to create magnetoplasmonic crystals with highly tunable optical and magneto-optical responses. We investigate the optical and magneto-optical properties of 2D square-arrays of ellipsoidal nickel nanodisks by means of electromagnetic simulations, via Coupled Dipole Approximation [4] and Finite-Difference Time-Domain [5] techniques, and state-of-the-art experiments. Our findings reveal a notable difference in the LSM behavior depending on whether the incident electric field is applied along either the long- or short-axis of the NAs. We show not only that the LSM behavior is spectrally tunable, but also that, by playing with the NA size and lattice periodicity, the optical and MO response can be actively tuned at wish, for instance, to achieve either transparency or enhancement of the MOA. The results of our study show the advantages of combining anisotropic ferromagnetic metal nanoantennas with lattice diffraction, paving the way for the realization of a new class of highly tunable magnetoplasmonic nanodevices.

References [1] [2] [3] [4] [5]

Maccaferri N., et al., Phys. Rev. Lett., 111 (2013) 167401.

Lodewijks K., et al., Nano Lett., 11 (2014) 7207-7214.

Auguié B. and Barnes W. L., Phys. Rev. Lett., 101 (2008) 143902.

Zou S., et al., J. Chem. Phys., 120 (2004) 10871.

FDTD Solutions, software from Lumerical Inc. (www.lumerical.com).

31

Figures

Figure 1: (a) Schematic illustration of periodic distributed elliptical nickel antennas immersed in a homogeneous medium, magnetized by an external static magnetic field H and hit by an external electromagnetic field E applied along the short axis of the NAs. The ferromagnetic nature of the NAs originates an electric field also along the long long-axis. Both optical and magneto-optical ptical responses are influenced by the surface lattice resonances due to the periodic pattern. (b) Experimental (dashed lines) and FDTD simulated (solid lines) MOA spectra for incident electric field lying along the long long-axis (red-curves) and the short-axis (blue curve) of the antennas. The Fano-like like feature appearing for both illuminations around 750 nm is the consequence of the interference between the antenna LSP and the array diffraction order.

32

Graphene, other 2D crystals and hybrid superstructures for energy and (opto)electronic applications Francesco Bonaccorso Istituto Italiano di Tecnologia, Graphene Labs, Via Morego 30, 16163 Genova, Italy francesco.bonaccorso@iit.it

Graphene, thanks to its excellent material properties, has the opportunity to improve the performance of existing devices or enable new ones [1-6] that are also environmentally friendly. [7] Graphene is just the first of a new class of two dimensional (2D) crystals, derived from layered bulk crystals. [2] The assembly of such 2D crystals (heterostructures) will provide a rich toolset for the creation of new, customised materials.[1,2] A key requirement for applications such as flexible (opto)electronics and energy storage and conversion is the development of industrial-scale, reliable, inexpensive production processes, [2] while providing a balance between ease of fabrication and final material quality with on-demand properties.

Liquid-phase exfoliation [2] is offering a simple and cost-effective pathway to fabricate various 2D crystalbased (opto)electronic and energy devices, presenting huge integration flexibility compared to conventional methods. Here, I will present an overview of graphene and other 2D crystals for flexible and printed (opto)electronic and energy applications, starting from solution processing of the raw bulk materials, [2] the fabrication of large area electrodes [3] and their devices integration. [6-12]

33 References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12]

A. C. Ferrari, et al., Nanoscale, 7, 4598-4810 (2015).

F. Bonaccorso, et al., Materials Today, 15, 564-589, (2012).

F. Bonaccorso, et. al., Nature Photonics 4, 611-622, (2010).

F. Bonaccorso, Z. Sun, Opt. Mater. Express 4, 63-78 (2014).

G. Fiori, et al., Nature Nanotech 9, 768-779, (2014).

F. Bonaccorso, et. al., Science, 347, 1246501 (2015).

G. Calogero, et al., Chem. Soc. Rev. 44, 3244-3294 (2015).

J. Hassoun, et al. Nano Lett. 14, 4901-4906 (2014).

F. Bonaccorso, et al. Adv. Funct. Mater. 25, 3870-3880 (2015).

P. Cataldi, et al. Adv. Electr. Mater. 1, DOI: 10.1002/aelm.201500224 (2015).

S. Casaluci, et al. Nanoscale 8, 5368-5378 (2016).

H. Sun, et al., J. Mater. Chem. A DOI: 10.1039/C5TA08553E (2016).

Vanadium nitride thin films and nanoclusters: combined XPS and electrochemical characterization O. Bondarchuk, E. Goikolea, Y. Zhang, T. Rojo and R. Mysyk CIC energiGUNE, MiĂąano, Alava, Spain abondarchuk@cicenergigune.com

Pseudocapacitive or electrochemically active materials can achieve capacitance values up to 10-100 times higher than those obtained by materials working only using an electric double layer (EDL) mechanism. The pseudocapacitive behavior of several transition metal oxides has been extensively studied in the last decades and assigned to redox reactions occurring at the surface of the material. Very recently, transition metal nitrides such as MoxN, VN or TiN have emerged as promising electrode materials for electrochemical capacitors. These materials are relatively inexpensive and feature a high molar density, good chemical resistance, and, most importantly, in contrast to oxides, they exhibit a very high electronic conductivity value. Extremely high specific capacitance values of 1340 F g-1 were reported for nanostructured VN [1]. To shed some light on the underlying mechanism of capacitive behaviour of VN we have taken the surface science approach – using thin films and/or supported nanoclusters as model systems and applying surface sensitive techniques (XPS, AFM etc.) in combination with electrochemical testing.

34

VN films of various thicknesses have been successfully fabricated by direct nitridation of the predeposited pure vanadium film. Stoichiometric and virtually oxygen free VN films were grown on Ta foil in a customized UHV XPS system (XPS) which featured high pressure cell, where V metal film was heated up to 800 oC in 1 bar of pure nitrogen gas. VN nanoclusters were grown on HOPG (Figure below). The experimental system also featured an integrated electrochemical cell where sample could be transferred without exposing to air for cyclic voltammetry under Ar atmosphere. We have carried out a combined XPS and electrochemical study of as-prepared and cycled vanadium nitride films in various electrolytes ranging from basic to acidic, and also in industrial organic electrolyte 1.5M TEA+BF4-/ACN. A dependence of capacitance on the film thickness was established, showing a saturation of capacitance values once film thickness reaches ~100 nm. At saturation impressive specific capacitance values between 2000 and 3000 ÂľF/cm2 were achieved in the cyclic voltammetry mode in 1M KOH for scan rates up to 1 V/s. This capacitance two orders of magnitude higher than could be expected from EDL. In the same time cyclic voltammograms and XPS examinations do not reveal redox peaks and vanadium oxidation state variations respectively. Therefore we argue that the pseudocapacitive mechanism evoked in [1] and assigned to redox events involving OH- species cannot explain detected anomalous surface capacitance of the VN films and its dependence on the film thickness. In contrast we believe that the observed electrochemical properties of the VN films can be related to the space charge formed at the semiconductor-electrolyte interface. On the practical side, high surface-related capacitance values at the high rate shows the promise that VN films hold for microsupercapacitor applications.

References [1]

D. Choi et al., Adv. Mater., 18(2006) 1178.

Figures

HOPG

0,020

VN 1nm on HOPG 0,015

scan rate=100mV/s

0,010

<I> (mA)

0,005 0,000 -0,005 -0,010 -0,015 -0,020 -0,8

-0,7

-0,6

-0,5

-0,4

-0,3

Eew (V vs Ag/AgCl)

Figure 1: VN clusters on HOPG: AFM image and cyclic voltammmogram.

35

Nanomaterials for different applications: sensing, energy storage and memories Paolo Bondavalli Head of Nanomaterial topic team, Physics Depart. Thales/CNRS joint team UMR137 Member of Nanocarb Lab., joint team, Ecole Polytechnique/Thales

The contribution deals with the research work developed at the central research lab of Thales on applications for carbonaceous nanomaterials. Firstly we will talk about the research on the theory and fabrication and test of gas sensing devices based on carbon nanotubes. Secondly we will talk about the activity on supercapacitors in the frame of the Graphene Flagship and FIBRALSPEC project FP7, the main challenges and the bottlenecks to overcome to achieve an effective component. Finally we will present the new activity on memory based on Graphene oxide and Carbon nanofibers (H2020 project MODCOMP) that can open a new field of â&#x20AC;&#x153;objectsâ&#x20AC;? such as the flexible or printed memories. The common characteristics of these activities is that all exploit the deposition technique by spraying that has been developed at Thales Research and Technology that allow to take advantage of the nanomaterial properties and to fabricate devices in a suitable industrial way.

36

Kondo effect and magnetic exchange inversion in neutral and stable organic radical single molecule break junctions Enrique BurzurĂ­, R. Gaudenzi, R. Frisenda, S. T. Bromley, Marta Mas-Torrent, C. Rovira, J. Veciana, H. S. J. van der Zant Kavli Institute of Nanoscience. Delft University of Technology, Lorentzweg 1, Delft, The Netherlands e.burzurilinares@tudelft.nl

Organic radicals are neutral, purely organic molecules exhibiting an intrinsic magnetic moment due to the presence of an unpaired electron in the molecule in its ground state. This property, added to the low spinorbit coupling makes organic radicals good candidates for molecular spintronics insofar as the radical character is stable in solid state electronic devices.

We show that the magnetism of the PTM radical molecule, in the shape of a Kondo anomaly is preserved in two- and three-terminal solid-state devices, regardless of mechanical and electrostatic changes. Indeed, our results demonstrate that the Kondo anomaly is robust under electrodes displacement and changes of the electrostatic environment, pointing to a localized orbital in the radical as the source of magnetism.

Strong support to this picture is provided by density functional calculations and measurements of the corresponding nonradical specie [1].

We further study polyradical molecules, where several unpaired spins are coupled via exchange in a single high-spin purely organic molecule. We show that the local environment can induce a sign reversal of the exchange interaction, from ferro to antiferro, inducing a change in the magnetic ground state [2].

References [1] [2]

R. Frisenda et al., Nano Lett., 15 (2015) 3109â&#x20AC;&#x201C;3114.

R. Gaudenzi et al., Accepted in Nano Letters 2016.

Figures

Figure 1: (a) Schematics of an organic radical molecular junction. (b) dI/dV color plot showing the zerobias resonance splitting in magnetic field. (c) Magnetic spectra of (b).

37

Graphene-based composites for thermal management applications I. Bustero, B. Pérez, B. Iraola, M. Chapartegui, S. Flórez, I Gaztelumendi, M. Jurado, M. Mendizábal, R. Seddon, I. Obieta TECNALIA Paseo Mikeletegi 2, 20009 San Sebastián, Spain izaskun.bustero@tecnalia.com

The superb thermal conduction of graphene establishes it as an excellent material for thermal management. With the increase of power densities in electronic devices together with the continuing trend of reduction in device dimensions there is a need for novel materials to design appropriate thermal management systems to ensure electronic devices operate within their specification.

Tecnalia has developed Graphene based composites for potential applications where more efficient thermal dissipation materials are needed. Two potential applications have been addressed: Thermal Interface Materials (TIMs), such as thermally conductive adhesives and lightweight high performance CFRP composite parts with conductive properties.

1.

Thermally conductive adhesives based in graphene. Commercially available conductive adhesives contain high concentrations of metallic particles resulting in high viscosities. Instead, the use of nanoparticles with good thermal properties helps in obtaining high conductivities with lower percentages of filler materials. This work compiles the development of graphene based thermal interface materials (TIMs). The addition of different types of graphene in thermoset matrixes and the compatibility adhesive-nanofiller is studied by rheological measurements and correlated to the microstructure observed by SEM. Moreover, the complete campaign designed to optimize the adhesive not only from the thermal point of view but also taking into account electrical and mechanical properties is analyzed.

38

2.

Electronic enclosures. Highly thermally conductive Carbon Fiber composites based on graphene have been developed and tested for spacecraft electronic boxes. Heat transfer capabilities of the new thermal composite were similar to the Aluminum reference housing and 43% weight reduction with respect to the current aluminum design.

References [1]

[2]

[3]

[4]

R. Seddon*, B. Pérez, B. Iraola, I. Bustero, S. Flórez, Graphene based thermally conductive adhesive for thermal interface materials, 11th European Advanced Technology Workshop on Micropackaging and Thermal Management. Oral contribution. La Rochelle France. February 2016.

B. Pérez, B. Iraola, I. Bustero, S. Flórez. Adhesivos conductores térmicos base grafeno como materiales de interfaz térmica. XVI Congreso de Adhesión y Adhesivos 24,25 Septiembre 2015.

Elda, Alicante.

S. Flórez*, M. Chapartegui, I. Bustero, I Gaztelumendi, M. Mendizábal, B. Iraola, G. Atxaga, M. Jurado, Graphene and its application in polymer composites. ECCM16 - European Conference on Composite Materials, Seville, Spain, 22-26 June 2014.

R. Rodriguez, B. Pérez & S. Flórez. The Journal of Adhesion, 90:10 (2014) 848-859.

Figures

2850 g

1610 g

39

43% weight

PLGA nanoparticles as paclitaxel delivery system for the treatment of breast cancer Laura Cabeza1,2, Julia Jiménez-Lopez1,2, Mazen El-Hammadi3, Gloria Perazzoli1,2, María Carmen Leiva1,2, Lucia Martín-Balderas3, Raul Ortiz4, Jose Prados1,2, Consolación Melguizo1,2 1

Institute of Biopathology and Regenerative Medicine (IBIMER), 18100 Granada, Spain Biosanitary Institute of Granada (ibs.GRANADA), SAS-Universidad de Granada, Granada, Spain 3 Department of Pharmacy and Pharmaceutical Technology, University of Sevilla, 41012 Sevilla, Spain 4 Department of Health Science, University of Jaén, 23071 Jaén, Spain melguizo@ugr.es 2

The treatment of breast cancer with the chemotherapeutic drug paclitaxel (PTX) is not entirely effective because of its low specificity for tumor tissues resulting in nonspecific toxicity [1]. Besides, the high PTX insolubility requires the use of the solvent Cremophor® EL which produces severe side effects [2].

Nanotechnology allows the use of nontoxic drug transporters that may enhance the specificity of drug for tumor tissues and avoid the use of toxic solvents. One example of these carriers are poly(lactic-co-glycolic acid) (PLGA) nanoparticles, one of the nanocarriers most studied in nanomedicine because of their biodegradability and good biocompatibility [3]. Thus, the aim of this study is to study the antitumor effect of drug PTX carried by PLGA nanoparticles and to compare with the free drug.

40

For this purpose toxicity studies were carried out by hemolysis assay with human erythrocytes exposed to PLGA blank nanoparticles. Furthermore, human breast cancer cell lines (MCF-7, MDA-MB-231) and a no tumor cell line (MCF-10A) were treated with PTX, PTX-PLGA, and PLGA for cytotoxicity and cell cycle assays. The cellular uptake of nanoparticles was studied with PLGA nanoparticles loaded with the fluorophore nile red (NR) by confocal microscopy and flow cytometry. Also, multicellular tumor spheroids were generated and exposed to the same treatments above for a preliminary study before the in vivo assays.

The results showed a good biocompatibility of PLGA nanoparticles in the hemolysis assay and the proliferation study with cell lines. It was also observed a higher cytotoxic activity of PTX when is loaded to PLGA nanoparticles. Tumor cells treated with PTX-PLGA showed a greater reduction of the PTX IC50 value (58,74% MCF-7, 23,5% MDA-MB-231), however the pattern of cell cycle was not altered. This higher antitumor effect was also observed in multicellular tumor spheroids. Cellular internalization studies showed a higher cell uptake of NR when is loaded to PLGA nanoparticles in comparison with a NR solution.

These differences are greater with high exposure times.

From these preliminary results, we suggest that PTX-loaded nanoparticles could be a safe and useful tool to be used for the treatment of breast cancer because of their biocompatibility, good tumor cell uptake and higher drug cytotoxicity.

References [1] [2] [3]

Gornstein, E., and Schwarz, T.L., Neuropharmacology, 76 (2014) 175–183.

Weiszhár, Z., Czúcz, J., Révész, C., Rosivall, L., Szebeni, J., Rozsnyay, Z., Eur. J. Pharm. Sci., 45 (2012) 492–498.

Danhier, F., Ansorena, E., Silva, J.M., Coco, R., Le Breton, A., Préat, V., J. Control. Release, 161 (2012) 505–522.

Figures

Figure 1: MDA-MB-231 prolifferation study (A), confocal images of MCF-77 cells treated with NR and NR NR-loaded PLGA nanoparticles (B) and MCF-7 cell uptake study by flow cytometry (C).

41

Advanced CVD systems for the synthesis of two-dimensional materials beyond graphene Nuria Campos1, Joaquín Fernández1, Byung Hee Hong2,3 1

Graphene Square Europe, C/ Marqués de Teverga 3, Avilés, Spain Graphene Square Inc., Inter-University Semiconductor Research Center, 1 Gwanak-ro, Seoul 08826, South Korea 3 Seoul National University, Department of Chemistry, Seoul 152-742, South Korea euinfo@graphenesquare.com

2

In the last years, an increasing interest in two dimensional materials beyond graphene is becoming apparent caused by the new possibilities of application that emerge from their ouststanding electrical, optical and mechanical properties. In particular, most of the recent works in the field deal with issues as their band-gap tunning [1] and the tailored properties of heterostructures created by combining graphene, hexagonal boron nitride and/or transition metal dichalcogenides, (TDMCs) such as molybdenum disulfide or diselenide [2].

Up to the date, mechanical exfoliation has been the most widely used technique to obtain these heterostructures, presenting problems as poor repeatability, low throughput and high cost, which hinder the scalability of the process, being the synthesis of these materials with large area homogeneity a major challenge.

42

To overcome those problems, chemical vapor deposition has been repeatedly proposed for the synthesis of two-dimensional materials beyond graphene (see, for example [3]), given that it is a well established technique for the obtaining of the last. However, adapting this well-know method for the synthesis of other two-dimensional materials is not trivial, and often will require the modification of the systems employed to carry out the CVD growth.

Our aim is to review the main current challenges to grow these 2d materials by means of CVD, as well as the solutions proposed by Graphene Square Inc. to overcome them, which have been taken into account in the design of brand new scientific equipment optimized for this task.

Specifically, the custom-designed models which appear in Figure 1 will be presented, optimized for the synthesis of graphene, h-BN and TMDCs from chip to wafer-scale on various substrates by using gas- phase or solid precursors and metal organic sources.

References [1] [2] [3]

Q. Ma et al., ACS Nano, 8 (2014) 4672.

X. Wang, F. Xia, Nature Materials, 14 (2015) 264.

Y. Lee et al., Nanoscale, 6 (2014) 2821.

Figures

Figure 1: TCVD-RF100CA and TCVD-DC100CA for the synthesis of graphene, h-BN and TMDCs.

43

Graphene status and needs for industry integration Alba Centeno GRAPHENEA S.A, Tolosa Hiribidea 76, E-20018 San Sebastian, SPAIN a.centeno@graphenea.com

The unique properties of graphene demonstrate at laboratory scale the strong potential of this material to be implemented into technological applications such us electronics, opto-electronics, sensors, touch screen and display technology among others. However, each application requires specific properties and therefore a customized graphene material. The right graphene format, film or powder, needs to be selected and its production and final properties adjusted to the desired application. In this sense, in order to make this material disruptive and competitive to promote commercial applications there are still some needs that have to be fulfilled.

44

The presentation assesses the current status of graphene production, up-scaling and integration. We discuss a series of items that influence graphene time to market. Chemical Vapour Deposition (CVD) represents the most competitive production method for monolayer graphene. The transfer process and the substrate are two of the keys for graphene performance. Here we show the need to develop the right transfer process depending on the substrate where graphene is deposited and the required properties. In addition, sometimes graphene needs to be doped [1], multilayer stacked or encapsulated.

Characterization techniques for large area analysis become essential in order to ensure the good quality of the films [2]. Similarly, we will also review the status of the graphene powder.

References [4]

[5]

Lorenzo D'ArsiĂŠ, Santiago Esconjauregui, Robert Weatherup, Yuzheng Guo, Sunil Bhardwaj, Alba Centeno, Amaia Zurutuza, Cinzia Cepek, and John Robertson, Applied Physics Letters 105, (2014) 103103.

Jonas D. Buron, David M. A. Mackenzie, Dirch. H. Petersen, Amaia Pesquera, Alba Centeno, Peter Bøggild, Amaia Zurutuza, and Peter U. Jepsen, Optics Express, 23(24) (2015) 30721.

Electronic transport in 1D atomic carbon chains and in 2D conjugated polymer networks Jean-Christophe Charlier University of Louvain, Institute of Condensed Matter and Nanosciences, Belgium

Carbyne, the sp1-hybridized phase of carbon, is still a missing link in the family of carbon allotropes.

Recently, detailed electrical measurements and first-principles electronic transport calculations have been performed on monoatomic carbon chains [1]. When the 1D system is under strain, the currentvoltage curves exhibit a semiconducting behavior, which corresponds to the polyyne structure of the atomic chain with alternating single and triple bonds. Conversely, when the chain is unstrained, the ohmic behavior is observed in agreement with the metallic cumulene structure with double bonds. These measurements confirm recent theoretical predictions, namely that a metal-insulator transition can be induced by adjusting the strain in carbyne [2]. The key role of the contacting leads is also scrutinized by ab initio quantum conductance calculations, explaining the rectifying behavior measured in monoatomic carbon chains in a non-symmetric contact configuration.

Two-dimensional conjugated polymers exhibit electronic structures analogous to that of graphene with the peculiarity of π–π* bands which are fully symmetric and isolated. Realistic 2D conjugated polymer networks with a structural disorder such as monomer vacancies (unavoidable during bottom-up synthesis) are investigated using both ab initio and tight-binding techniques in order to check their suitability for electronic applications. As expected, long mean free paths and high mobilities are predicted for low defect densities. At low temperatures and for high defect densities, strong localization phenomena originating from quantum interferences of multiple scattering paths are observed in the close vicinity of the Dirac energy region while the absence of localization effects is predicted away from this region suggesting a sharp mobility transition [3].

References [1] [2]

[3]

Electrical transport measured in atomic carbon chains O. Cretu, A. R. Botello-Méndez, I. Janowska, C. Pham-Huu, J.-C. Charlier, and F. Banhart Nano Letters 13, 3487-3493 (2013).

Strain-induced metal-semiconductor transition observed in atomic carbon chains A. La Torre, A. R. Botello-Méndez, W. Baaziz, J.-C. Charlier, and F. Banhart Nature Communications 6, 6636 (2015).

The electronic and transport properties of 2D conjugated polymer networks including disorder J.-J. Adjizian, A. Lherbier, S.M.-M. Dubois, A.R. Botello-Méndez, and J.-C. Charlier Nanoscale 8, 1642 (2016).

45

From “beneficial properties” to the “benefits” of nanos: a social process Patrick Chaskiel Lab.: Certop UMR 5044 (CNRS, Université Jean Jaurès, Université Paul Sabatier) Toulouse, France University: Paul Sabatier-Toulouse 3 patrick.chaskiel@univ-tlse3.fr

1° The nanos topic has emerged as a public problem in a long-term tendency which has questioned the legitimacy of many industrial, technological and scientific activities as: nuclear, chemical processes and products (Seveso plants, asbestos), GMO, and now “nanos”: nanoproducts, nanotechnologies and nanosciences. This tendency has been institutionalized through many and major regulations, like “Reach” (Registration, Evaluation, Authorization of Chemical substances).

2° If we concentrate on the risks (environment and health) aspect (without regarding others as “enhanced human being” or “civil rights” dimensions), the challenge facing scientists and social scientists is enormous since knowledge on toxicity and ecotoxicity of nanos appears to be quite weak. This knowledge is improving but since “each case is a case”, addressing nanos uniquely through the risks aspects could lead to a deadlock. In order to move, it seems necessary and relevant to go towards the “benefits” aspect. But this aspect is much more complicated than generally supposed.

46

3° There is classically a confusion between beneficial properties and benefits (of nanos or any material).

Beneficial properties are determined by scientific researches which can say if, for instance CNT (or graphene) is more conductive or more resistant than other particles; or if nanosilver is a better biocide than silver in its bulk form. Benefits represent some kind of social utility. Thus from “beneficial properties” to “benefits”, there is a social process which needs to be formalized (I will rely on a research dealing with the conception of a nanomedical device to illustrate the difference between both notions).

4° This distinction has consequences and paves the way towards a new paradigm for researches on nanos.

Firstly, it creates room for concrete cooperation between sciences and social sciences on applications. In that optics, the social process of transformation of beneficial properties into benefits must be taken into account as soon as the research begins. Secondly, this approach opens a way to master the risks dimensions because it supposes that nanos used in shaping applications should be evaluated before their use.

To that extent, nanos could rebuilt as a public question.

Luminescent nanoribbons based on 1D coordination polymers with Cu-I chains Javier Conesa-Egea1, G. Donati2, Sergio G. López2, Stefano Toffanin2, Salomé Delgado1, Pilar AmoOchoa1, Félix Zamora1,3 1

Universidad Autónoma de Madrid. Facultad de Ciencias, Departamento de Química Inorgánica and Condensed Matter Physics Center (IFMAC). 28049 Madrid, Spain.

2 Istituto per lo Studio dei Materiali Nanostrutturati. Via P. Gobetti 101, 40129 Bologna, Italy.

3 Ins. Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanociencia), Cantoblanco, 28049 Madrid, Spain. javier.conesa@uam.es

Modifying the synthesis conditions of the 1D coordination polymer [Cu(MeIN)I]n, where MeIN is methyl isonicotinate (by fast precipitation with a poor solvent [1-2]), we have been able to obtain nanoribbons of the same polymer. These nanoribbons have been characterized by Scanning Electron Microscopy and powder X-ray diffraction. The last technique confirms that the nanoribbons keep the original crystal structure of the polymer. The SEM images show that the nanoribbons tend to aggregate into microribbons with sizes ranging from 2 to 5 µm (Figure 1a). We have proceeded to do a comparative study of the luminescent properties of the bulk material and these ribbons, observing a slight increase of the emission wavelength (Figure 1b-d) [3] and a decrease of the quantum yield, due to the size reduction. Furthermore, we have studied the variation of the emission of the nanoribbons with temperature.

References [1] [2] [3]

A. Carné, C. Carbonell, I. Imaz, D. Maspoch, Chem. Soc. Rev., 40 (2011), 291.

J. Della Roca, D. Liu, W. Lin, Acc. Chem. Res., 44 (2011), 957.

K. Hassanein, J. Conesa-Egea, S. Delgado, O. Castillo, S. Benmansour, J. I. Martínez, G. Abellán, C. J. Gómez-García, F. Zamora, P. Amo-Ochoa, Chem. Eur. J., 21 (2015) 1728.

Figures

Figure 1: a: SEM images of the [Cu(MeIN)I]n nanoribbons. b: Luminescence spectrum of the bulk material. C: Confocal microscopy image of the [Cu(MeIN)I]n ribbons. d: Localized luminescence spectra of the four areas detailed in image c.

47

Photocontrol of antibacterial capacity based on Z/E isomerism Elena Contreras-García, David Martínez-López, Eduardo Santamaría-Aranda, Carmen Lozano, Carmen Torres, Diego Sampedro, Pedro J. Campos Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja, Madre de Dios, 53, 26006, Logroño, La Rioja, Spain. elcontre@unirioja.es

Molecular switches are widely used for different applications as control of peptide conformations or data storage. In this work, a series of compounds with their structure based on both molecular switches and antibiotics have been studied. [1] As the antibiotic part, ciprofloxacin and nalidixic acid, both of them belonging to the group of quinolones, have been selected. The molecular switch part is composed by compounds capable of perform Z/E isomerization under the right stimulus. The result of the union of these two parts are various structures which are expected to have bactericidal properties and, in addition, the ability to control these bactericidal properties by a light-activated Z/E isomerism. With this purpose, an analysis of the photochemical features was made to check whether the synthesized structures can be used as molecular switches. Finally a study to determine their bactericide properties was performed, more specifically two parameters were measured: minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC).

References

48

[1]

Figures

Velema, Willem A.; van der Berg, Jan Pieter; Hansen, Mickel J.; Szymanski, Wiktor; Driessen, Arnold J. M.; Feringa, Ben L. Nature Chemistry 2013, 5 (11), 924-928.

Near-field radiative heat transfer at the nanoscale Juan Carlos Cuevas Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, Madrid, 28049, Spain juancarlos.cuevas@uam.es

Radiative heat transfer between objects at different temperatures is of fundamental importance in applications such as energy conversion, thermal management, lithography, data storage, and thermal microscopy [1]. It was predicted long ago that when the separation between objects is smaller than the thermal wavelength, which is of the order of 10 m at room temperature, the radiative heat transfer can be greatly enhanced due to the contribution of evanescent waves (or photon tunneling) [2]. In recent years, different experimental studies have confirmed this long-standing theoretical prediction [1]. However, in spite of this progress, there are still many basic open questions in the context of near-field radiative heat transfer (NFRHT). Thus for instance, recent experiments exploring the radiative thermal transport in nanometric gaps have seriously questioned the validity of fluctuational electrodynamics [3], which is presently the standard theory for the description of NFRHT. In this talk, I will review our recent theoretical and experiment efforts to shed new light on the problem of NFRHT at the nanoscale. In particular, I will discuss the following two fundamental issues: (i) The enhancement of NFRHT in polar dielectric thin films [4] and (ii) the radiative heat transfer in the extreme near-field regime when objects are separated by nanometer-size distances [5].

References [1] [2] [3] [4] [5]

B. Song, A. Fiorino, E. Meyhofer, and P. Reddy, AIP Adv. 5, 053503 (2015).

D. Polder and M. Van Hove, Phys. Rev. B 4, 3303 (1971).

L. Worbes, D. Hellmann, and A. Kittel, Phys. Rev. Lett. 110, 134302 (2013).

B. Song, Y. Ganjeh, S. Sadat, D. Thompson, A. Fiorino, V. Fernández-Hurtado, J. Feist, F.J. GarcíaVidal, J.C. Cuevas, P. Reddy, and E. Meyhofer, Nature Nanotechnology 10, 253 (2015).

K. Kim, B. Song, V. Fernández-Hurtado, W. Lee, W. Jeong, J. Feist, M.T.H. Reid, F.J. García-Vidal, J.C. Cuevas, E. Meyhofer, and P. Reddy, Nature 528, 387 (2015).

Figures

Figure 1: Radiative thermal radiation between an AFM tip and a surface both made of SiO2 and separated by a few nanometers.

49

Particle size determination of metal oxides and metallic (nano-)particles in consumer products by DLS, AF4-MALLS-ICP-MS and SP-ICP-MS Inmaculada de la Calle1,2, Marlène Klein1, Mathieu Menta1, Fabienne Séby1 1

Ultra Trace Analyses Aquitaine UT2A/ADERA. Hélioparc Pau-Pyrénées, 2 avenue du Président Angot, 64053 PAU cedex 9, France.

Departamento de Química Analítica y Alimentaria, Área de Química Analítica, Facultad de Química, Universidad de Vigo, Campus As Lagoas-Marcosende s/n, 36310 Vigo, Spain. incalle@uvigo.es

2

Nanoparticles (NPs) have been recently used in consumer products mainly as anticaking agents, white pigments, UV filters and antimicrobial agents. The European Commission has established that the word “nano” should be included in the label of the product if NPs are present at 50 % or more in the size range of 1-100 nm. For the moment, in food products the presence of calcium carbonate (E170) and vegetable carbon (E153) NPs is allowed. In the following years (2015-2018), other additives that could be added in nano-form will be evaluated (including TiO2 (E171), iron oxides and hydroxides (E172), Ag (E174), Au (E175), SiO2 (E551), calcium silicate (E552), magnesium silicate (E553a) and talc (E553b)). Therefore, in order to accomplish these regulations, characterization of NMs becomes now necessary in daily products.

Nevertheless, so far, there is no standardized analytical method to evaluate the presence and the size of NPs in these samples.

50

In this work, we develop a methodology for the evaluation of the presence of NPs in different consumer products including foods, drinks and personal care products. Several techniques have been compared such as Dynamic Light Scattering (DLS), Asymmetrical Flow Field-Flow Fractionation coupled to Multiangle Laser Light Scattering and Inductively-coupled Plasma Mass Spectrometry (AF4- MALLS-ICP-MS) and Single Particle Inductively-coupled Plasma Mass Spectrometry (SP-ICP-MS). A suitable sample preparation has been applied for the different consumer products: defatting with hexane and resuspension in water (sunscreens and toothpaste), extraction in water (sugar coated chocolate candies, chewing gum, pastry decoration pearls), suspension in water (cappuccino powder) and filtration (energetic drinks, wines, beer, fruit juices, coffee, hot chocolate).

Firstly, the analytical methodology has been validated using NPs reference materials of diverse nature, metallic and non metallic (e.g. polystyrene nanospheres, Au, SiO2 and TiO2). The size detection limits by SPICP-MS were 18 nm (Au), 20 nm (Ag), 32 nm (TiO2) and 200 nm (SiO2). The limits of detection in concentration were in the order of ng/L (SP-ICP-MS), µg/L (AF4-MALLS-ICP-MS) and mg/L (DLS). Results achieved for personal care products showed the presence of TiO2 particles in sunscreens labeled as “nano”, and more than 50 % of the particles have a size in the nm range, being the Ti concentration of 13 mg/g and the particle size 86 ± 5 and 80± 10 nm achieved by AF4-MALLSICP-MS and SP-ICP-MS, respectively. Furthermore, TiO2 particles were also found in toothpaste (50 - 125 nm). In the same way, TiO2 particles (80 - 200 nm) were also detected in chocolate candies and chewing gum. The analysis of extracts of the covering of pearl decoration pastries shows the presence of Ag NPs. Finally, in the case of drinks, the particle size obtained by DLS was in the range of 10 - 300 nm that could correspond to metallic NPs, polysaccharides, micelles or biopolymers. Concretely, in some wine samples, Cu NPs were observed but in a very low concentration. For cappuccino powder and multifruit juice, some particles of Ti and Al can appear. Moreover, for hot chocolate, Al and organic particles were observed.

To conclude, this work shows the complementarities of several techniques for NPs size analysis. DLS gives only information of the hydrodynamic diameter of the particles. However, the use of AF4-MALLS-ICP-MS

and SP-ICP-MS allows obtaining simultaneously information of the particle size and composition of the particles. SP-ICP-MS is a very fast technique, which will be in future years selected as NP screening technique.

Acknowledgements I de la Calle thanks Xunta de Galicia for financial support as a post-doctoral researcher of the I2C program and cofinancing by the European Social Funding P.P. 0000 421S 140.08 and the UT2A/ADERA for giving her the opportunity to work in their research centre.

51

Effect of organic stabilizers over silver nanoparticles fabricated by femtosecond pulsed laser ablation Pablo Díaz-Núñez1,2, Jesús González-Izquierdo2, Guillermo González-Rubio2,3, Andrés GuerreroMartínez2, Antonio Rivera1, José Manuel Perlado1, Luis Bañares2 and Ovidio Peña-Rodríguez1,* 1

Instituto de Fusión Nuclear, Universidad Politécnica de Madrid, José Gutiérrez Abascal 2, E-28006 Madrid, Spain Dep. de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain 3 BioNanoPlasmonics Laboratory, CIC biomaGUNE, Paseo de Miramón 182, 20009 Donostia - San Sebastián, Spain ovidio.pena@upm.es

2

Femtosecond Pulsed Laser Ablation (fs-PLA) is a versatile technique used in diverse applications. When applied in a liquid environment, this process is able to synthesize colloidal solutions of nanoparticles from the ablated material in a complex process [1]. Silver nanoparticle fabricated by femtosecond laser ablation was first reported in [2], where very low concentrated solutions were produced. In this work we have used femtosecond laser ablation to generate highly concentrated silver colloidal nanoparticle solutions. When performed in pure water, such concentrations usually lead to a high level of agglomeration making the solutions nearly useless. To avoid this problem, we have employed two different organic stabilizers, the ionic surfactant hexadecyltrimethylammonium bromide (CTAB) and the anionic polymer polyvinylpyrrolidone (PVP), and studied its effect on the size distribution, structural characteristics and concentration of the solutions by means of Transmission Electron Microscopy and optical absorption spectra. Our results show that the agglomeration can be considerably reduced or even completely eliminated with those stabilizers.

52

References [1] [2]

V. Amendola and M. Meneghetti, Physical Chemistry Chemical Physics, 15(9) (2013) 3027-3046.

T. Tsuji, T. Kakita amd M. Tsuji. Applied Surface Science, 206 (2013) 314-320

Figures

Figure 1: TEM micrograph of silver nanoparticles fabricated by pulsed laserablation in H2O+PVP

Embedded silver nanoparticle multilayers fabricated by femtosecond pulsed laser deposition Ovidio Peña-Rodríguez1,2,*, Pablo Díaz-Núñez1,2, Jesús González-Izquierdo3, Antonio Rivera2, Gabriel Balabanian2,4, José Olivares5,6, José Manuel Perlado2 and Luis Bañares3 1

CEI Campus Moncloa, UCM-UPM, Avda. Complutense, Madrid, Spain Instituto de Fusión Nuclear, Univ. Politécnica de Madrid, José Gutiérrez Abascal 2, E-28006 Madrid, Spain 3 Dep. de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain 4 Carl Zeiss Microscopy GmbH, Geschäftsführung: Dr. Frank Stietz., Sitz der Gesellschaft: 73447 Oberkochen, Germany 5 Centro de Micro-Análisis de Materiales, Universidad Autónoma de Madrid, Cantoblanco, E-28049 Madrid, Spain 6 Instituto de Óptica, Consejo Superior de Investigaciones Científicas, C/ Serrano 121, E-28006 Madrid, Spain ovidio.pena@upm.es 2

Deposits of exposed and embedded silver nanoparticles were grown on Si(100) and silica substrates by laser ablating high-purity silver and SiO2 targets in vacuum using a femtosecond Ti:sapphire laser delivering 45 fs pulses at 804 nm and 1 kHz repetition rate. The effect of the laser fluence and irradiation time on the obtained nanostructures was investigated using several fluences between 650 mJ/cm2 and 3.2 J/cm2 and deposition times in the range of 1-20 minutes. Optical response of the deposits was characterized using optical absorption spectroscopy and the surface morphology was studied by scanning electron microscopy (SEM). Samples with the optimal optical response were obtained by depositing three successive Ag/SiO2 bilayers at the main laser wavelength (804 nm) under vacuum at substrate room temperature. They were composed of silver nanoparticles with an average diameter of 6 nm and a narrow size distribution; each layer of these nanoparticles was then separated by silica layers of approximately 100 nm. The laser fluence and deposition time for Ag (SiO2) were 650 mJ/cm2 (3.2 J/cm2) and 1 min (10 min), respectively.

Figures

Figure 1: SEM micrograph of the transversal section of a multilayer structure (Ag/SiO2/Ag/SiO2/Ag/SiO2) deposited on a silica substrate.

53

Towards the nanotechnology in the footwear sector Álvaro Díez, Adela Eguizábal, Marisa García, Jorge García Footwear Technology Center of La Rioja (CTCR), Pol. Ind. El Raposal 65, 26580, Arnedo, Spain adiez@ctcr.es

The Footwear Technology Center of La Rioja (CTCR), located in the Spanish town of Arnedo (La Rioja), serves as the hub of the sector and the area, providing with its highly qualified staff and excellent facilities, innovative research and development solutions. The Industry of Nanomaterials and Nanotechnology has been growing exponentially continuously, especially in the last 8 years, reaching 2.6 billion dollars in 2014 (5.5 expected for 2016). Within this context, in 2009, the CTCR launched new research into Nanotechnology, incorporating a product line manager, and an analysis and control technician, modifying its laboratories. Since that date, the department has been growing, and nowadays, 5 people contribute to introduce the Nanotechnology into the footwear. The main goal for this new line of development was, and still is, to test new materials from a nanotechnological point of view and apply them in some of the components used in the footwear industry. We can then easily obtain new or better properties, which could increase competitiveness in the regional footwear industry by enhancing and distinguishing their products through the use of new ways of working.

Thus, in the last few years, the CTCR has developed different research projects involving nanotechnology, highlighting:

54

- Footwear for urban motorcycle drivers: Today, the market offers a wide range of protective clothing for occupants of two-wheeled vehicles, but this offer is especially focused on the professional riders and those who use these vehicles as an element of entertainment, leaving aside the large number of urban and intercity motorists who use the motorcycle or scooter as transportation. In the specific field of protective footwear manufacturers, they are specialists on producing safety shoes that comply with the regulations for use by professional drivers. However, this shoe lacks the necessary degree of comfort and ergonomics for its use spread among the other users. The project allowed the development of a new kind of comfortable shoes for motorists with the especial protection that a nanoparticle-based material confers to the created footwear.

- Bactericide rubber: Poor hygiene and unventilated shoes favor the presence of bacteria such as Staphylococci and aerobic Coreniforme that grow in the alkaline conditions found in the footwear, and also favored by poor ventilation and moisture. These bacteria grow easily in this medium where dead skin or other organic components are present, exceeding 420,000 colony forming units on average, in a shoe, including E. coli, responsible for many intestinal diseases. This high number of bacteria, besides being a health problem, is also responsible for the appearance of unpleasant odors due to the formation of several volatile chemicals. The footwear industry is committed to highest quality materials and design. The introduction of nanoparticles before the vulcanization process, allows obtaining bactericide soles, tested against the most commonly found bacteria in footwear.

- Reduction of vulcanization time: One of the main chemical reactions in the footwear sector is the vulcanization process, which allows a rubber to show adequate physical properties to be used as soles. By using nanoparticles, now it is possible to reduce the vulcanization time up to a 40%, which represents a money saving and allows an increment in the shoe production.

Figures

55

CdSe/ZnS Quantum Dots for Improving Detection Capabilities in Analytical Processes Gema M. Durán, Ana M. Contento and Ángel Ríos Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha, Camilo José Cela Avenue s/n, 13004, Ciudad Real, Spain GemaM.Duran@alu.uclm.es

Currently, the use of nanomaterials as analytical tools is one of the most exciting trend in (bio)chemical analysis, providing new opportunities in the development of innovative approaches in the different steps of the analytical process. In this way, a clear example is the use of "quantum dots" nanoparticles (QDs).

The growing importance of this type of nanoparticles as tools in nanoscience and nanotechnology resides in their exceptional optoelectronic properties at nanoscale range due to “quantum confinement” effects and its very reactive surface. These features confer many of the interesting and, sometimes, unexpected properties of QDs [1]. Due to their exceptional optical properties, QDs have found vast applications in analytical research as the next generation fluorescent probes and new sensoring assays. Therefore, QDs are now involved in many analytical applications as analytical tools.

56

In this way, the aim of this communication is to show several analytical procedures for the modification/solubilization of CdSe/ZnS QDs, and their subsequent use as analytical tools, contributing to improve the detection and then the determination of compounds of interest in the several fields, such as environmental [2, 3], food [4, 5] and clinical [6]. Thus, CdSe/ZnS QDs can be used in paper strips for a rapid screening of glucose at concentrations of clinical interest based on the different fluorescence color of the paper. CdSe/ZnS QDs can be functionalized with different types of ligands in order to introduce the appropriate selectivity for target compounds. Thiol ligands are very useful ligands. For instance, L-cysteine increases the fluorescence of CdSe/ZnS QDs in the presence of sulfonylurea herbicides, whereas cysteamine produces a quenching of fluorescence with the same type of pesticides. CdSe/ZnS QDs coated with 3-mercaptopropionic acid was used for the sensitive detection and quantification of paraquat in water samples. The modification with cyclodextrin ligands introduces interesting analytical possibilities, such as the fluorimetric determination of vanillin in food samples. Other different ligands can be used for a strategic modification of CdSe/ZnS QDs for new analytical purposes, as this communication reports.

Acknowledgements Financial support from the Spanish Ministry of Economy and Competitiveness (CTQ2013-48411-P) and Junta de Comunidades of Castilla-La Mancha (PEIC-2014-001-P) is gratefully acknowledged.

References [1] [2] [3] [4] [5] [6]

G.M. Durán, A.M. Contento, Á. Ríos, Current Organic Chemistry, 19 (2015) 1134.

G.M. Durán, A.M. Contento, Á. Ríos, Anal. Chim. Acta, 801 (2013) 84.

G.M. Durán, M.R. Plata, M. Zougagh, A.M. Contento, Á. Ríos, J. Colloid Interface Sci., 428 (2014) 235.

G.M. Durán, A.M. Contento, Á. Ríos, Talanta, 131 (2015) 286.

G.M. Durán, A.M. Contento, Á. Ríos, Anal. Methods, 7 (2015) 3472.

G.M. Durán, T.E. Benavidez, Á. Ríos, C.D. Garcia, Microchim. Acta, DOI 10.1007/s00604-0151685-3.

Mesoporous silica, periodic mesoporous organosilica, and mesoporous silicon nanoparticles for drug delivery and two-photon Photodynamic Therapy Jean-Olivier Durand CNRS, France durand@univ-montp2.fr

Mesoporous silica nanoparticles (MSN) have attracted much attention the last decade for nanomedicine applications due to their biocompatibility, flexible functionalisation, tunable pore size and diameter. We describe here MSN engineered for two-photon triggered drug delivery or photodynamic therapy, in MCF-7 breast cancer cells. The two-photon triggered drug delivery system was based on a FRET mechanism from a two-photon dye in the walls of the MSN to an azobenzene moiety in the pores of the MSN (nanoimpellers). Concerning photodynamic therapy, a two-photon photosensitizer was encapsulated in the walls of the MSN. Two-photon photodynamic therapy was performed in vitro and in vivo on mice bearing colon xenografted tumors. We also studied the use of porous silicon nanoparticles (pSiNP) functionalized with both a photosensitizer and a targeting agent. Porous silicon is a biocompatible and biodegradable material which can generate 1O2 when excited by visible light due to quantum-confinement effect. pSiNP had been shown to be degraded into non-toxic silicic acid byproducts in vivo. The multifunctionalized pSiNP studied here were able to target, image and kill cancer cells in vitro by photodynamic therapy mechanisms both with 1-photon and 2-photon excitation. Alternatively, the synthesis of disulfidebased biodegradable Periodic Mesoporous Organosilica Nanoparticles (nanoPMOs) was realized and the nanoparticles were efficient in delivering doxorubicin in cancer cells.

References Mannose-6-Phosphate Receptor, A Target for Theranostics of Prostate Cancer. Ophélie Vaillant, Khaled El Cheikh, David Warther, David Brevet, Marie Maynadier, Elise Bouffard, Frédéric Salgues, Audrey Jeanjean, Puche Pierre, Catherine Mazerolle, Philippe Maillard, Olivier Mongin, Mireille Blanchard-Desce, Laurence Raehm, Xavier Rébillard, Jean-Olivier Durand, Magali Gary-Bobo, Alain Morère and Marcel Garcia Angewandte Chemie International Edition, 2015, 54, 5952-5956.

Two-Photon Excitation of Porphyrin-Functionalized Porous Silicon Nanoparticles for Photodynamic Therapy. Emilie Secret , Marie Maynadier , Audrey Gallud , Arnaud Chaix , Elise Bouffard , Magali Gary-Bobo, Nathalie Marcotte , Olivier Mongin , Khaled El Cheikh ,Vincent Hugues , Mélanie Auffan , Céline Frochot , Alain Morère , Philippe Maillard , Mireille BlanchardDesce , Michael J. Sailor , Marcel Garcia , Jean-Olivier Durand , Frédérique Cunin Advanced Materials, 2014, 26, 7643–7648.

Biodegradable Ethylene-Bis(Propyl) Disulfide-Based Periodic Mesoporous Organosilica Nanorods and Nanospheres for Efficient In-Vitro Drug Delivery. Croissant Jonas, Cattoen Xavier, Wong Chi Man Michel;, Gallud Audrey, Raehm Laurence, Trens Philippe, Maynadier Marie, Durand Jean-Olivier. Advanced Materials 2014, 26, 6174-6180.

Two-Photon-Triggered Drug Delivery in Cancer Cells Using Nanoimpellers. Croissant Jonas, Maynadier Marie, Gallud Audrey, Peindy N'Dongo Harmel, Nyalosaso Jeff L., Derrien Gaelle, Charnay Clarence, Durand Jean-Olivier, Raehm Laurence, Serein-Spirau Francoise, Cheminet Nathalie, Jarrosson Thibaut, Mongin Olivier, Blanchard-Desce Mireille, Gary-Bobo Magali, Garcia Marcel, Lu Jie, Tamanoi Fuyuhiko, Tarn Derrick, Guardado-Alvarez Tania,M., Zink Jeffrey I. Angew. Chem. Int. Ed., 2013, 52, 13813-13817.

57

Surface Attophysics P.M. Echenique Dpto. de FĂ­sica de Materiales UPV-EHU, Donostia International Physics Center (DIPC) and Material Physics Center (CFM), P. Manuel de Lardizabal 4, 20018 San SebastiĂĄn, Basque Country, Spain

Femtosecond and subfemtosecond time scales typically rule electron dynamics at metal surfaces. We shall analyze briefly electron dynamics at surfaces and nanostructures with emphasis on surface attophysics, namely streaking experiments and spin dependence of charge transfer at adsorbates.

58

Approaching Nanoscience to the Footwear Sector Adela Eguizábal, Marisa García, Álvaro Díez, Jorge García-Barrasa Footwear Technology Center of La Rioja (CTCR), Pol. Ind. El Raposal 65, 26580, Arnedo, Spain aeguizabal@ctcr.es

The footwear industry is deeply rooted in La Rioja region. From household production of espadrilles to industrial production of footwear today, the shoe industry has been adapting to the continuous market changes, keeping its competitiveness. Nowadays this sector is configured as a driver of the economy of the area. With this aim in mind, the Footwear Technology Center of La Rioja (CTCR) works as a support to the footwear industry by offering the latest technologies and as a promoter of R&D+i. Particularly, the Department of Nanotechnology and New Materials applies the nanoscience principles to the improvement of both products and processes in the footwear sector.

When the particles change from centimeter to nanometer scale, the surface area and the surface energy increase several orders of magnitude, according to the nanoscience principles. In this way, the surface reactions become faster and more efficient. The CTCR has developed a project where the size of the charges of the formulation rubber has been reduced to nanometer scale. This has allowed a reduction of the vulcanization rate up to 40 %, thus increasing the production of outsoles.

The nanoscience also allows designing nanostructures and nanoparticles with desired properties. When the nanoparticles are suspended in a liquid is possible to obtain a nanofluid. Some of these nanofluids present non-newtonian properties, which are useful in various applications. The non-newtonian nanofluid materials are able to harden under the action of an impact and remain fluid in others circumstances. A nanofluid prepared in the CTCR has been included in an urban motorbike boot. This boot is able to absorb up to 90% of the energy of an impact, in order to prevent injuries due to its hardening. Moreover, the nanofluid behaves as a liquid that offers flexibility and comfort.

The surface chemistry of nanomaterials makes possible its modification keeping its intrinsic properties.

The CTCR has carried out a project where bactericide nanomaterials have been superficially functionalized to improve compatibility and dispersion within the rubber matrix, with the aim to avoid the bacterial growth in some workplaces.

Nanoporous and microporous materials are accessible by designing nanostructures as zeolites.

Nanoporous materials are capable of hosting molecules and nanoparticles inside their pores and in their external surface. In the CTCR, zeolites with special “guest” particles have been included in rubber to get fireproof outsoles with halogen-free compounds.

Summarizing, these depicted cases show how nanotechnology provides great advantages in the footwear industry for the differentiation in the market.

59

Mesoscopic thermodynamics in nanostructures Klaus Ensslin ETH Zurich, Switzerland

The second law of thermodynamics is one of the pillars of our understanding in modern physics. For nanostructures individual charge carriers may violate this law, while averages over many charging events agree with predictions for macroscopic systems. As nanostructures contain fewer and fewer carriers, fluctuations become ever more important and their understanding is at the heart of mesoscopic thermodynamics. In this talk I will show results on time-resovled single electron transport through semiconductor and graphene quantum devices. This technique allows to measure directional transport at zero applied bias and enables the test of fluctuation theorems that connect measured quantities in nonequilibrium situation to well-known equilibrium quantities. This work was done in collaboration with A. Hofmann, V. Maisi, C. Roessler, B. Kueng, and T. Ihn.

60

Photosensitizer-Silica Nanoparticle as Platform for Photodynamic Therapy Nerea Epelde-Elezcano1,2, Virginia Martinez-Martinez1, Iñigo Lopez-Arbeloa1, Sylvie Lacombe2 1 University of the Basque country UPV-EHU, Aptd 644 48080, Bilbao, Spain IPREM, UMR CNRS 5254, Université de Pau et des Pays de l'Adour, Hélioparc 64039, Pau, France nerea.epelde@ehu.eus

2

The photodynamic therapy (PDT) is a non-invasive treatment of cancers based on photodynamic reactions involving Reactive Oxygen Species (ROS).

Appropriate dye molecules denoted photosensitizers are able to generate singlet oxygen (cytotoxic species) for PDT applications, should present several properties to kill tumour cells; low toxicity, selective accumulation on cancer cells, high absorption in the Visible/near-IR region to have the maximum light absorbed in the skin, and efficient intersystem crossing (ISC) to obtain high singlet oxygen quantum yield.

In order to perform this photomedical technique, it would be suitable to use a mesoporous silica coreshell of several nanometers size as drug carrier of photosensitizer. Mesoporous silica core-shell nanoparticles are selected due to their low-toxicity, tuneable size and a surface which is easily functionalized. In this sense different photosensitizers are grafted on the external surface of the nanoparticle. The silica nanoparticles were synthesized by so-gel process in order to control the particles size (around 30 nm), shape (spherical) and porosity.

Different photosensitizers are selected to be grafted at the external surface of the shell of silica NP: commercial Rose Bengal and new halogenated Boron DiPyrromethene (BODIPY) because of their strong VIS/NIR absorption bands and the high intersystem crossing (ISC) efficiency which shows high singlet oxygen production.

References [1] [2] [3]

Indrajit Roy, Tymish Y. Ohulchanskyy, Haridas E. Pudavar, Earl J. Bergey, Allan R. Oseroff, Janet Morgan, Thomas J. Dougherty, Paras N. Prasad, J. Am. Chem. Soc. 125 (2013) 7860.

Ronzani, F; Blanc, Sylvie; Bordat, P; Pigot, T; Cugnet, C; Arzoumanian, E; Oliveros, E; Sarakha, M; Richard, C; Lacombe, S. Phys. Chem. Chem. Phys, 15 (2013) 17219.

Ortiz, M.J; Agarrabeitia, A.R; Dueran-Sampedro, G; Bañuelos Prieto, J; Arbeloa Lopez, T; Massad, W.A; Montejano, H.A; Garcia, N.A, Lopez Arbeloa, I. Tetrahedron, 68 (2012) 1153.

Figures

Figure 1: (left) Silica Nanoparticle Core-Shell TEM image and (right) the schematic representation of BODIPY grafted on nanoparticle shell.

61

Synthesis of luminescent hybrid silica-based materials C. Ezquerro1, A. Sepulveda1, M. Rico2, S. Ruiz1, E. Serrano2, J. R. Berenguer1, E. Lalinde1, J. Garcia-Martinez2 1

Organometallics Molecular Materials, Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, C/ Madre de Dios 54, Logroño, La Rioja, Spain.

2 Molecular Nanotechnology Lab, Inorganic Chemistry Dpt., Univ. de Alicante, Ctra. Alicante-S. Vicente s/n, Alicante, Spain. www.nanomol.es ciezquer@unirioja.es

62

Mesoporous silica materials have attracted considerable attention during the past decades, being mainly used as support for catalytic applications. Due to their chemical inertness, adequate functionalization is required to develop novel nanostructured materials with innovative properties in different fields such as sustainable energy, environment sensing and remediation, biomaterials, pharmaceutical industry and catalysis, among others. In recent years, our group has developed a new synthetic strategy to obtain hybrid periodic mesoporous metal complex-silica (PMMs).[1][2] This new method is based on the cocondensation of the appropriate silica precursor (like TEOS) with metal complexes containing ligands with terminal trialkoxysilane groups. By this new strategy, the first luminescent complex-silica hybrid material has been synthetized.[2] Following with this work, and considering the growing interest in luminescent silica materials due to their potential photonic, photocatalytic or biomedical applications, we have recently extended this study to the synthesis of emissive complexes of other d6 (IrIII) and d8 (PtII) metallic ions and their incorporation in silica gels. The as-synthesized luminescent Pt and Ir complex-silica gels show good stability and excellent emissive and textural properties, and have been synthesized to be used as mesoporous luminescent materials.

References [1] [2]

Serrano, E.; Linares, N.; Berenguer, J. R.; García-Martínez, J.: Chem. Commun., 5 (2013) 844.

Rico, M.; Sepúlveda, A. E.; Ruiz, S.; Serrano, E.; Berenguer, J. R.; Lalinde, E.; Garcia-Martinez, J.: Chem. Commun., 48 (2012) 8883.

Figures

Acknowledgements We thank the Spanish MINECO (Projects CTQ2013-45518-P and CTQ2014-60017-R) and the Comunidad Autónoma de La Rioja for financial support

Self-assembly of organic molecules onto surfaces: computer simulations Jordi Faraudo, Thomas Roussel Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, C/ dels Til¡lers s/n E-08193 Bellaterra (Spain) jfaraudo@icmab.es

The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. We show here how a novel simulation technique (Self-Assembly of Nano Objects, SANO) is able to perform atomistic simulations of hundreds of organic molecules over large surfaces (50x50 nm2) self-assembling in thermodynamic equilibrium. The technique is illustrated with several examples. We consider (a) [1] the self-assembly patterns of di-indenoperylene (DIP) molecules over different reconstructions of the Au(111) surface [1] and (b) tri-adamantyl (TAB) benzene molecules onto Ag(111) [2]. In both cases, we compare with experimental STM images.

The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilizing the chosen reconstruction pattern.

63 References [1] [2]

Roussel, T. J.; Barrena, E.; Ocal, C.; Faraudo, J. Nanoscale 6 (2014), 7991.

Calmettes, B.; Estrampes, N.; Coudret, C.; Roussel, T. J.; Faraudo, J.; Coratger, R. Phys. Chem.

Chem. Phys. (2016), doi:10.1039/c5cp06733b.

Smart nanomaterials built up from functional organic molecules and photosynthetic microorganisms Gianluca M. Farinola Dipartimento di Chimica Università degli Studi di Bari “Aldo Moro”, Via Orabona 4, 70126 Bari, Italy gianlucamaria.farinola@uniba.it

Photosynthetic microorganisms represent a plentiful source of functional micro/nano structures optimized by billions of years of evolution. Combining such specialized structures with tailored molecules paves the way for intriguing new materials for photonics, electronics and biomedicine. The lecture will present smart nanohybrid materials obtained by chemical modification of silica microstructures from diatoms algae.

Diatoms are single-cell photosynthetic algae characterized by beautiful nanopatterned microscopic silica shells (frustules) with hierarchically-porous 3D morphology and intriguing mechanical and photonic properties. The possibility to manage these biosilica structures as multifunctional scaffolds by chemical modifications opens up the way to biotechnologically-produced nanomaterials with applications including bio-medicine, photonics, filtration, sensing and catalysis [1].

64

We use two approaches for the functionalization of diatoms biosilica with tailored organic molecules. The first is based on covalent attachment of the molecules on the silica shells, after removal of the organic cellular matrix. The second approach is based on in vivo incorporation of the molecules into the biosilica during the cells’ growth.

The lecture will discuss examples of the two approaches. In the first case, in vivo incorporation of several classes of light emitting molecules (fluorescent conjugated compounds or phosphorescent organometallic complexes) in living diatoms results in nanostructured light emitting materials. For the second approach, the lecture will present covalent functionalization of biosilica with 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) (figure), an efficient scavenger of reactive oxygen species (ROS) in biological systems.

Drug delivery properties of the TEMPO-biosilica for Ciprofloxacin, an antimicrobial against orthopedic implant related infections, will be discussed. The TEMPO-biosilica, combining Ciprofloxacin drug delivery with anti-oxidant properties, is demonstrated to be a suitable material for bone cells growth [2].

Our study points out at the combination of biotechnological production and chemical modification as a convenient approach to the synthesis of functional nanostructured materials.

References [1] [2]

W. Yang, P. J. Lopez, G. Rosengarten Analyst,136 (2011) 42.

S. R. Cicco, D. Vona, E. De Giglio, S. Cometa, M. Mattioli Belmonte, F. Palumbo, R. Ragni, G. M. Farinola ChemPlusChem, 80 (2015) 1063..

Improved Method for Probing Resistivity and Doping Concentration of Semiconductors at the Nanoscale Using Scanning Microwave Microscopy (SMM) Matthias A. Fenner1, Enrico Brinciotti2, Georg Gramse3, Ferry Kienberger2 1

Keysight Technologies Deutschland GmbH, Lyoner Strasse 20, 60528 Frankfurt, Germany Keysight Technologies Austria GmbH, Keysight Labs, Gruberstrasse 40, 4020 Linz, Austria 3 Johannes Kepler University, Biophysics Institute, Gruberstrasse 40, 4020 Linz, Austria

2

We describe an improved method using a combination of AFM and local microwave measurement (SMM) for a quantitative determination of resistivity and doping concentration of semiconductor materials on a nanometer scale. The microwave reflection signal (S11) is converted into calibrated resistance and capacitance data via a three error parameters workflow which does not require a calibration step on a known dopant standard sample [1]. By means of an analytical model for the junction of AFM tip and semiconductor the resistance can be converted into resistivity and dopant density data. The method was applied on a silicon sample with p and n doped implant regions and yields a good quantitative agreement with the data-sheet values.

References [1]

Calibrated complex impedance and permittivity measurements with scanning microwave microscopy, Gramse et al. ,2014, Nanotechnology 25 (2014) 145703.

Figures

Figure 1: Comparison of of measured resistivities to data sheet values for doped silicon.

65

The Science of the Small: Understanding the Coalescence of Nanoparticles by Advanced Transmission Electron Microscopy Paulo J. Ferreira Materials Science and Engineering. University of Texas at Austin Austin, TX, 78712, USA

66

Nanoparticles possess many unique properties that are distinct from that of bulk materials, which allows them to be used in applications such as in catalysis and in optical, magnetic and electronic devices. Among these properties, the coalescence behavior of nanoparticles is expected to be quite different from that of bulk materials, especially if the particles experience elevated temperatures. In this work, in-situ heating experiments were performed in a transmission electron microscope (TEM) to monitor the thermal stability of silver nanoparticles. For nominally isothermal experiments, the observed sublimation temperatures generally decreased with decreasing particle size, in agreement with the predictions from the Kelvin equation. However, sublimation of smaller nanoparticles was often observed to occur in discrete steps, which led to faceting of the nanoparticles. In addition, due to their large surface area-tovolume ratio, nanoparticles have a strong tendency to coalesce and sinter during processing or usage over short time scales. Hence, in-situ TEM heating was used to investigate the effects of particle size, temperature and carbon capping layers on sintering in silver and platinum nanoparticles. For the first time, we make direct and real-time measurements of nanoparticle size, neck growth, dihedral angle and grain boundary motion during sintering, which are then used to calculate fundamental material transport parameters such as surface diffusivity and grain boundary mobility [1-3].

References [1] [2]

[3] [4]

M.A. Asoro, P.J. Ferreira, D. Kovar, “In Situ TEM and STEM Studies of Sintering of Ag and Pt Nanoparticles”, Acta Materialia, Vol. 81, pp. 173–183 (2014).

M.A. Asoro, D. Kovar, P.J. Ferreira, “Effect of surface carbon coating on sintering of silver nanoparticles: in situ TEM observations”, Chemical Communications, Vol. 50, pp. 4835-4838, (2014).

Michael Asoro, Desiderio Kovar, Paulo Ferreira, "In-situ Transmission Electron Microscopy Observations of Sublimation in Silver Nanoparticles", ACS Nano, Vol. 7, pp. 7844-7852, (2013).

M.A.Asoro, D. Kovar, Y. Shao-Horn, L.F. Allard, P.J. Ferreira, “Coalescence and sintering of Pt nanoparticles: In-situ observation by aberration-corrected HAADF STEM”, Journal of Nanotechnology, Vol. 21, pp. 025701-025706 (2010).

GRAPHENET: The Spanish Graphene Network Mar Garcia Hernandez Instituto de Ciencia de Materiales de Madrid CSIC

We here present the scope of the recently created Spanish Graphene Network. The network is a network of excellence linked to the Graphene Flagship but not limited to the flagship Partners. One major objective of GRAPHENET is the creation of the Spanish industrial group with interest in graphene. We also aim at defining a good practice code for graphene producers when labeling their materials so as to help the final users to make the best material choice for a particular application. Promoting synergies between academy and industry to apply in all kind of calls related to graphene activity (national and international) is also a must.

67

Sensing Performance of Hybrid Magnetoplasmonic Nanohole Arrays A. Garcia-Martin1, B. Caballero1, J.C. Cuevas2 1

IMM-Instituto de Microelectrónica de Madrid (CNM-CSIC), Isaac Newton 8, PTM, Tres Cantos, E-28760 Madrid 2 SPAIN Departamento de Física Teórica de la Materia Condensada and Condensed Matter Physics Center (IFIMAC, Universidad Autónoma de Madrid, 28049, Madrid, Spain a.garcia.martin@csic.es

Plasmonic structures are widely used in low-cost, label-free biosensors, and the investigation of how to improve their sensitivity or to widen their range of applications is a central topic in the field of plasmonics.[1,2] The most commonly used plasmonic sensors are based on the concept of surface plasmon resonance (SPR) and, in particular, on the sensitivity of these resonances to changes in the refractive index of the medium surrounding a metallic structure.

In the search for an improved bulk sensitivity of SPR-based sensors, researchers have proposed different strategies. Thus, for instance, it has been shown that the use of the magneto-optical properties of layered systems containing magnetic materials can, in principle, enhance the sensitivity of these sensors.[3,4] Another possibility that is becoming increasingly popular is the use of nanohole arrays or perforated metallic membranes featuring arrays of subwavelength holes. [5,6] These sensors make use of the extraordinary optical transmission phenomenon, which originates from the resonant excitation of surface plasmons in these periodically patterned nanostructures.

68

We present here a theoretical study that shows how the use of hybrid magnetoplasmonic crystals comprising both ferromagnetic and noble metals leads to a large enhancement of the performance of nanohole arrays as plasmonic sensors. In particular, we propose using Au−Co−Au films perforated with a periodic array of subwavelength holes as transducers in magnetooptical surface-plasmon-resonance sensors, where the sensing principle is based on measurements of the transverse magnetooptical Kerr effect (TMOKE). We demonstrate that this detection scheme may result in bulk figures of merit that are two orders of magnitude larger than those of any other type of plasmonic sensor.[7] The sensing strategy put forward here can make use of the different advantages of nanohole-based plasmonic sensors such as miniaturization, multiplexing, and its combination with microfluidics.

References [1] [2] [3] [4] [5] [6] [7]

O. Tokel, F. Inci, U. Demirci, Chem. Rev. 114, (2014) 5728.

M.-C. Estevez, M. A. Otte, B. Sepulveda, L. M. Lechuga, Anal. Chim. Acta 806, (2014) 55.

A. Calle, L.M. Lechuga, G. Armelles, Opt. Lett. 31, (2006) 1085.

M.G. Manera, et al., Biosens. Bioelectron. 58, (2014) 114.

A.A. Yanik, et al., Proc. Natl. Acad. Sci. U. S. A. 108, (2011) 11784.

A.E. Cetin, et al., ACS Photonics 2, (2015) 1167.

B. Caballero, A. García-Martín, and J. C. Cuevas, ACS Photonics 3, (2016) 203.

Figures

Figure 1: Left: TMOKE signal as a function of wavelength for varying values of the environment refractive index. Top-right: sketch of the structure used for the study. Bottom-right: figure of merit of obtained from the TMOKE curves.

69

Genotoxicity Assessment of Air-Borne Engineered Nanomaterials using the BEAS-2B and A549 in vitro system Alba García, Laura Rubio, Ricard Marcos, Alba Hernández Grup de Mutagènesi, Departament de Genètica i de Microbiologia, Facultat de Biociències, Universitat Autònoma de Barcelona, Bellaterra, Spain; CIBER Epidemiología y Salud Pública, ISCIII, Spain alba.garcia.rodriguez@uab.cat

Nanomaterials (NMs) display many unique and useful physico-chemical properties. For this reason, since many years ago, Nanothechnology has become increase such as a new discipline in order to design and synthesize engineered nanomaterials (ENMs). Furthermore, the ENMs are being commonly used in a wide range of applications in the industrial, electrical, pharmaceutical and biomedical fields and are included in several consumer products such as cosmetics, food packaging, aerosols-like products, etc. Inhalation is one of the major routes of exposure to the ENPs and is considered to be the primary route by which humans get exposed to the air-borne ENPs. After inhalation, the ENPs are likely to get deposited in different regions of the respiratory tract depending on the particle size. Several kinds of sicknesses can be expected from exposure to ENPs, including asthma, bronchitis, lung and liver cancer and others (Gasser et al., 2012, Nemmar, Holme, Rosas, Schwarze, & Alfaro-moreno, 2013, Farcal et al., 2015).

70

In the present study, the in vitro genotoxicity of two different air-borne ENMs (MWCNT and CeO2) was evaluated in two cellular models representing the lung as a target organ/system. The cells lines were BEAS-2B a transformed normal human bronchial epithelium and A549 a human lung carcinoma. Sub-toxic concentrations from each NM were used to perform a Comet Assay of 24 hours treatment. In this case, the results lead us to the conclusion that there is no presence of genotoxic damage neither oxidative damage for both cell system and for both ENMs. References Farcal, L., Andón, F. T., Cristo, L. Di, Rotoli, B. M., Bussolati, O., Bergamaschi, E., … Bai, R. doi:10.1371/journal.pone.0127174. Comprehensive In Vitro Toxicity Testing of a Panel of Representative Oxide Nanomaterials : First Steps towards an Intelligent Testing Strategy. (2015).1–34.

Gasser, M., Wick, P., Clift, M. J. D., Blank, F., Diener, L., Yan, B., Rothen-rutishauser, B. Particle and Fibre Toxicology. Pulmonary surfactant coating of multi-walled carbon nanotubes (MWCNTs) influences their oxidative and pro-inflammatory potential in vitro. (2012).1–13.

Nemmar, A., Holme, J. A., Rosas, I., Schwarze, P. E., & Alfaro-moreno, E. BioMe Research International. Recent Advances in Particulate Matter and Nanoparticle Toxicology : A Review of the In Vivo and In Vitro Studies, 2013.

1–22.

Figures

Figure 1: Oxidative damage and general damage assessed by the Comet Assay. Results regarding two cell lines, BEAS-2B and A549, and treated with two different air-borne ENPs, Multi-wall Carbon Nanotube (MWCNT) and Cerium dioxide (CeO2). As a positive control for the Genotoxic damage we used MMS, and for the Oxidative damage we used KBrO3.

71

Bulk graphene preparation for energy and composites applications Julio Gomez Cordon1, Elvira Villaro2,3, Jesus Ruben Berenguer4 and Imanol Recio1,4 1

AVANZARE, Avda Lentiscares 4-6, Navarrete, Spain Instituto de Tecnologías Químicas Emergentes de La Rioja; San Francisco, 11 Navarrete, Spain 3 Departamento de Química Inorgánica y Técnica, UNED. Senda del Rey, 9, Madrid, Spain 4 Departamento de Químicas. Universidad de La Rioja, Madre de Dios, 53 Logroño, Spain julio@avanzare.es

2

The bulk graphene market will exponentially grow in the next few years. Its applications in composites will be the largest segment, followed by energy storage applications. [1] Different synthetic methods can be used for the production of graphene and graphene related materials. [2] However, most of the materials labeled as graphene in the market are far from the classification and nomenclature for Graphene-Based Materials [3] and there is a lot of production capacity, especially of nanographite materials in factories, but lacks a killer application.[1c] Several reviews analyzed the applications of the different graphene and related products in energy [4,1b] and in composites applications. [5, 1b]

72

In this communication, 3 different methods for the production of bulk graphene or reduce graphene oxide: liquid exfoliation, reduced graphene oxides and high expansion were compared with other production methods and products in the market.

The complete characterization of graphene and highly reduce graphene oxide using TEM, SEM, AFM, XPS, DRX, Laser diffraction, etc will be presented.

Different types of graphene materials with variation in lateral size, defects and defects concentration, thickness, etc, have been used to obtain graphene-thermoplastic and thermoset composites. The different effects of the incorporation of liquid exfoliated graphene, highly reduced graphene oxide and graphene nanoplatelets on electrical, thermal conductivity and fire retardant properties of epoxy were investigated.

Related to electrical properties, some of these composites show lower percolation threshold limits than the previously reported values, also obtaining ultralow percolation limits (Figure), opening a new range of applications and markets.

Other factors as processing technique, the compatibility between graphene and matrix and dispersion have an extremely high importance in the results.

The use of different graphene materials and decorated graphene materials in energy applications, from batteries to supercapacitors with ultrahigh energy density, will be also presented.

References [1] [2]

a) Zh Ma, R. Kozarsky, M. Holman., GRAPHENE MARKET UPDATE. LUX RESEARCH (2014). b) Ferrari A Cet al Nanoscale 7 (2015) 4598–810, c) M. Peplow, Nature 522, (2015), 268.

W. Ren, H.-M. Cheng, Nature Nanotechnology 9, (2014) 726–730.

[3] [4] [5]

P. Wick et all, Angew. Chem. Int. Ed. 53 (2014)7714–7718. b) R. Hurt et all, Carbon, 65 (2013) 16.

The role of graphene for electrochemical energy storage. Nature Materials 14 (2015) 271–279. a) P Samorì, I A Kinloch, X Feng and V Palermo, 2D Mater. 2 (2015) 030205 b) R. J. Young, I. A. Kinloch, L. G., Kosty. S. Novoselov, Composites Science and Technology, 72 (2012) 1459–1476.

Figures

Figure 1: Electric percolation and Scheme of the transport in a composite.

73

Mechanical properties of fluctuating graphene 1

Julio Gómez-Herrero , G Lopez-Polin1, Gomez-Navarro1, R Roldan2, M Katsnelson3, F Guinea2, Maria Ortega1, J. G. Vilhena1 and Rubén Perez1 1

Departamento de Física de la Materia Condensada and IFIMAC, UAM, Campus de Cantoblanco, Madrid 2 Instituto Ciencia de Materiales de Madrid, CSIC and IMDEA Nanociencia, Madrid 3 Institute for Molecules and Materials, Radboud University Nijmegen. julio.gomez@uam.es

Bendable membranes (with bending rigidity comparable to their thermal energy) exhibit entropic effects in the form of out of plane fluctuations that bring out exotic mechanical properties such as size dependent elastic constant and negative thermal expansion coefficient [1]. Graphene is the nature’s thinnest elastic membrane. It is highly bendable, stiff and anharmonic. Therefore the above mentioned phenomena should apply to it.

In this work we measure, by means of indentation experiments, the dependence of the elastic modulus of graphene both as a function of controlled induced defects [2] and a as a function of external strain [3]. Our results support renormalization of the elastic constants of graphene at room temperature. We experimentally observe that graphene stiffens up to the double of its initial value when low densities of carbon vacancies are induced. It also presents a substantial increase in Young´s modulus at high external strains. We attribute these observations to the suppression of out of plane oscillations both by defects and strain.

74

Finally, we report experimental and theoretical evidence that point out that the negative expansion coefficient of graphene decreases in absolute value as a function of the irradiation dose supporting again the suppression of out plane oscillations with punctual defects.

References [1] [2] [3]

W. Helfrich, Z. Naturforsch. 28, 693 (1973).

G. Lopez-Polin et al., Nature Physics 11, 26–31 (2015). arXiv:1504.05521v1.

Study of the grain thermal stability in the nanostructured tungsten coatings N. Gordillo1, C. Gómez de Castro2, J. del Rio3, E. Tejado4, M. Panizo-Laiz1, G. Balabanian1,5, J. M. Perlado1 and R. Gonzalez-Arrabal1 1

Ins. de Fusión Nuclear, ETSI de Industriales, UPM, C/ José Gutierrez Abascal, 2, E-28006 Madrid, Spain.

Departamento de Física de Materiales, Facultad de CC. Químicas, UCM, Ciudad Universitaria s/n, E-28040 Madrid, Spain.

3 Dep. de Física de Materiales, Facultad de CC. Físicas, UCM, Ciudad Universitaria s/n, E-28040 Madrid, Spain.

4 Department of Materials Science- Research Centre on Safety and Durability of Structures and Materials (CISDEM) , UPMCSIC, C/ Profesor Aranguren s/n,E- 28040, Madrid, Spain 5 Carl Zeiss Microscopy GmbH, Carl-Zeiss-Straße 22, 73446 Oberkochen, Germany nuria.gordillo@upm.es 2

Tungsten has been proposed as a potential material to be used as plasma facing material (PFM) applications in both magnetic and inertial confinement fusion power plants. The main role of the PFM is to protect the wall vessel from the heat loads and curb the irradiation. Nowadays, the capabilities of nanostructured materials for such applications are being attracted much attention due to their radiationresistant and self-healing behaviour. In this context, the thermal stability of the nanostructures is an important subject to be considered.

In this work the thermal stability and texture of nanostructured W (NW) coatings is investigated in the temperature range from RT to 1473 K. The coatings with a thickness of 5 µm in were deposited by combining pulsed and DC magnetron sputtering. The microstructural evolution was characterized by using in situ thermo-diffractometer. The grain size evolution was determined from XRD data combined with atomic force microscope (AFM) and scanning electron microscope (SEM) images. The grain growth activation energy was determined within the nanometre range. From Rietveld analysis of X-Ray patterns, two behaviours in the deformation parameter are observed: (i) From room temperature to 1000 K the micro deformation parameter softly decreases, indicating a small reduction in the induced stress during the NW coating growth (ii) at higher temperatures, a drastic decrease in the micro deformation parameter is followed which is associated with a thermal annealing and stress reduction. Texture analysis using X-ray diffraction was carried out prior to and after annealing indicating that the preferential orientation and columnar structure is preserved after the thermal treatment.

The results of this study suggest that the nanostructures growth starts around 1000 K, however it is important to notice that the average grain size remains in the submicron-sized even for samples annealed at 1473 K.

75

Interface-assisted Sign Inversion of Magnetoresistance in Spin Valves based on Novel Lanthanide Quinoline Molecules Sara G. Miralles, Amilcar Bedoya-Pinto, Saül Velez, Pierluigi Gargiani, Manuel Valvidares, Fèlix Casanova, Eugenio Coronado and Luis.E. Hueso ICMol, Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain sara.gomez.miralles@uv.es

A spin valve is a magnetic device in which the electrical resistance is controlled by an external magnetic field. In this work we fabricated molecular spin valves in which we control the sign of the magnetoresistance by the device stack design. When Permalloy is directly connected to the organic semiconductor layer, a clear negative spin valve effect resistance is observed. This effect may be due to the interaction between the organic layer at the interface Permalloy-molecule.

References [1] [2] [3]

76 Figures

V. A. Dediu, L. E. Hueso, I. Bergenti, C. Taliani, Nat. Mater. 2009, 8, 707–16.

S. Sanvito. Nat Phys 2010, 6, 8, 562–564.

X. Sun, M. Gobbi, A. Bedoya-Pinto, O. Txoperena, F. Golmar, R. Llopis, A. Chuvilin, F. Casanova, L. E. Hueso, Nat. Commun. 2013, 4, 2794.

Spicing Graphene with electroactive inorganic compounds: Graphene hybrid nanocomposites for energy storage Pedro Gรณmez-Romero*, Deepak P. Dubal, Jullieth Suarez-Guevara, Vanesa Ruiz Catalan Institut of Nanoscience and Nanotechnology, ICN2 (CSIC-CERCA) Campus UAB, 08193 Bellaterra (Barcelona), Spain pedro.gomez@cin2.es

Ten years ago graphene became the new kid in nanocarbon Town. Fundamental studies and potential applications have grown ever since like for no other material in recent times.

What could be better than a material stronger than steel, harder than diamond, with great thermal conductivity, modulated electronic conductivity, light as plastic and simple as carbon? The answer is hybrid materials made of it and any other material with complementary functionalities, such as electroactive redox materials.

We have developed a prospective line of work dealing with the synthesis of hybrid nanocomposites of nanocarbons with a variety of extended oxides (MnO2, CuO) as well as with molecular polyoxometalates, alike of metal oxide molecular clusters. [1-2] This approach has been applied to Graphenes leading to materials [3-5] with a perfect combination of properties for their use as active electrode materials in energy-storage devices, namely, a combination of conductivity-electroactivity as well as a combination of double-layer capacitive energy storage (graphene) and faradaic energy storage in a single material with a dual energy storage mechanism.[6] We will discuss examples of this type of materials and their improved energy storage properties, together with efforts for the integral development of low-cost high-performance electrodes based on sponge macro and microstructures of graphene and oxides.

References [1] [2] [3] [4] [5] [6]

V. Ruiz, J. Suรกrez-Guevara, P. Gomez-Romero Electrochemistry Communications 24 (2012) 35.

J. Suarez-Guevara, V. Ruiz and P. Gomez-Romero J.Mat.Chem.A, 2 (2014) 1014.

J. Suรกrez-Guevara, V. Ruiz and P. Gomez-Romero*, Phys. Chem. Chem. Phys. 16(38), (2014) 20411.

D. P. Dubal*, R. Holze, P. Gomez-Romero*. Scientific Reports (NPG) (2014) 4 : 7349.

D. P. Dubal*, N.R. Chodankar, G. S. Gund, R. Holze, C.D. Lokhande, P. Gomez-Romero* Energy Technology, 3(2), (2015) 168.

D. P. Dubal, O. Ayyad, V. Ruiz, and P. Gomez-Romero* Chemical Society Reviews, 44 (2015) 1777.

77

Figures

Figure 1: Polyoxometalate-rGO hybrid electrodes and their performance in supercapacitors.

78

Detection of Inorganic Molecules on reactive MoS2 defects by ab-initio Atomic Force Microscopy Simulations César González Facultad de Ciencias Universidad de Granada, Granada E-18071, Spain Service de Physique de l'Etat Condensé, SPEC/IRAMIS/CEA, CNRS, Université Paris Saclay, 91191 Gif-Sur-Yvette, France. cesar.gonzalez.pascual@gmail.com

Since graphene was discovered some years ago [1], the interest in two dimensional (2D) materials has grown exponentially. The so-called transition-metal dichalcogenides have recently attracted a great attention due to their promising properties. One of the most studied compounds is the MoS2 due to its potential nanoelectronic, optoelectronic and spintronic applications [2]. Very recently, this material has been proposed as a fundamental part in gas sensors [3]. In those cases, the molecules were weekly bonded by van der Waals (vdW) forces to the poorly reactive MoS2 substrate, changing the electric current measured in the sensor.

In this work, we have performed density functional theory (DFT) simulations based in the VASP code [4] in order to find the most stable structures of small inorganic molecules (such as H2O, NO and CO2) adsorbed on different point defects of the MoS2 monolayer [5]. Our results show that the molecules can be bonded to the Mo atoms in the substitutional defects. In our analysis, the Sulphur divacancy occupied by two Mo atoms has been selected as the most interesting defect. Once the molecules are absorbed over this point, they can be identified using an atomic force microscope (AFM). Following the original idea of chemical identification proposed some years ago [6], each molecule will lead to a different force curve when an AFM tip is approached. In figure 1, the forces of H2O, NO and CO2 molecules are represented. The resulting value and position of the minimum force characterize the kind of molecule that has been scanned by the AFM. Finally, a comparison between a reactive metallic tip and a low reactive Si tip will define the best option for future experimental measurements.

References [1] [2] [3] [4] [5] [6]

J K. S. Novoselov et al., Science, 306 (2004) 666.

B. Radisavljevic et al., Nat. Nanotechnol., 6 (2011) 147; J. Yoon et al., Small, 9 (2013) 3295; Q. H. Wang et al., Nat. Nanotechnol., 7 (2012) 699.

H. Li, et al., Small, 8 (2012) 63; Q. Y. He, et al., Small, 8 (2012) 2994.

G. Kresse and J. Hafner, Phys. Rev. B, 47 (1993) R558.

C. González, B. Biel and Y. J. Dappe, sent to J. Phys. Chem. C. Y. Sugimoto et al., Nature, 446 (2007).

79

Figures

Figure 1: Force curves of a Cu tip contacting to three different molecules adsorbed on a defect formed by the substitution of two S by two Mo atoms in the MoS2 monolayer. The ball and stick models of the contact point (minimum force) are shown: on the left side, a H2O molecule (blue triangles), on the right side a CO2 molecule (red circles) and on the inset a NO molecule (black squares).

80

Industrial Graphene nanoplatelets possibilities Lucía González Bermúdez GrapheneTech, C/ María de Luna, Nave 1, Zaragoza, Spain lgonzalez@graphene-tech.net

GrapheneTech is a dynamic company graphene producer, working day after day to become a world leader in graphene technology adapted to the specific needs of each client.

Graphene manufacture as nanoplates, we specialize in large-scale production for various industrial applications using our patented method that allows us to offer suitable to industrial needs, complex and costly than other methods do not allow prices.

Six years of experience with nanomaterial of high performance are behind us. The multidisciplinary team formed by PhD in chemistry and physics of our firm has a R&D extensive experience and share with the clients the vision to develop our services with accurate communication, consistent and direct.

Graphene nanoplatelets are mainly obtained by two kinds of production: Chemical exfoliation leads to graphene oxide (GO) with very poor electrical conductivity, which, if further reduced to increase conductivity (reduced graphene oxide, rGO), tends to lead graphene defective, not fully reduced and carrying many non-carbon elements from the hazardous chemicals used (as in Hummers o Brodie methods), hence limiting its quality for potential industrial uses. In contrast, mechanical exfoliation protocols use shear forces to separate graphene stacks in graphite and are currently producing nonoxidised graphene nanoplatalets (GNPs) with a broad range of quality, number of layers, conductivity, surface area and mechanical performance depending on the success degree of exfoliation. As a result mechanical exfoliation appears to be the most promising route for the mass manufacturing of high quality bulk graphene.

Industrial applications for Graphene nanoplatelets are mainly based on composites, however is needed to modify the graphene, specially graphene oxide, for the final application; via reduction, [1] dopping [2] with others metal or atoms, functionalizasing [3] with aliphatic chains or molecules… Then, is it a real final application?

References [1]

[2]

a) Shao, Y., Wang, J., Engelhard, M., Wang, C., & Lin, Y. (2010). Facile and controllable electrochemical reduction of graphene oxide and its applications.Journal of Materials Chemistry, 20(4), 743-748. b) Chen, L., Tang, Y., Wang, K., Liu, C., & Luo, S. (2011). Direct electrodeposition of reduced graphene oxide on glassy carbon electrode and its electrochemical application. Electrochemistry Communications, 13(2), 133-137. a) Wang, Y., Shao, Y., Matson, D. W., Li, J., & Lin, Y. (2010). Nitrogen-doped graphene and its application in electrochemical biosensing. ACS nano, 4(4), 1790-1798. b) Wang, H., Maiyalagan, T., & Wang, X. (2012). Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. Acs Catalysis, 2(5), 781-794. c) Zhang, C., Mahmood, N., Yin, H., Liu, F., & Hou, Y. (2013). Synthesis of phosphorus-doped graphene and its multifunctional applications for oxygen reduction reaction and lithium ion batteries.

Advanced Materials, 25(35), 4932-4937.

81

[3]

82

a) Xu, Y., Bai, H., Lu, G., Li, C., & Shi, G. (2008). Flexible graphene films via the filtration of watersoluble noncovalent functionalized graphene sheets. Journal of the American Chemical Society, 130(18), 5856-5857. b) Chen, D., Feng, H., & Li, J. (2012). Graphene oxide: preparation, functionalization, and electrochemical applications. Chemical reviews, 112(11), 6027-6053. c) Kuila, T., Bose, S., Mishra, A. K., Khanra, P., Kim, N. H., & Lee, J. H. (2012). Chemical functionalization of graphene and its applications. Progress in Materials Science, 57(7), 10611105.

3+

3+

Tunable size Ln:BaGdF5 (Ln= Eu and Nd ) nanoparticles.

Luminescence, magnetic properties, and biocompatibility D. González Mancebo1, E. Cantelar2, F. Cussó2, G. Stepien3, J.M. de la Fuente4, M. Ocaña1 and A.I. Becerro1 1

Instituto de Ciencia de Materiales de Sevilla (CSIC-US). c/ Américo Vespucio, 49, 41092 Seville (Spain).

2 Dpto. Física de Materiales, C-04. Universidad Autónoma de Madrid, 28049 Madrid (Spain).

Instituto de Nanociencia de Aragón, Univ. Zaragoza. c/ Mariano Esquilor s/n. 50018 Zaragoza (Spain).

4 Instituto de Ciencia de Materiales de Aragón, (CSIC/UniZar), C/ Pedro Cerbuna, 12. 50009 Zaragoza (Spain) anieto@icmse.csic.es 3

Lanthanide-doped rare earth fluoride nanoparticles (NPs) have become a research focus in the last few years in the biomedical field because of their interesting luminescent properties which confer to them important applications as biosensors and optical bioprobes. [1,2] In comparison with oxygen-based systems, fluorides possess very low vibrational energies, which helps to improve their luminescence emission. [3] Among the fluoride systems, the Ln:BaGdF5 compositions (Ln= optically active lanthanide ion) shows, apart from their excellent luminescent properties, interesting added advantages due to the properties of both, Ba2+ and Gd3+ ions. The former show a large k-edge value as well as high X-ray mass absorption coefficients, which allows Ba-based NPs to be optimal contrast agents for X-ray computed tomography (CT). [4] On the other hand, Gd3+ ions show a large magnetic moment and nanoseconds electronic relaxation time, which makes Gd-based NPs very useful contrast agents for magnetic resonance imaging (MRI). [5,6] Most of the synthesis methods reported up to now to obtain BaGdF5 particles led either to uniform >100 nm particles [7,8] or to smaller NPs (12 – 75 nm) with illdefined morphology or poorly dispersed. [9,10] Only the use of oleic acid as capping agent led to monodispersed BaGdF5 nanospheres (3 to 10 nm). [11] The latter method required, however, the use of very high temperatures (300 oC) and rendered hydrophobic NPs, which needed then to be acid treated to remove the oleate ligands to obtain hydrophilic NPs suitable for bioapplications.

Herein, we report the synthesis of bifunctional and highly uniform Eu:BaGdF5 and Nd:BaGdF5 NPs using a solvothermal method consisting in the aging at 120 °C of a glycerol solution containing Ln (Gd, Eu and Nd) acetylacetonates (acac) as the Ln source, Ba(NO3)2 as the Ba source, and the ionic liquid butylmethylimidazolium tetrafluoroborate ([BMIM]BF4) as the source of fluoride anions. Both the acac and the ionic liquid allowed the controlled release of ions into the solution thus allowing the precipitation of uniform, spherical NPs, without the need of a capping agent. The NP diameter could be tuned from 45 nm to 85 nm, depending on the cations concentration of the starting solution (Fig. 1). The obtained NPs showed a hydrophilic surface due to the absence of surfactants or oleic acid in the reaction medium. The NPs were bifunctional because they showed both optical and magnetic properties. The optical properties were due to the doping ions Eu3+ and Nd3+ which were selected here for the following reasons: The luminescence of Eu3+ is located in the red region of the electromagnetic spectrum, where the autofluorescence of tissues is minimal, while Nd3+ is excited and emits within the second biological window (1000-1400 nm), in which the radiation is only weakly attenuated by tissues thus improving the sensitivity of the assays. The luminescence decay curves of the nanospheres doped with different amounts of Eu3+ and Nd3+ were recorded in order to determine the optimum dopant concentration in each case, which resulted to be 5% Eu3+ and 0.5% Nd3+ (Fig. 2). On the other hand, the presence of the paramagnetic gadolinium ion conferred the NPS with interesting magnetic properties. In this sense, proton relaxation times were measured at 1.5 T in water suspensions of the optimum particles found in the luminescence study. Both NPs types (5%Eu:BaGdF5 and 0.5%Nd:BaGdF5) exhibited r2/r1 values lower than 5, which suggest that they could be used as positive contrast agents for MRI. Finally, it was demonstrated that both

83

the 5% Eu3+ and 0.5% Nd3+-doped BaGdF5 NPs showed negligible cytotoxicity for VERO cells for concentrations up to 0.25 mg mL-1 (Fig. 3).

References [1] [2] [3]

Chatterjee, D. K.; Gnanasammandhan, M. K.; Zhang, Y., Small 6 (2010) 2781.

Naccache, R.; Yu, Q.; Capobianco, J. A., Adv. Opt. Mater. 3 (2015) 482.

Renero-Lecuna, C.; Martín-Rodríguez, R.; Valiente, R.; González, J.; Rodríguez, F.; Kramer, K. W.; Gudel, H. U., Chem. Mater. 23 (2011) 3442.

[4] Lusic, H.; Grinstaff, M.W. Chem. Rev. 113 (2013) 1641.

[5] Yang, L.W.; Zhang, Y. Y.; Li, J. J.; Li, Y.; Zhong, J. X.; Chu, P. K., Nanoscale 2 (2010) 2805.

[6] Naccache, R.; Chevallier, P.; Lagueux, J.; Gossuin, Y.; Laurent, S.; Vander Elst, L.; Chilian, C.;Capobianco, J. A.; Fortin, M. A. Adv. Healthcare Mater. 2 (2013) 1478.

[7] Yang, D.; Kang, X.; Shang, M.; Li, G.; Peng, C.; Li, C.; Lin, L., Nanoscale 3 (2011) 2589.

[8] Zhao, Q.; Lei, Z.; Huang, S.; Han, X.; Shao, B.; Lü, W.; Jia, Y.; Lv, W.; Jiao, M.; Wang, Z.; You, H., ACS Appl. Mater. Interfaces 6 (2014) 12761.

[9] Zhang, C.; Wang, J.; Song, C.; Shang, Y.; Shen, S., Mater. Letters 118 (2014) 88.

[10] Zeng, S.; Tsang, M.; Chan, C.; Wong, K.; Hao, J. Biomaterials 33 (2012) 9232.

[11] Sarkar, S.; Hazra, C.; Mahalingam, V., Dalton Trans. 42 (2013) 63.

Figures

84 Figure 1: Left: TEM micrograph showing uniform spherical (~45 nm diameter) NPs. Right: Exponential decay of the average diameter of the particles with increasing Gd3+ and Ba2+ concentrations.

Figure 2: Evolution of the average lifetimes, recorded at the dominant emission of Nd3+ and Eu3+, with the ion contents.

Figure 3: Evolution Cytotoxicity profiles of 5% Eu3+ and 0.5%Nd3+-doped BaGdF5 NPs (top and bottom, respectively) with Vero cells, determined by MTT assay. Percentage of viability of cells was expressed relative to control cells (n = 5).

Results are represented as mean ± standard deviations.

CO2-based-surfactant-free microemulsions-like system as futurist universal green medium for chemical processes N. Grimaldi1, P.E. Rojas2, J.J. Schuster3, S. Salad2, A. Cordob1, J. Veciana2,4, J. Faraudo2 , A. Triolo5, A. Braeuer3 , N. Ventosa2,4 1

Nanomol Technologies SA, Módul de Recerca B, Campus Universitari de Bellaterra, 08193 Cerdanyola del Vallès, Spain.

Ins. de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus Univ. de Bellaterra, 08193 Cerdanyola del Vallès, Spain.

LTT and SAOT Friedrich-Alexander Universitaet Erlangen-Nuernberg, Paul-Gordan-Strasse 6, 91052 Erlangen, Germany.

4 CIBER-BBN: Campus Río Ebro - Edificio I+D Bloque 5, 1a planta C/ Poeta Mariano Esquillor s/n, 50018 Zaragoza, Spain.

5 Laboratorio Liquidi Ionici, Istituto Struttura della Materia, Consiglio Nazionale delle Ricerche, 00133 Rome, Italy ngrimaldi@icmab.es

2

3

Microemulsions are thermodynamically stable systems consisting of a ternary mixture of oil, water and a surfactant. They are macroscopically homogeneous, but microscopically structured. As they contain both, a polar and a nonpolar solvent, microemulsions can be considered as universal solvents and they have been extensively used either as commercial products or as reaction media for chemical processes. [1] Unfortunately, the purification of the products both from the organic solvent and from the surfactant is time and chemicals consuming. Minimizing the amount of surfactant and organic solvent used for preparing microemulsions is now on demand. [2] In our laboratories, the existence of “waterrich” nanodomains in equilibrium with “water-lean” nanodomains in the macroscopically homogeneous ternary mixture water/acetone/liquid CO2 has been observed. These nanodomains have also shown the solvent capability of a microemulsion, solubilizing either hydrophilic or hydrophobic molecules. [3] The fine supramolecular structure of this new surfactant-free microemulsion like systems has been determined through a combination of Raman Spectroscopy and SANS measurements. Molecular dynamics simulations studies have also supported the experimental findings, clarifying the interactions among the components.

It has been found that the composition as well as the working conditions (temperature and pressure) can be used as tools for tuning the fine structure of such microemulsions. Furthermore, other solvents in presence of water and compressed CO2 have shown a similar behavior to that of acetone, extending the range of applications of such systems. The systems here presented have the potential of behaving as nanoreactors for particles formation and becoming green universal solvent for chemical processes, showing the solvation properties of both bulk water and organic solvents and the attractive pressure tunable characteristics of compressed CO2, without the recourse to surfactants.

References [1] [2] [3]

Microemulsions: Background, New Concepts, Applications, Perspectives, ed. C. Stubenrauch, Wiley, 2009.

M. L. Klossek, D. Touraud, T. Zemb and W. Kunz, ChemPhysChem, 2012, 13, 4116.

R. F. Hankel, P. E. Rojas, M. Cano-Sarabia, S. Sala, J. Veciana, A. Braeuer, N. Ventosa, Chem.

Commun. 2014, 50, 8215.

85

Facile and inexpensive biocatalytic method for resizing of semiconductor cadmium sulfide nanoparticles Ruta Grinyte*, L. Saa, G. Garai-Ibabe and V. Pavlov Biofunctional Nanomaterials Unit, CIC BiomaGUNE, Parque Tecnolรณgico de San Sebastiรกn, Paseo Miramรณn 182, DonostiaSan Sebastiรกn, 20009 Spain rgrinyte@cicbiomagune.es

Chemical and physical properties of semiconductor nanoparticles (NPs) or quantum dots (QDs) are defined by three dimensional structure of NPs, therefore very slight changes in shape and size lead to drastic variation in absorption and emission spectra. [1] Further post-processing for resizing and tailoring of already prepared semiconductor NPs is often necessary. Etching technology is considered to be a particularly important process to resize semiconductor NPs and to tune their luminescence properties. We report for the first time that semiconductor CdS NPs treated with HRP in the present of different concentrations of H2O2 gradually decreased in size (Scheme 1). [2] It was proved by the blue-shift of emission peak, decrease in the intensity of the in fluorescence and by transmission electron microscopy images.

86

This phenomenon was also applied for the first time to monitor photoluminescence during etching of CdS NPs in real time. For this experiment CdS NPs where immobilized on the surface of microbeads and after adding all components fluorescence was measured. In order to take images of CdS NPs during etching wide field fluorescence microscopy was used.

The present approach discovered by us could find a broad range of applications in analytical chemistry and open up a new path for enzymatic modification and modulation of bioelectronic devices based on semiconductor NPs. References [1] [2]

Parak, W. J.; Manna, L.; Simmel, F. C.; Gerion, D.; Alivisatos, P. In Nanoparticles; Wiley-VCH Verlag GmbH & Co. KGaA, (2005) 4-49.

R. Grinyte, L. Saa, G. Garai-Ibabe, V. Pavlov. Chem. Commun., Chem. Commun., 2015, 51, 17152-17155.

Figures

Figure 1: Enzymatic etching of CdS NPs.

Bio-based polyamide/carbon nanotube nanocomposites Itziar Otaegi*, Gonzalo Guerrica-Echevarría and José Ignacio Eguiazábal Department of Polymer Science and Technology and POLYMAT Faculty of Chemistry, University of the Basque Country UPV/EHU Paseo Manuel de Lardizabal 3, 20018, Donostia (Spain) itziar.otaegi@ehu.eus

Polyamides (PA) are engineering polymers with very good thermo-mechanical properties, widely used, among others, in electric, electronic and automotive applications. Most commercial polyamides are produced by polycondensation of diamines and dicarboxylic acids. Diamines are mainly derived from fossil fuel, but dicarboxylic acids can be obtained from renewable resources such as castor oil (1), producing a bio-based polyamide. Currently available commercial bio-based polyamides include PA1010, PA410 and PA610 Polyamide/carbon nanotube nanocomposites (PA/CNT) have been widely studied (2). One of the most important benefits of CNT addition to polymeric matrixes is the possibility to obtain electrically conductive materials (3). Conductivity is achieved when a three-dimensional network of interconnected nanotubes is formed within the matrix. This occurs upon reaching the named electrical percolation concentration (pc).

Moreover, it is well known that incorporation of CNTs improves mechanical properties of polymeric materials. PA/CNT nanocomposites show enhanced mechanical and conductive properties with respect to the pure matrix, with percolation concentrations varying between 0.4-4 wt. % CNT (4, 5).

Materials and methods The bio-based polymeric matrix was a polyamide 410 provided by DSM. Its properties are comparable to those of conventional technical polyamides such as PA6 or PA66, but as it is based on dicarboxylic acids derived from castor oil (that constitutes some 70% of the polyamide), its carbon footprint is reduced in almost 100% with respect to its competitors. Multi-walled carbon nanotubes (MWCNT), with an outside diameter of 20-30 nm and purity higher than 95%, were provided by Cheaptubes. In an attempt to improve the dispersion of the nanotubes and, consequently, reduce the percolation concentration achieved when the pristine nanotubes were directly added to the PA410, a PA6/MWCNT masterbatch containing 15 wt. % of MWCNT (Plasticyl® PA 1503, provided by Nanocyl) was also used.

PA410/MWCNT nanocomposites containing from 1 to 6 wt. % of MWCNT were prepared by melt-mixing in a twin-screw extruder at 270ºC and a screw speed of 200 rpm. Alternatively, PA6/MWCNT masterbatch containing 15 wt. % of MWCNT was diluted with PA410 to obtain nanotube contents of 1-4 wt. %. Thus, PA410/PA6/MWCNT nanocomposites were also prepared by melt-mixing at the same processing conditions of PA410/MWCNT nanocomposites. Standard test specimens for tensile tests were obtained by injection molding, and compression molding was used to generate standard sheets for electrical conductivity measurements. The mechanical properties of the nanocomposites were measured by tensile tests. The nanostructure of the composites was analyzed by transmission electron microscopy (TEM), whilst a multimeter and a picoammeter were used to perform the electrical conductivity measurements.

Results and discussion The Young’s moduli of the PA410/MWCNT and PA410/PA6/MWCNT nanocomposites are shown in Figure 1. As can be observed, the addition of the nanofillers caused, in both cases, an increase in the Young’s modulus. However, the increase raised up to 4.6% in the case of 5% nanofiller loading for PA410/MWCNT

87

nanocomposites, and to 9.4% in the case of 4% nanofiller loading for PA410/PA6/MWCNT nanocomposites, with respect to the pure matrix.

The electrical conductivity of PA410/MWCNT and PA410/PA6/MWCNT nanocomposites is shown in Figure 2. As can be seen, in PA410/MWCNT nanocomposites, conductivity increased with MWCNT content leading to an electrical percolation threshold between 3 and 5 wt. %. The percolation concentration decreases significantly in PA410/PA6/MWCNT nanocomposites, which falls between 0 and 1 wt. % due to the use of the masterbatch. Moreover, in this case, the conductivity values obtained are higher â&#x20AC;&#x201C;3 orders of magnitudeâ&#x20AC;&#x201C; than in the first approach. The calculated value for the electrical percolation threshold for PA410/MWCNT nanocomposites was 3.98 wt. %, whereas for PA410/PA6/MWCNT nanocomposites it was 0.65 wt. %. TEM micrographs of PA410/MWCNT and PA410/PA6/MWCNT containing 4 and 1 wt. % of MWCNTs, respectively, which correspond to the concentrations closest to the percolation concentration in each case, are shown in Figure 3. As can be observed, PA410/PA6/MWCNT nanocomposites show a much better dispersion level of MWCNTs, with carbon nanotubes appearing very finely dispersed within the matrix. This fact is directly related to the better mechanical properties, as well as the lower percolation concentration, observed in the case of the ternary nanocomposites.

Conclusions Bio-based polymeric nanocomposites have been obtained with enhanced electrical conductivity and rigidity by the addition of MWCNTs to a polyamide 410. A significant reduction in the percolation concentration, together with better mechanical properties, was achieved by using a PA6/MWCNT masterbatch. Further work is still needed to improve the deformation and impact properties by, for instance, adding an impact modifier

88

References [1] [2] [3] [4] [5] [6]

M. Niaounakis. Biopolymers: Reuse, Recycling, and Disposal, Elsevier, 2013, 1-75.

H. Meng, G.X. Sui, P.F. Fang, R. Yang. Polymer, 2008, 49(2), 610-620.

I. Alig, P. Poetschke, D. Lellinger, T. Skipa, S. Pegel, G.R. Kasaliwal, T. Villmow. Polymer, 2012, 53(1), 4-28.

G. Gorrasi, S. Bredeau, C. Di Candia, G. Patimo, S. De Pasquale, P. Dubois. Macromolecular Materials and Engineering, 2011, 296(5), 408-413.

O. Meincke, D. Kaempfer, H. Weickmann, C. Friedrich, M. Vathauer, H. Warth. Polymer, 2004, 45(3), 739-748.

M. Weber, M. R. Kamal. Polymer Composites, 1997, 18(6), 711-725.

Figures

Figure 1: Young’s nanocomposites (○) nanocomposites (●).

modulus and of

of PA410/MWCNT PA410/PA6/MWCNT

Figure 2: Electrical conductivity of PA410/MWCNT nanocomposites (○) and of PA410/PA6/MWCNT nanocomposites (●).

89

Figure 3: TEM micrographs of PA410/MWCNT nanocomposite containing 4 wt. % of MWCNTs (on the left) and of PA410/PA6/MWCNT nanocomposite containing 1 wt. % of MWCNTs (on the right) (x25000).

Patentometric Study of Nanotechnology in Spain Björn Jürgens1, Victor Herrero-Solana 1

CITPIA Patent Information Centre, Agency of Innovation and Development of Andalusia, Seville, Spain 2 SCImago-UGR (SEJ036) Universidad de Granada, Granada, Spain bjurgens@agenciaidea.es;victorhs@ugr.es

In this work, which is based on a PhD thesis [1] in the framework of a funded project [2], a patentometric study of Spanish nanotechnology is done for the years 2004 to 2014. Based on an adapted search query [3] and the use of the patent database Espacenet as the one with the best data coverage for the purpose [4] more than 3400 nanotechnology related patent records were retrieved that had Spanish authorship. After an exhaustive data harmonization process subsequently a detailed analysis was performed using the patent statistics software tool Matheo Patent.

First, Spanish patenting in Nanotechnology was compared to worldwide patenting and publishing. We could identify two types of countries. On the one hand we detected a group comprising the United States, Japan and South Korea where the production of patents is relatively higher than the scientific production.

On the other hand we identified a group with the opposite behavior, which includes especially China and to a lesser extent the UK and Spain.

90

Spain intervenes at 1% of the patents on nanotechnology in the world, but has more than double the representation for scientific papers. There is no doubt that the country has made great efforts to strengthen the scientific field, but it has an emphasis on the public and academic sector. The initiative of private enterprises has not had the same luck in recent years.

Regarding the Spanish Nanotechnology thematic profile we compared it with worldwide patenting and could identify an above average patenting in the field of nano-medicine and nano-biotechnology. On the contrary we found a deficit in patents related to nano-optics, nano-magnetism and nanotechnologies related to information and communication technologies (ICT). In the field of materials science related to nanocomposites, production is equivalent in relative terms to the rest of the world.

Regarding the nanotechnology patenting output of Spain the temporal evolution has found to be steady for several years and the most productive provinces were Barcelona, Madrid, Valencia, Sevilla and La Coruña. If we analyze the patent output according to its applicant’s sector affiliation the universities are prevalent (37%), followed by private enterprises (24%), the CSIC (20%) and other research centres (16%).

From the academic world we can point out the Universidad de Sevilla and the Universidade de Santiago de Compostela, followed by the Universitat Polytechnic of Valencia. Among the CSIC stands out in both, its production of patents and papers, the Instituto de Ciencia de Materiales de Madrid. The only two companies which appear in the ranking are Advancell and Nanobiomatters.

In order to measure the effort of internationalization we describe an indicator, which is a ratio between the number of patent registrations (in different offices) and patent families (the invention or innovation itself) and can be used to measure the value of patents. When we analyze the rate of internationalization in Spain, we find that the highest values are presented by the companies, whose business model is based on the protection of such innovations and therefore are willing to such an effort. Some universities appear to have higher capacity of internationalization than the CSIC centres.

The institutions which really stand out are the Universidad de Sevilla and the Universidade de Santiago de Compostela. Both have such a positive productive behaviour that a further study of their technology transfer offices (TTO) would be of interest.

Finally, by analyzing the co-authoring and co-applicant behaviour of Spanish Nanotechnology patents, we could reveal collaboration patterns of institutions and researchers which are visualized via network maps (example in figure 1). Furthermore by analyzing the patent classifications we could define thematically the relationships of the most important patent applicants (example in figure 2).

References [1] [2]

[3] [4]

Jürgens, B. (2016). Nanotechnology in Spain: technology watch by patents (Unpublished doctoral dissertation). University of Granada.

Framework project “Vigilancia tecnológica de la nanotecnología Española a través de sus patentes”, grant by Spanish Ministry of Science and Economy (Plan Nacional de I&D&i 20082011, project code: CSO2012-38801).

Maghrebi, M., Abbasi, A., Amiri, S., Monsefi, R., & Harati, A. (2010). A collective and abridged lexical query for delineation of nanotechnology publications. Scientometrics, 86(1), 15-25.

Jürgens, B., Herrero-Solana,V. (2015). Espacenet, Patentscope and Depatisnet: A comparison approach. World Patent Information. Vol. 42. doi:10.1016/j.wpi.2015.05.004.

Figures

91

Figure 1: Applicant collaboration network from Universidad del Pais Vasco.

Figure 2: Inventor-Technology (left) and Inventor-Applicant (right) networks of Jose Maria Lagaron Cabello.

Nanoimaging and manipulation of polaritons in graphene and boron nitride Rainer Hillenbrand CIC nanoGUNE and IKERBASQUE. San Sebastian, Spain r.hillenbrand@nanogune.eu

A promising solution for active control of light on the nanometer scale are plasmons in graphene, which offer ultra-short wavelengths, long lifetimes, strong field confinement, and tuning possibilities by electrical gating. Here, we apply scattering-type scanning near-field optical microscopy (s-SNOM) for real-space imaging of plasmons [1-3] in tailored disk and rectangular graphene nanoresonators [4] at mid-infrared frequencies. The near-field images exhibit intriguing patterns and features, indicating the interference of manifold plasmon excitations. A simple model well reproduces the two-dimensional experimental patterns, allowing us for identifying edge and sheet modes, as well as for separating them either spatially or in energy. We anticipate that real-space analysis of graphene plasmons could be of great benefit for the development and quality control of emerging graphene plasmonic technologies, particularly when novel design concepts and 2D material heterostructures have to be tested and verified. As another application of s-SNOM we discuss its combination with time-domain interferometry, which allowed for visualizing in time and space the propagation of hyperbolic phonon polaritons in boron nitride slabs, revealing negative phase velocity and group velocities as small as 0.002c [5].

References

92

[1] [2] [3] [4] [5]

J. Chen, et al., Nature 487, 77 (2012).

Z. Fei, et al., Nature 487, 82 (2012).

P. Alonso-Gonzรกlez, et al., Science 344, 1369 (2014).

A.Y. Nikitin, et al., submitted.

E. Yoxall, Nat. Photon. 9, 674 (2015).

Figures

Figure 1: Near-field imaging of plasmonic graphene disk resonators.

Nanomedicine, from PoC to reality: the importance of an industrial perspective and GMP scale up O. Ibarrola, A. del Pozo, E. Gainza BioPraxis AIE, Hermanos Lumière 5, 01510 Miñano, Spain oibarrola@praxisph.com

Nanotechnology and specially its application to improvement of Human health (Nanomedicine) is expected to be one of the pillars of novel products and processes in the next future, in this case to get innovative therapies. Nano-enabled therapies , together with cell and gene therapies and personalized medicine will pave the way for a revolution in the treatment of several diseases which currently have no treatment or low efficacy ones. There is a common consensus on the potential of nanomedicine to contribute to this global improvement, but this will only be possible if all the nano medicine community is able to foster the translation of the promising results obtained at laboratory scale to real products applicable at clinical settings. This full deployment of nanomedicine must be based on the identification of the existent gaps for translation, at different levels, and on the industrialization of nanomedicines production, taking into account Good Manufacture Practices (GMP) and regulatory aspects.

From Biopraxis, the Research and Innovation Unit of the pharmaceutical Group Praxis, we have developed an intensive work to identify and propose solutions for many of those gaps. In the current moment Biopraxis holds the Chairmanship of the Nanotherapeutics Working Group in the European Technology Platform for Nanomedicine, making us a privileged stakeholder to receive inputs from the nanomedicine community and to highlight our contributions to the translation of nanomedicines. In this communication, we aim to share all these lessons learned when trying to move nanomedicine to the next steps. To do this, we have identified and proposed solutions to the different challenges at different levels, and, due to our industrial commitment, with a special focus in GMP up scale of nanomedicines production. Main challenges are the following: -

-

-

-

Society: There is a need of higher acknowledgment and support for nanomedicine, avoiding a potential “nano-fobia”.

Risks: We identify risks at two main levels: safety and environment impact, and propose preventive and corrective actions.

Regulation: medicines market is a highly regulated market, and there is a need for the definition of the regulatory requirements for nanomedicines. We set the problem at three different levels: Preclinical development, clinical research and market access.

Technology implementation: There is a huge amount of technology offers, which has to be discerned by industry. An open innovation scheme is proposed as a potential solution to this challenge.

Industrialization: Biopraxis is specialized scaling up the manufacturing of diferent nanoformulations from milligram-scale laboratory synthesis up to multigram-scale production to generate sufficient material for clinical and regulatory assays. We standardise the up-scale production of nanoparticles under GMP (Fig 1) considering the main bottleneck aspects: reproducibility, stability, and non-immunogenicity (sterility and non-pyrogenicity). At the same time, we consider critical aspects of the GMPs design such as: continuous quality control, risk assessment for manufacturing process, specifications for excipients, intermediates and finished products; rooms classification, equipment, supplies (water, heat, stirring, gases…).

Business models: New paradigms need also innovative approaches to business models.

93

As it has been shown, current landscape for nanomedicines is full of potential, but presents a series of challenges, which need to be solved, and in many cases, only the commitment and driving action of the industry can bridge this potential valley of death. At Biopraxis we are managing several projects for the development of nanomedicines, and we want to share our experiences and potential answers to contribute to nano-enabled therapies in the next future, in a context with the view from the Industry is sometimes difficult to find. Nanomedicines still present some weakness on this sense, i.e. detailed cost evaluations.

Figures

94 Figure 1: Figure illustrating the production of nanoparticles under GMP.

Scalability of the graphene/semiconductor barristor targeting digital applications Ferney Chaves, David Jiménez Departament d’Enginyeria Electrònica, Escola d’Enginyeria, Universitat Autònoma de Barcelona, Carrer de les Sitges s/n, 08193 Bellaterra, Spain david.jimenez@uab.es

We have investigated the electrostatics and current-voltage characteristics of the graphene/semiconductor barristor [1] (see Fig. 1) considering effects of Fermi-level pinning (FLP) arising by possible presence of surface states, similarly to the metal-semiconductor junction [2]. Our study suggests that the barristor is a graphene logic device achieving high on/off current ratio, potentially of great interest for switching applications. When FLP dominates, the barristor's electrostatics the gate electrode cannot modulate the Schottky barrier height (SBH) and rectification could be totally lost [3]. On the other hand, our model has revealed that the Barristor exhibits changes of the threshold voltage by the sourcedrain voltage, similar to the Drain Inducend Barrier Lowering in conventional short channel MOSFETs. It turns out that the barristor has to be biased at low Vds to get a sufficient ON-OFF current ratio. As a final note, we have investigated the impact that a non-ideal interface might have in the barristor operation, and we have pointed out the role of oxide thickness scaling could have to get appropiate digital performance (Fig. 2).

References [1] [2] [3]

H. Yang, J. Heo, S. Park, H. J. Song, D. H. Seo, K.-E. Byun, P. Kim, I. Yoo, H.-J. Chung,K. Kim, Science 336, (2012) 1140.

S. M. Sze, K. N. Kwok, Physics of Semiconductor Devices, John Wiley and Sons, 2006.

W. Kim, C. Li, F. A. Chaves, D. Jiménez, R. D. Rodriguez, J. Susoma, M. A. Fenner, H. Lipsanen, J. Riikonen, Adv. Mat., DOI: 10.1002/adma.201504514 (2015).

Figures

Figure 1: (a) Skecht of the barristor device, (b) Figures of merit of the barristor for different oxide thickness as a function of defects concentration at the graphene/semiconductor interface.

95

Enhanced delivery of Paclitaxel using PLGA nanoparticles: therapeutic effect in lung cancer cell cultures Julia Jiménez-Lopez1,2, Laura Cabeza1,2, Mazen El-Hammadi3, Maria Carmen Leiva1,2, Gloria Perazzoli1,2, Lucia Martín-Balderas3, Raul Ortiz4, Consolación Melguizo1,2, Jose Prados1,2 1

Institute of Biopathology and Regenerative Medicine (IBIMER), 18100 Granada, Spain; Biosanitary Institute of Granada (ibs.GRANADA), SAS-Universidad de Granada, Granada, Spain; 3 Department of Pharmacy and Pharmaceutical Technology, University of Sevilla, 41012 Sevilla, Spain; 4 Department of Health Science, University of Jaén, 23071 Jaén, Spain jcprados@ugr.es 2

96

Lung cancer is the main cause of death by cancer worldwide. Paclitaxel (PTX), an antimitotic drug which causes the kidnapping of the cell in the G2 phase of the cell cycle, is widely administered with carboplatin or cisplatin for the treatment of choice for this type of cancer and other solid tumours. However, PTX has many limitations such as the small amount of drug that reach the site of action, poor stability or low solubility and produces many undesirable effects like neutropenia, neurotoxicity or hypersensitivity reactions. These limitations require the development of new delivery systems to encapsulate PTX. In this study, proliferation assays were performed with two human lung tumor cell lines (A549 and NCI-H460) and a human non-tumor cell line (L132), comparing the antiproliferative efficacy of PTX-loaded PLGA nanoparticles (NPs) and the free drug. The results obtained in proliferation assays showed significant dose reduction IC50 with NP-PTX up to 3.63 and 3.79 times lower in A549 and NCI-H460, and 2.96 times lower in L132, compared to free PTX. Moreover, important accumulations in G2 phase were observed in cell cycle assays in all cell lines treated with PTX-loaded PLGA NPs. Also, intracellular uptake studies with Nile red (NR) and NR-loaded NPs by fluorescence microscopy showed that NPs improved the incorporation of NR inside the cells at different incubation times. Finally, the MCTS assays showed a significant reduction in the volume of spheroids when these were treated with free PTX (46%) and NP-PTX (73%). No significant difference was observed between MCTS untreated and treated with blank NPs. In short, PLGA NPs provide a potential strategy as a mechanism for PTX encapsulation and could allow increasing the therapeutic index of this drug.

References [1] [2] [3] [4]

Babu, A., Templeton, A. K., Munshi, A., & Ramesh, R., Journal of Nanomaterials, 2013 (2013) 1– 11.

Gelderblom, H., Verweij, J., Nooter, K., & Sparreboom, A. European Journal of Cancer, 37 (2001) 1590–1598.

Ma, P., & Mumper, R. J., Journal of Nanomedicine & Nanotechnology, 02 (2013) 1-16.

Sadat Tabatabaei Mirakabad, F., et al, Asian Pacific Journal of Cancer Prevention, 15 (2014) 517–535.

Figures

97

Figure 1: 1. Proliferation assays in A549 (A), NCI-H460 (B) and L132 (C) cell lines. 2. Cell cycle assays in A549 (A) and L132 (B) cell lines. 3. Intracellular uptake with RN and NP-loaded RN in A549 cells. 4. Analysis of the NP-PTX effect in MCTs of A549 cells.

Characterization of polymer based nanopharmaceuticals by Asymmetrical Flow Field Flow Fractionation Marlene Klein1, Damien Plaa1, Christine Gleyzes1, Fabienne Seby1 Jose Crecente-Campo2, Desirée Teijeiro-Osorio2, Maria José Alonso2, Mathieu Menta1 1

ADERA-UT2A, Technopole Helioparc, 2 avenue du Président Angot 64053 PAU Cedex 9, France Center for Research in Molecular Medicine & Chronic Diseases (CIMUS), Universidade de Santiago de Compostela, Santiago de Compostela, Spain marlene.klein@univ-pau.fr

2

The rapid development of nanotechnologies strongly impacts advancement of the pharmaceutical industry. Polymeric particles have been extensively studied in the field of drug delivery. In order to be effective as drug delivery systems, nanoparticles (NPs) must have some specific features since their physical properties such as size, shape and optical properties strongly influence their therapeutical action [1]. The European Commission recommends the development of analytical methods for the quality control and characterization of NPs to avoid limitation of the implementation of nanotechnology to the real application. Since the definition of “size” (e.g. geometrical, hydrodynamic or optical radius) is methoddependent, the development of only one analytical technique to fully characterize complex NPs samples is not sufficient. Thus, it is often better to compare results obtained by different techniques even if data interpretation is not always easy.

98

In that objective, we develop different approaches to characterize nanopharmaceuticals based on different principles: DLS (Dynamic Light Scattering) for hydrodynamic diameter determination and A4F (Asymmetrical Flow Field Flow Fractionation) hyphenated to UV (Ultraviolet-Visible), MALLS (Multi-Angle Laser Light Scattering) and RI (Refractometer) detectors. Contrary to DLS, A4F-UV-MALLS-RI is not limited by disperse samples and provides a wide number of information but it requires a high level of analytical development and expertise. A4F is a device based on size separation and allows separation and isolation of NPs while maintaining native conditions for further characterization when associated with online or offline detectors. It offers the possibility to analyze a wide variety of macromolecules and particles ranging from the nanometer to the micrometer with a high resolution [2]. MALLS hyphenated with RI and UV as concentration detectors can give information about the molar mass, polydispersity, gyration radius, size distribution, conformation, PEGylation degree and encapsulation efficiency of NPs. As a partner of NanoPilot H2020 European project, UT2A is responsible of the characterization of three different nanopharmaceuticals produced in the frame of this project. A4F-UV-MALLS-RI is used for the characterization of materials thoughout the synthesis process of nanopharmaceutical, from the control of raw materials to the final product.

First studies were focused on the determination of the molar mass and the polydispersity of raw materials as they are considered critical parameters for the formulation. This step was necessary to validate analytical methodologies and defined the most appropriate raw materials for further synthesis. In process formulation analysis, the presence of NPs with a size around 100nm was found but other compounds that should normally form NPs are also present. Results obtained allow us to propose A4F to control the efficiency and to optimize the process according to GMPs. The research from the NanoPilot project leading to these results has receiving funding from the EU Framework Programme for Research and Innovation HORIZON 2020 under Grant Agreement 646142. The

objective of this four-year long project is to set-up a pilot plant operating under Good Manufacturing Practices (GMPs) for the production of polymer-based nanopharmaceuticals.

References [1] [2]

M.Gaumet, A.Vargas, R.Gurny, F.Delie, European Journal of Pharmaceutics and Biopharmaceutics, 69 (2008) 1-9.

M.Wagner, S. Holzschuh, A. Traeger, A. Fahr, U. S. Schubert, Analytical chemistry, 86 (2014) 5201-5210.

99

Photons, Plasmons and Electrons meet in 2d materials Frank Koppens ICFO-Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, 08860 Castelldefels (Barcelona), Spain ICREA – Institució Catalana de Recerça i Estudis Avancats, Barcelona, Spain.

The optoelectronic response of two-dimensional (2D) crystals, such as graphene and transition metal dichalcogenides (TMDs), is currently subject to intensive investigations. Owing to its gapless character, extraordinary nano-photonic properties and ultrafast carrier dynamics [3], graphene is a promising material for nano-optoelectronics and high-speed photodetectors [4], whereas TMDs have emerged as potential candidates for sensitive photodetection thanks to their enhanced photon absorption [1].

Vertically assembling these crystals in so-called van der Waals heterostructures allows the creation of novel and versatile optoelectronic devices that combine the complementary properties of their constituent materials.

100

Here we present a various new device capabilities, varying from nano-photonic devices to ultrafast and broadband electrical detectors. We applied femtosecond time-resolved photocurrent measurements on 2d material heterostructures, which probes the transit of photoexcited charges across the photoactive TMD layer – and thus current generation – directly in the time domain [2]. In addition, we apply for the first time infrared photocurrent nanoscopy [4] to high-quality graphene devices. We image the plasmonvoltage conversion in real space, where a single graphene sheet serves simultaneously as the plasmonic medium and detector for both infrared and THz frequencies [6,7].

References [1] [2] [3] [4] [5] [6] [7]

Photodetectors based on graphene, other two-dimensional materials and hybrid systems F. H. L. Koppens et al. Nature Nanotechnol. 9, 780-793 (2014).

Picosecond photoresponse in van der Waals heterostructures M. Massicotte et al., Nature Nanotechnology 11 (2016).

Hot-carrier photocurrent effects at graphene–metal interfaces K. J. Tielrooij et al. J. Phys.: Condens. Matter 27, 164207 (2015).

Generation of photovoltage in graphene on a femtosecond timescale through efficient carrier heating K. J. Tielrooij et al., Nature Nanotechnology 10, 437-443 (2015).

Near-field photocurrent nanoscopy on bare and encapsulated graphene A. Woessner, et al., accepted in Nature Communications (2016) arXiv:1508.07864.

Thermoelectric detection of propagating plasmons in graphene M.B. Lundeberg et al., arXiv (2016) arXiv:1601.01977.

Ultra-confined acoustic THz graphene plasmons revealed by photocurrent nanoscopy P. AlonsoGonzález et al., arXiv (2016) arXiv:1601.05753.

Figures

101

Nanoparticles with optimized properties: from chemical synthesis to assembly A bottom-up approach for nanostructured materials Lise-Marie Lacroix1,2, Evangelia Anagnostopoulou1, Christophe Gatel2,3, Raul Arenal2,4 and Guillaume Viau1 1

LPCNO, UMR 5215 INSA-CNRS-UPS, 135 av. de Rangueil, 31077 Toulouse, France Transpyrenean Advanced Laboratory for Electron Microscopy (TALEM), INSA - INA, CNRS - Universidad de Zaragoza, Spain 3 Centre d’Elaboration de Matériaux et d’Etudes Structurales, CEMES-CNRS, 29 rue Jeanne Marvig, B.P. 94347, 31055 Toulouse, France 4 Laboratorio de Microscopias Avanzadas (LMA), Instituto de Nanociencia de Aragon (INA), U. Zaragoza, C/ Mariano Esquillor s/n, 50018 Zaragoza, Spain lmlacroi@insa-toulouse.fr

2

Synthesis of nanoparticles (NPs) exhibiting controlled size and shape has been a long-sought goal in developing various applications ranging from ultra-sensitive sensors to active catalysts.[1] Liquid phase synthesis based on inorganic precursors can lead to peculiar morphologies, far from the shapes thermodynamically favoured. We will present the examples of Pt and Au nanoparticles which can lead to 5 fold stars, porous dendrites or even ultrathin nanowires (Figure 1). [2,3]

102

A fine balance between attractive and repulsive forces lead to the self-assembly of Au nanowires (NWs) directly in solution to form unique expended hexagonal super-lattices, the parameters of which could be tune by modifying the surface chemistry of the objects. Remarkable conductivity properties, such as quantum phenomena at room temperature, were measured on such assemblies thanks to the unique 1D feature of the nanowires. [4] To go further, isolated NWs were trapped by nanoxerography to study the electronic properties of single NW [5], however Rayleigh instability is faced [6].

In a second part of the talk, bottom-up approach, consisting in the synthesis and assembly of particles, will be discussed as a very promising way to get new hard magnetic materials. We have recently demonstrated that rare-earth free permanent magnets could be elaborated using cobalt nanorods, assembled under external magnetic field. [7] Their performances, characterized by an energy product (BH)max exceeding 150 kJ.m-3 , already competes in the permanent magnets panorama.

References [1] [2] [3] [4] [5] [6] [7]

R. J. White, R et al. Chem. Soc. Rev. 38 (2009) 481.

L.-M. Lacroix et al. Angew. Chem. Int. Ed. 51 (2012) 4690.

A. Loubat et al. Langmuir 30 (2014) 4005.

A. Loubat et al. Nano Res 6 (2013) 644.

P. Moutet et al. Langmuir 31 (2015) 4106.

L.-M. Lacroix, A. Arenal, G. Viau, J. Am. Chem. Soc. 136 (2014) 13075.

E. Anagnostopoulou et al. Nanoscale (2016) in press.

Figures

Figure 1: Transmission electron microscopy images of Pt a) stars and b) dendrites and c) ultrathin Au nanowires.

103

Luminescent platinum systems based on the chromophore 2-phenylbenzothiazole Rebeca Lara, Nora Giménez, Elena Lalinde, M. Teresa Moreno Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja, 2006, Logroño, Spain relara@unirioja.es

In the last years, luminescent platinum complexes have been widely studied for their rich photochemistry and wide applicability in optical technologies. [1] Thus, they have been employed as dopants in electroluminescent materials, chemosensors, photocatalysts, probes for bioimaging, photosensitizers for dyesensitized solar cells and singlet-oxygen generation and photodynamic chemotherapy. In this regard, a good number of studies concentrate on trans-(alkynyl)bis(phosphine)Pt(II) chromophores and Pt(II) systems with cyclometalated or polypyridyl ligands, while related works on Pt(IV) derivatives are scarce.

104

In this work, we have used three ligands based on the chromophore 2-phenylbenzothiazole (Scheme 1. Br-bt L1, Me3SiC≡C-bt L2, HC≡C-bt L3), which present a great versatility of coordination, via nitrogen (κN) or cyclometalated (κC^N) and in the case of L3 , coordination as an alkynyl ligand (C≡C-bt- ) upon deprotonation.

Thus, we have prepared the series of Pt(II) derivatives cis-[Pt(L-κN)2(C6F5)2] (L= L1 1, L2 2, L3 3) containing the ligands coordinated through the nitrogen atom. Activation of 1 produces the metalation of the pendant coordinated N^CH ligand to give the cyclometalated Pt(II) derivative [Pt(L1 - κC,N)(L1 -κN)(C6F5)] 4, which can be oxidized to the bis(cyclometalated) Pt(IV) species [Pt(L1 - κC,N)2(C6F5)Cl] 6. Adequate substitution reactions afford cyanide Pt(II) and Pt(IV) derivatives (5 and 7), which allow modify the electronic characteristics, tuning the photophysical properties. Finally, by using the ligand L3, we have synthesized a series of transplatinum(bis-alkynyl) derivatives trans-[Pt(C≡Cbt)2L2]n (n = 0, L = PPh3 8, PEt3 9, PTA 10, n = 2-, L = CN- 11).

Detailed structural and photophysical studies on these Pt(II) and Pt(IV) derivatives have been carried out.

Acknowlegements We thank to the Spanish MINECO (Project CTQ 2013-45518-P) and to the Comunidad Autónoma de La Rioja (CAR).

References [1]

V. W. W. Yam, V. K. M. Au, S. Y. L. Leung, Chemical Reviews, 115 (2015) 7589.

Dynamics of the SPIN-ice states with magnetic charges F. López-Bara and F. López-Aguilar Electromagnetism Group, Department of Physics, Autonomous Barcelona University, Campus de Bellaterra, E-08193, Barcelona, Spain

The magnetic monopoles have always been a theoretical concept, but recently, structural entities discovered in the spin-ices have similar behaviour to the magnetic charges. These entities are low energy excitation states in these magnetic structures which are produced via a spin flip between two contiguous tetrahedrons of its crystal structure. The proliferation of these spin-flips can produce sufficient free positive and negative charges in such a way that the system behaves in similar way to a neutral cold magnetic plasma which has been experimentally detected in specific heat measurement (1). Another sharp peak at lowest energy appears for decreasing temperature and which is produced by the Coulomb interaction among magnetic charges. This interaction generates a first phase transition toward a condensation of poloantipole pairs, possibly having a Bose-Einstein condensate structure when the existence of poleantipole pairs excludes free magnetic charges(2). These pairs can freely travel inside of the spinice compounds and then, the electromagnetic propagation it is possible. The electromagnetic wave interaction over the spin-ice in an unconfined system assisted by an intense and constant electric field allows us to determine the linear response, the effective mass of the magnetic monopoles, plasmon frequency of the plasma state and precession frequency of magnetic charges. This precession frequency coincides with a strong EM absorption of the system, and therefore it allows establish a true test for existence the magnetic charges. On the other hand, we carry out a second electromagnetic guided wave propagation analysis taking into account the existence of free magnetic charges. With this analysis, we can determine the frequency dependent conductivity, the cut-off propagation frequency, phase difference between current and field and the different expressions of the fields. All these EM propagation properties depend crucially on the magnetic charge density (3). This suggests that there are potential applications of these materials for constructing “Magnetronic” devices (dual concept of electronic devices) in order to propagate energy and information..

References [1]

[2] [3]

L. Bovo, J.A. Bloxsom, D. Prabhakaran, G. Aeppli, & S.T. Bramwell, “Brownian motion and quantum dynamics of magnetic monopoles in spin ice”, Nature Comunications, February (2013).

W. H. Toews, S.S. Zhang, K.A. Ross et al. “Thermal cpmductivity of along [1,1,1] direction”, Phys. Rev. Lett. 110, 217209 (2013).

J. Costa-Quintana, F. López-Aguilar, “Fresnel coefficients in materials with magnetic monopoles”, Optic Express, 19, 3742-3757 (2011).

105

Do strong surfactant/swcnt-cooh interactions assure good dispersion quality?

M. López-López1, E. Bernal2, M. L. Moyá2 and P. López-Cornejo2 1

Departamento de Ingeniería Química, Química Física y Ciencias de los Materiales. Universidad de Huelva Campus ‘El Carmen’, Facultad de Ciencias Experimentales, E-21071, Spain Departamento de Química Física. Universidad de Sevilla. c/ Prof. García González 1. 41012 Sevilla ,Spain manuel.lopez@diq.uhu.es

2

106

Carbon nanotubes, CNT, are building blocks used in the construction of molecular assemblies. Due to their mechanical, optical and electronic properties, they can be used in diverse fields. For instance, CNT have been used as sensor or as vectors in gene transfection. [1] The separation (dispersion) of the carbon tubules, that is their solubilization, can be improved by chemical methods. One of these consists on the use of surfactants. Several studies about the interactions between surfactants and carbon nanotubes have been carried out. [2] However, the mechanism of such interaction is not clear yet. In order to shed light on the surfactant/carbon nanotube interactions, quantitative information about the interactions (or adsorption) of cationic and anionic surfactants with functionalized carbon nanotubes (SWCNT-COOH) were obtained. The surfactants investigated were hexadecyltrimethylammonium bromide –CTAB-, dodecyltrimethylammonium bromide -DoTAB-, octyltrimethylammonium bromide –OTAB- and sodium dodecysulphate –SDS. Electromotive forces of solutions containing surfactant and SWCNT-COOH were measured by using selective electrodes of the different surfactants previously prepared by us. Results showed a sigmoidal dependence of the free surfactant concentration on the nanotube concentration (see Figure 1). This behaviour demonstrates the cooperative character in the surfactant/nanotube binding.

Interaction (adsorption) of anionic and cationic surfactants with functionalized singlewalled carbon nanotubes (SWCNT-COOH) are driven by hydrophobic interactions between the hydrocarbon tails and the nanotube walls. Electrostatic interactions practically exert no influence. Driving forces in the dispersion processes seem to be different.

References [1]

[2]

(a) J. Chen, T.O. Tran, M. T. Ray, D. B. Brunski, J. C. Keay, D. Hickey, M. B. Johnson, D. T. Glatzhofer and D. W. Schmidtke, Langmuir 29 (2013) 10586. (b) L. Shi, D. Shi, M. U. Nollert, D. E. Resasco and A. Striolo, J. Phys. Chem. B 117 (2013) 6749. (a) Y. Chen, R.N. Gunasinghe, X.-Q. Wang and Y. Pang, RSC Advances 3 (2013) 25097. (b) B. Sohrabi, N. Poorgholami-Bejarpasi and N. Nayeri, J. Phys. Chem. B 118 (2014) 3094.

Figures

Figure 1

Figure 2

A thorough spectroscopic study about the interaction of surfactants with carboxylated singlewalledcarbon nanotubes Manuel López-López1, Eva Bernal2, María Luisa Moyá2, Pilar López-Cornejo2 1

Department of Chemical Engineering, Physical Chemistry and Material Science. Faculty of Experimental Sciences.

University of Huelva. Avda. Tres de Marzo s/n. Campus El Carmen. 21071 Huelva, Spain 2 Department of Physical Chemistry. Faculty of Chemistry. University of Sevilla. c/ Profesor García González s/n. 41012 Sevilla, Spain manuel.lopez@diq.uhu.es

Carbon nanotubes (CNT) are currently one of the most interesting nanomaterials due to their remarkable mechanical, optical and electrical properties. They have a wide range of applications as sensors [1], electronic components [2], etc. For many applications a uniform and stable dispersion is needed.

Surfactants (cationic, anionic and nonionic) have been shown to be efficient CNT dispersing agents [3].

Most works in the literature are aimed at the study of the properties and stability of CNTsurfactant systems, establishing criteria for designing optimal dispersion [3].

In this work a through study of the SWCNTCOOH aqueous dispersions in the presence of several surfactants was carried out. Different techniques were used in order to gain precise information about the interactions operating in these SWCNTCOOH-surfactant systems. Results indicate that the interaction of the surfactants with SWCNTCOOH depends on the surfactant charge as well as on the surfactant hydrocarbon tail length, as is shown by the surfactant adsorption at the CNT surface (Figure 1). The negatively charged CNT used in this work attracts (repels) the cationic (anionic) surfactants. On the other hand, the hydrocarbon tail length plays an important role in the CNT-surfactant interactions due to the self-organization of surfactants on the CNT surface. Both surfactant monomers and micelles influence the physicochemical properties of the CNT aqueous dispersions.

References [1] [2] [3]

R. Moscoso, J. Carbajo, M. Lopez, L.J. Núñez-Vergara, J. A. Squella, Electrochem. Commun. 13 (2011) 217.

E. Frackowiak, F. Beguin, Carbon, 40 (2002) 1775.

P. Angelikopoulos, H. Bock, PCCP 14 (2012) 9546.

Figures

Figure 1: Influence of CTAB (A) and SDS (B) concentration on the UV-vis spectra of SWCNTCOOH dispersions.

107

SnO2 humidity interferometric sensor based on photonic crystal optical fiber and Fast Fourier Transform D. Lopez-Torres, N. De Acha, C. Elosua and F.J. Arregui Nanostructured Optical Devices Laboratory, Electric and Electronic Engineering Department, Public University of Navarre, Edif. Los Tejos, Campus Arrosadía, 31006, Pamplona, Spain.; diego.lopez@unavarra.es

In this paper we report a sensor based on a SnO2 nanocoating sputtered onto an optical fiber interferometer for relative humidity (RH). This deposition technique achieves high reproducibility, a good long-time stability and precise control in the thickness of the coated nanofilm. The device consists of a photonic crystal optical fiber segment (PCF) spliced between two standard mono mode fibers. In the first spliced region, the voids of the PCF are collapsed allowing the recombination of PCF core and cladding modes [1]; when the modes reach the second spliced region, they yield to an interferometric response.

Along the PCF segment, the cladding modes interact with SnO2 nanofilm which is highly sensitive to RH. Figure A shows how different RH values shift the interferometric pattern due to the interaction with the SnO2 coating. Fast Fourier Transform (FFT) is applied to the interferometric signal, using the phase variations to follow RH changes. FFT method offers some advantages such as the nondependence of the signal amplitude and also avoids the necessity of tracking the wavelength evolution in the spectrum which improves the post process of the sensor response [2]. As it can be seen in Figure B, the resulting phase follows HR changes along the measuring range (20-90% RH) with a sensitivity of 0.01 rad/HR%; moreover, it shows a negligible cross correlation with temperature.

108

Acknowledgements Financial support from the Spanish Economy and Competitiveness Ministry TEC2013-43679-R Research Grant as well as Public University of Navarre PhD Grants Program are acknowledged.

References [1] [2]

O. Letters, “Refractometry based on a photonic crystal ber interferometer,” Opt. Lett., vol. 34, no. 5, pp. 617–619, 2009.

D. Leandro, M. Bravo Acha, A. Ortigosa, and M. Lopez-Amo, “Real-time FFT analysis for interferometric sensors multiplexing,” J. Light. Technol., vol. 8724, no. c, pp. 1–1, 2015.

Figures

Figure A: Spectral shifts for different RH values

Figure B: Evolution of the FFT phase component for varying RH conditions

109

Transition metal chalcogenides in the 2D limit: superconductivity in 2H 2H-TaS2 Pinilla-Cienfuegos1, Andrés Samuel Mañas-Valero1, Efrén Navarro-Moratalla1, Joshua O. Island2, Elena Pinilla Castellanos-Gómez2, Jorge Quereda3, Gabino Rubio-Bollinger3, Luca Chirolli4, Jose Angel Silva-Guillén4, Gary A. Steele2, Francisco Guinea4, Herre van der Zant2 and Eugenio Coronado1 1 Universidad de Valencia (ICMol), Catedrático José Beltrán Martínez nº 2, 46980, Paterna, Spain Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands 3 Dep. de Física de la Materia Condensada. Univ. Autónoma de Madrid, Campus de Cantoblanco. EE-28049 Madrid, Spain 4 Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia), encia), Calle Farady 9, Madrid, Spain samuel.manas@uv.es 2

Graphene [1] is one of the most studied materials due to its unique properties such as hardness, flexibility and high electric and thermal conductivity. However, probably the best quality of graphen graphene is that it has opened the field to many other 2D crystals [2] including superconductors and topological insulators.

In this work, the synthesis and characterization of metal chalcogenides from bulk to thin layers are discussed. As an example, transport measurements in thin layers of 2H-TaS2 are presented: it is observed a superconducting critical temperature enhancement by decreasing the number of atomic layers (from 0.8 K in the bulk sample to ca. 2K in a ~3 nm layer; Figure 1). This behaviour is the opposite pposite of the one reported in other superconductor 2D crystals [3]. This result brings superconductivity into the flatland and may open the door for their future use in magnetic sensors or low energy applications.

References

110

[1] [2] [3]

K. S. Novoselov et al., Science 306 (2004) 666.

L. Britnell et al., Science 340 (2013) 1311.

M. M. Ugeda, M. et al., Nature Physics 12 (2015) 92–97; M. S. El-Bana Bana et al., Superconductor Science and Technology 26 (2013) 1; A. W. Tsen et al., Nature Physics (2015), online, doi: 10.1038/nphys3579.

Figures

Figure 1: a) Variation of the Tc as a function of the thickness of the TaS2 layers. Devices exhibiting non non-zero RRR are plotted in blue. Inset: Stack of two layers of 2H-TaS2 made out of sulfur (X) and tantalum (M). b) Variation of Bc2 (circles) and G G-L length values (triangles) as a function of thickness. A dashed red line has been placed at the Tc and Bc2 values found for bulk flak flakes to serve as a reference for establishing the thick layer limit.

Improvement of the toughness of PMMA-based acrylic resin for dental application by adding small amounts of graphene nanoparticles José Miguel Martín-Martínez1, María Alejandra Moyano2, Miguel Ángel Torres del Castillo2, Antonio García-Pellicer2 1 Adhesion and Adhesives Laboratory. University of Alicante. 03080, Alicante, Spain.

2 iDental. R&D Department. Cruz de Piedra 4. 03015 Alicante. Spain. jm.martin@ua.es

Polymer nanocomposites have received much attention due to their enhanced mechanical, thermal, optical and gas barrier properties in comparison to conventional composites. Incorporation of small quantities of graphene nanoparticles causes noticeable improvement in the properties of the nanocomposites as long as a homogeneous dispersion of the nanoparticles in the matrix is achieved [1].

The adequate dispersion requires the creation of strong interactions between the graphene nanoparticles and the polymer matrix and this involves the destruction of the strong van der Waals forces between the graphene nanoparticles [2]. Graphene nanofibers have higher aspect ratio than graphene nanoplatelets but these are difficult to disperse because they interact more effectively with polymers containing aromatic rings in their structure.

In this study the influence of the addition of different small amounts of graphene nanofibers and graphene nanoplatelets to a self-polymerizing two-component polymethyl methacrylate (PMMA)-based acrylic resin for dental application were studied, paying particular attention to the improvement in toughness of the acrylic nanocomposite. The nanoparticles and the solid component of the acrylic resin mixtures were prepared in orbital double centrifugal Speed Mixer® equipment at 3400 rpm for 6 minutes. Transmission electron microscopy (TEM) was used to analyze the distribution of nanoparticles in the polymer matrix.

The residual polymerization of the nanocomposites was determined by differential scanning calorimetry (DSC), the viscoelastic properties were obtained by dynamic mechanical thermal analysis (DMA) and mechanical properties 3-point bending tests.

The graphene nanoplatelets disperse worse in the acrylic matrix than graphene nanofibers (Figure 1), promoting lower degree of polymerization and higher extent of crack formation under compression stresses, probably due to inadequate nanoparticle-matrix interaction. On the other hand, the addition of small quantities of graphene nanofibers (0.12-0.46 wt%) improves the toughness of the nanocomposites avoiding crack formation without altering its degree of polymerization. Optimal properties of the nanocomposites (greater increase in elastic modulus at 37°C, absence of cracking and less dimensional variation under compressive stresses) are obtained by adding 0.49 wt% of graphene nanofibers to the PMMA-based acrylic resin.

References [1] [2]

Goncalves G, Marques P, Barros-Timmons A, Bdkin I, Singh MK, Emami N, Grácio J. Journal of Materials Chemistry, 20 (2010), 9927-9934.

Thomassin JM, Trifkovic M, Alkarmo W, Detrembleur C, Jerome C, Macosko C. Macromolecules, 47 (2014), 2149-2155.

111

Figures

Figure 1: TEM micrographs of PMMA nanocomposites containing 0.49 wt% graphene nanofibers (left) and 0.50 wt% graphene nanosheets (right).

112

Bimodal HD-KFM and Resiscope Atomic Force Microcopy characterization of bidimensional materials and solar cells Nicolas F. Martinez1 and Louis Pacheco2 1

ScienTec Iberica, Rufino Sanchez 83, Las Rozas, Spain Concept Scientific Instruments, 17 Rue des Andes, Les Ulis, France f.martinez@scientec.es

2

Over the past 30 years, Atomic Force Microscopy has evolved from a microscope to measure just the surface topography to a wide variety of measurement modes that provides a way to characterize other atomic interactions or physical properties like magnetic field, electric field, nanoscale dissipation processes, thermal conductivity, electrical conductivity, resistance, surface potential, piezoresponse, Young modulus,… Electrical nanocharacterization with AFM has emerged as a powerful tool to map electrical properties at the nanoscale, like surface potential (work function) and conductivity. However, traditional setups in AFM make difficult to obtain accurate and repeteable results over several types of samples.

In this article we will show the capabilities of two new developed AFM modes: High Definition Kelvin Force Microscopy (HD-KFM) and (Soft)Resiscope that overcome the intrinsic difficulties of electrical nanocharacterization with AFM. This two techniques have been applied on a wide variety of substrates: bidimensional materials, like graphene or molibdene disulfide, organic solar cells and nanoparticles providing high stability, sensitivity and lateral resolution.

113 References [1] [2] [3] [4] [5] [6]

G. Binnig, C.F. Quate, Ch. Gerber, Phys. Rev. Lett. 56, 930 (1986).

Houzé F, Meyer R, Schneegans O, Boyer L.. Appl Phys Lett. 1996; 69:1975.

D.W. Abraham, et al, J. Vac. Sci. Technol. B 9,703 (1991).

T.R. Albrecht, P. Gr¨utter, D. Horne, D. Rugar, J. Appl. Phys. 69, 668 (1991).

T.R.Rodriguez and R.Garcia App. Phys. Lett. 84(3):449-451.

J. Colchero, A. Gil, A.M. Bar´o, Phys. Rev. B 64, 245403 (2001).

Figures

Figure 1: a) HD-KFM image on Graphene b) HD-KFM image on Molibdene disulfide.

On the peculiar mechanical and tribological behavior of polymer nanocomposites with nanotubes of WS2 and nanowires of Mo6S2I8 Johann G. Meier, Mariana Castrillón, Cristina Crespo, José A. Lorda ITAINNOVA, C/ María de Luna 7-8, Zaragoza, Spain jmeier@itainnova.es

Inorganic tubular and wire-like nanomaterials based on WS2 and MoSI are an interesting new alternative to carbon nanotubes [1, 2]. They show advantages such as easy synthetic access, good uniformity and solubility, and predefined electrical conductivity depending on the composition of the starting material.

One of the most outstanding properties of both types of nanoparticles is their low inter-particle shear modulus, while having comparable tensile moduli to CNTs. This has the advantage that they are potentially much easier to disperse than carbon nanotubes. Also common to both types of nanoparticles (metal base W and Mo) is their excellent lubrication property. This makes them highly attractive as additives for friction reduction and wear protection of polymers [3]. They are therefore very promising candidates as active fillers for polymers for mechanical reinforcement, improvement of toughness, fracture toughness and fatigue behavior together with improving the tribological properties of the polymer host [4]. Hence, they hold the promise to give answers to these technological paramount properties in polymers.

We report on the preparation and resulting mechanical and tribological properties of polymer nanocomposites (PNC) based on nanotubes of tungsten disulfide (WS2) and nanowires of Mo6S2I8 (MoSI) with both; a semicrystalline apolar and an amorphous polar thermoplastic polymer (i-PP, PC).

114

The PNCs were obtained by direct incorporation of the nanoparticles into the molten polymer using a labscale conical twin-screw extruder. We present the results of the mechanical and tribological properties of the PNC in function of NP-concentration and processing conditions.

Most, interesting is the fact that excellent reinforcement of both polymer matrices is obtained with both types of nanoparticle morphologies (wires and tubes). Up to 1.5 wt% nanoparticle concentration one observes a steady increase of Young’s modulus. Higher concentrations mark a plateau, which is ca. 25% higher than the pure polymer matrix. Employing the fibre reinforcement model of Halpin and Tsai one obtains estimates of the fibre aspect ratio that are well beyond any physical sense, marking the limits of the Halpin-Tsai model and a significant higher reinforcement that predicted by commonly accepted and very often successfully employed models. We point out that the extremely high reinforcing effect cannot be attributed to the induction of crystallinity, because the effect occurs in the amorphous matrix as well.

Studies of the tribological properties of the i-PP composites revealed a reduction of the friction coefficient by ca. 25% at a concentration of 1.5wt%. Composites with WS2-nanotubes performed better than nanowires of Mo6S2I8. Likewise wear rate was reduced by ca. 25%, although here the nanowires of Mo6S2I8 showed better results. It was observed that the pretreatment of nanoparticles before meltmixing has a significant influence on the obtained reduction of friction coefficient but surprisingly not the wear rate.

References [1] [2] [3] [4]

R. Tenne and G. Seifert, Ann. Rev. Mater. Res., 39 (2009) 387.

D. Mihailovic, Prog. Mater Sci., 54 (2009) 309.

J. G. Meier, A. Mrzel et al., physica status solidi (a), 210 (2013) 2307.

M. Naffakh, A. M. Díez-Pascual et al., Prog. Polym. Sci., 38 (2013) 1163.

Coupling, geometric phases, and properties of quantum dots: analytics and numerics for the Berry phase case Roderick Melnik, Sanjay Prabhakar MS2Discovery Interdisciplinary Research Institute, WLU, Waterloo, 75 University Ave W, ON, Canada BCAM - Basque Center for Applied Mathematics, Mazarredo 14, E48009, Bilbao, Bizkaia, Spain rmelnik@wlu.ca

Recent experimental spin-based realizations of universal geometric quantum gates [1] open new exciting opportunities for practical applications and pose new challenges for theoretical research on geometrical phases. They clearly highlight the importance of geometric phases in nanotechnology in general and in the design and control of low dimensional nanostructures in particular.

In this contribution, we analyze and quantify the influence of such geometric phases on the properties of quantum dots. We focus on the Berry phase and demonstrate its high sensitivity to electric fields coming from the interplay between the Rashba and Dresselhaus spin-orbit couplings. The Berry phase is induced by letting the quantum dots to move adiabatically in a closed loop in the 2D plane along a closed trajectory [2]. We demonstrate that the accumulated geometric phase can be induced from other available quantum states that differ only by one quantum number of the corresponding spin state. Moreover, the sign change in the g- factor can be reflected in this phase. We carry out the analysis for typical spatial scales in such situations, namely for spin-orbit length, hybrid orbital length, and orbital radius, and determine the key characteristics of the Berry phase for these scales. The technique, developed for our analysis of spin dynamics evolution during the transport of quantum dots as describe above, is based on a combination of analytical and numerical tools. The timedependent Schrodinger equation is solved by applying the Feynman disentangling technique supplemented by the finite element methodology. It is shown that the superposition effect can be observed during the transport process, while the Berry phase for the pure Rashba and pure Dresselhaus cases are well separated at smaller values of the spin-orbit lengths. Finally, applications of the observed effects are discussed.

References [1] [2]

C. Zu, W.-B. Wang, L. He, et al, Nature. 514 (2014) 72-76.

S. Prabhakar, R. Melnik, L. L. Bonilla, Phys. Rev. B. 89 (2014), 245310.

115

Diagnostic devices using graphene and other nanomaterials Arben Merkoรงi ICREA & Catalan Institute of Nanoscience and Nanotechnology (ICN2), Bellaterra (Barcelona), Catalonia, Spain www.nanobiosensors.org - www.icn.cat arben.merkoci@icn.cat

116

Development of novel diagnostic tools with interest for point of care applications represents one of the main research fields for the nanobiotechnology. Efforts are shown to either develop brand new devices or improve existing ones thanks to the use of nanomaterials and nanotechnologies. Between the various devices biosensing systems based on electrical or optical transducing schemes are overall in the focus of interest given the simplicity and cost efficiency of detection. Among the various biosensing system performance requirements the high sensitivity and selectivity of the response are crucial for applications in clinical diagnostics. The fulfilment of such requirements means the detection of low levels of clinical biomarkers in human fluids. Given the fact that biomarkers are present in very low concentrations the need for biosensing systems that can detect these analytes with high sensitivity and selectivity that include very low detection limits along with high reproducibility is an important challenge. To overcome the difficulties in accomplishing all these requirements the main efforts are driven toward signal amplification and noise reduction of biosensing systems by the incorporation of nanomaterials. Nanomaterials (NMs) such as carbon nanotubes, graphene, metallic nanoparticles, nanowires and quantum dots are showing to be excellent materials to be used as electrochemical transducers or labels in DNA (or genosensors) sensors beside enzymatic sensors, immunosensors, or cell sensors. The amplification of the detection of biorecognition events (ex. DNA hybridization reactions etc) are the most important objectives of the current bioanalytical chemistry. In this context integration of the catalytic properties of some biomolecules with those of nanomaterials is appearing to be a promising way to enhance the sensitivity of the bioassays.

Examples related to various clinical biomarkers as well as contaminants detection will be shown. The developed devices and strategies are intended to be of low cost while offering high analytical performance in screening scenarios beside other applications. Special emphasis will be given to lab-on-a-chip platforms with integrated electrochemical detection with interest for various applications. In addition simple paperbased platforms that operate in lateral flow formats with interest for various detections also will be shown.

Structure-property relation in atomically precise graphene nanoribbons on Au(111) N. Merino-Díez1,2,3, E. Carbonell-Sanromà1, M. Corso 1,3,4, D. Peña,5 J.I. Pascual1,4 and D. G. de Oteyza2,3,4 1

CIC nanoGUNE, 20018 Donostia – San Sebastián, Spain Donostia International Physics Center, 20018 Donostia – San Sebastián, Spain 3 Centro de Física de Materiales (CSIC/UPV-EHU) - Materials Physics Center, 20018 Donostia – San Sebastián, Spain 4 Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain 5 Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and Departamento de Química Orgánica, 15782 Universidad de Santiago de Compostela, Spain n.merino@nanogune.eu 2

Graphene nanoribbons (GNRs) are narrow stripes of graphene, whose electronic properties strongly depend on their detailed structure. As an example, GNRs with armchair shaped edges are predicted to be semiconducting, with a width-dependent band gap, while those with zigzag shaped edges are predicted to be semi-metallic and present localized spin-polarized edge-states [1]. Such variety of electronic behaviors places them as promising building blocks in next-generation nanoelectronic and optoelectronic devices.

However, since the electronic properties of GNRs are highly susceptible to minimum changes in their structure, their precise synthesis and consequently the experimental confirmation of the predictions has remained a key challenge. Recent advances in bottom-up synthesis have shown that the growth of atomically precise GNRs can be produced by pre-designing the chemical structure of molecular precursors [2].

By means of low-temperature Scanning Tunneling Microscopy (STM) and Spectroscopy (STS), we report the study of different GNRs synthesized on Au(111) from two organic precursors: 4,4’’-dibromo-pterphenyl (DBTP) and 2,2’-dibromo-9.9’-bianthracene (DBBA). In the case of DBTP molecules, carefully annealing-triggered molecular reactions (Fig. 1a) result in the formation of GNRs with different width on the same metallic substrate (Fig. 1b,c) [3], enabling us to study the predicted band gap dependence of armchair nanoribbons on their width. Our results confirm this size dependence in armchair shaped GNRs and are in good agreement with calculations [4]. In turn, the use of DBBA molecules leads to the synthesis of well-defined, chiral nanoribbons (Fig. 2) with a consequently lower bandgap. Fourier-transform STS analysis provides additional insight into the GNR’s band dispersion.

References [1] [2] [3] [4]

Kyoko Nakada et al., Physical Reviews B, 54 (1996) 17594.

Jinming Cai et al., Nature, 466 (2010) 470-473.

Andrea Basagni et al., JACS, 137 (2015) 1802-1808.

Li Yang et al., Physical Reviews Letters, 99 (2007) 186801.

117

Figures

Figure 1: a) Syntheiss scheme of DBTP nanoribbons.

Topographic images of poli-p-phenyl wires and c) interlinked GNRs with different width.

118

Figure 2: a) Syntheiss scheme and b) topographic image of DBBA nanoribbons.

High time resolution thermometry on a magnetic nanoheater. A new tool for hyperthermia Angel Millán1, Rafael Piñol1, Carlos D. S. Brites2, Rodney Bustamante1, Abelardo Martínez3, Nuno J. O. Silva2, José L. Murillo1, Rafael Cases1, Julian Carrey4, Carlos Estepa1, Cecilia Sosa5, Fernando Palacio1, Luis D. Carlos2 1

ICMA, CSIC–Universidad de Zaragoza, 50009 Zaragoza, Spain Departamento de Física and CICECO, Universidade de Aveiro, 3810–193 Aveiro, Portugal 3 Departamento de Electrónica de Potencia. I3A. Universidad de Zaragoza 50018 Zaragoza, Spain 4 Université de Toulouse, INSA, UPS, CNRS (UMR 5215), F-31077, Toulouse, France 5 Departamento de Toxicología, Universidad de Zaragoza, 50013 Zaragoza, Spain amillan@unizar.es 2

Magnetic induction heating of nanoparticles has already been approved for hyperthermia therapy of cancer and other diseases. Nowadays the clinical treatment involves a direct injection of nanoparticles into the tumor and the application of a magnetic field until the temperature at 2 cm from the tumor is reaching 43 oC. The amount of nanoparticles to be injected for this purpose is very high and that means a long process until the nanoparticles are cleared from the body. Thus, the development of local intracellular hyperthermia involving a smaller number of particles would be very desirable. In order to make this strategy effective an adequate monitoring of the nanoheaters local temperature will be required. Here we present a single magnetic nanoparticle [1] that incorporates a luminescent molecular thermometer [2].

The temperature readout is optical and the thermometric probes are Eu3+/Tb3+ lanthanide complexes encapsulated in the copolymer coating, around the iron oxide magnetic core. The thermometer shows an outstanding performance in terms of: sensitivity (5.8%⋅K−1 at 296 K), uncertainty (0.5 K), readout reproducibility (>99.5%), and fast time response (0.250 s). Experiments of time-resolved thermometry under an AC magnetic field reveal the existence of an unexpected temperature gradient between nanoheaters and surrounding media. A proof of concept of temperature mapping has been realized on cells that were incubated with the nanoparticles [3], (Fig 1). The heater/thermometer reported here shows great potential for the design of hyperthermia therapies based on localized manipulation of heat flows and short application times. In this way, local energy supply which is not immediately dissipated at the surrounding media could be enough to induce irreversible intracellular damage in tumor cells within a short time period, while maintaining the neighboring tissue temperature unchanged [4].

References [1] [2] [3] [4]

C. D. S. Brites, et al. Adv. Mater, 22 (2010) 4499.

R. Bustamante et al. Phys. Rev. B 88 (2013) 184406.

R. Pinol et al. ACS Nano 9 (2015) 3134.

A. Schroeder, et al. Nat. Rev. Cancer 12 (2012) 39

119

Figures

3+

3+

Figure 1: Imaging of Tb (A) and Eu (B) emissions from cell-internalized nanoparticles. Scale bars are 40 Âľm.

Pseudocolour maps of spot 1 in Fig A&B illustrating the co-localization of the Tb3+ (C) and Eu3+ (D) emissions, temperature map (E) computed from this emissions at every pixel, and (D) histogram of the temperature distribution near the cell nucleus. Scale bars correspond to 10 Âľm.

120

Ultrathin Gold-Silver Nanorods and Nanowires Stabilized with Long Alkyl Chain Carboxylic Acids: Synthesis and Plasmonic Properties Miguel Monge1, Julian Crespo1, José M. López-de-Luzuriaga1, M. Elena Olmos1, María Rodríguez-Castillo1, Teresa Tena1, Benôit Cormary2, Katerina Soulantica2, Matteo Sestu3, Andrea Falqui4 1

Departamento de Química. Centro de Investigación en Síntesis Química (CISQ). Universidad de La Rioja.

Complejo Científico Tecnológico, Madre de Dios 51, 26006 Logroño, La Rioja, Spain.

2 Université de Toulouse; INSA, UPS, CNRS, LPCNO, 135 avenue de Rangueil, 31077 Toulouse, France.

3 Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, 09042 Monserrato (CA), Italy.

4 King Abdullah University of Science and Technology (KAUST), Biological and Environmental Sciences and Engineering Division, 23955-6900 Thuwal, Kingdom of Saudi Arabia miguel.monge@unirioja.es

The control of the main features of nanostructures is a fundamental prerequisite for a deep study of their properties, which change with size, shape, composition and surface state. The use of organometallic complexes has permitted to achieve a plethora of well controlled metal nanostructures that have been obtained through the precise knowledge of the chemical structures and molecular chemistry of this type of metal precursors. [1] In this context, bimetallic one-dimensional gold-silver alloy nanostructures have been obtained through the reduction of organometallic perfluoroaryl Au(I)-Ag(I) precursors obtained when long alkyl chain carboxylic acids such as oleic or linoleic acid are used as capping agents.[2,3] When these long alkyl chain carboxylic acids are used as solvent and capping ligand ultrathin nanorods (UNRs) and ultrathin nanowires (UNWs) are obtained. If organic solvents are used in the presence of controlled amounts of carboxylic acids both spherical nanoparticles as well as 1-D nanostructures can be achieved, depending on the reaction conditions.

These 1-D gold-silver nanostructures display a length-dependent broad band from the NIR to the mid IR region that can be related to the longitudinal mode of the surface plasmon resonance (SPR) of these ultrathin nanostructures. .

References [1] [2] [3] Figures

C. Amiens, B. Chaudret, D. Ciuculescu-Pradines, V. Collière, K. Fajerwerg, P. Fau, M. Kahn, A. Maissonat, K. Soulantica, K. Philippot, New J. Chem 37 (2013) 3374-3401.

J. Crespo, A. Falqui, J. García-Barrasa, J. M. López-de-Luzuriaga, M. Monge, M. E. Olmos, M. Rodríguez-Castillo, M. Sestu, K. Soulantica, J. Mat. Chem. C, 2 (2014) 2975-2984.

J. Crespo, J. M. López-de-Luzuriaga, M. Monge, M. E. Olmos, M. Rodríguez-Castillo, B. Cormary, K. Soulantica, M. Sestu, A. Falqui, Chem. Commun,, 51 (2015) 16691-16694.

121

Electrophoretic vs. dielectrophoretic forces in 2D optoeletric nanoparticle patterning J. F. Muñoz-Martínez1,2, C. Arregui1, J.B. Ramiro1, A. Alcázar1, A. García-Cabañes2, M. Carrascosa2 1

Dpto. de Mecánica de Fluidos y Propulsión Aeroespacial, UPM, Pza. de Cardenal Cisneros, 3, 28040, Madrid, Spain 2 Dpto. Física de Materiales, UAM, C/ Francisco Tomás y Valiente 7, 28049, Madrid, Spain juanf.munnoz@uam.es

Photovoltaic tweezers (PVT) are a recently developed optoelectric technique for flexible particle trapping and patterning on the surface of certain ferroelectrics [1]. It is based on the light induced electric fields generated in those materials via the bulk photovoltaic effect. It has been already applied with both inorganic and biological objects and it is becoming a very competitive and flexible tool for particle manipulation and patterning (see [1] and references therein).

This technique has been mostly used with neutral micro and nanoparticles (NP), manipulated through dielectrophoretic (DEP) forces, although a few cases of electrophoresis (EP) of charged particles have been also reported [2,3]. Moreover, very few data on the comparison between EP and DEP particle patterning and on the different features of the obtained structures are available. In this work we have investigated this issue by theory and experiments to clarify the advantages of each regime.

122

Theoretical predictions are based on a previously developed theoretical model [4] for DEP forces that is here applied to calculate the EP and DEP potentials for arbitrary 1D and 2D light distributions. Simulations show different EP and DEP potentials for a given light distribution, so dissimilar features are expected also for the corresponding particle patterns. Specifically, DEP potential profiles seem to better reproduce the light pattern although they present an edge enhancement effect. To confirm these predictions we have addressed a number of experimental tests.

In the patterning experiments z-cut LiNbO3:Fe crystals are used to generate the photovoltaic electric fields by illumination and to trap aluminium NP (∅=70nm) on their surface. The light intensity distribution used is identical to that of the simulations. Afterwards, the crystal is immersed in a hexane suspension of the NP and the pattern is generated on its surface.

The experimental results on NP patterning basically agree with the theoretical predictions and confirm the differences between EP and DEP deposition and the better fidelity to the light pattern exhibited by DEPdeposited nanostructures. An example is presented in Figure 1 where the microscope images of the particle patterns obtained by illumination with a chequered light pattern are shown for charged (a) and neutral (b) aluminium NP. In the central column (c),(d), the corresponding averaged particle concentration profiles along the horizontal direction are plotted. Finally, on the right (e), (f), numerical simulations for the EP and DEP potentials generated by a single square are shown to compare with experiments. In both microscope images the periodic pattern can be clearly seen although the definition of the squares is much better for DEP deposition (b),(d) whereas the boundaries are blurred in the EP case (a),(c). These features are in a good accordance with the simulated DEP and EP potentials. Therefore, the obtained results confirm the ability of PVT to pattern neutral and charged NP, but showing differential features between the two cases. Moreover, the theoretical model successfully describes the experiments and should allow a further optimization of the obtained NP structures in both EP and DEP regimes, increasing their potential for applications in fields such as MEMS or plasmonics.

References [1] [2] [3] [4]

M. Carrascosa, A. García-Cabañes, M. Jubera, J. B. Ramiro, and F. Agulló-López, Appl. Phys. Rev 2 (2015) 040605.

X. Zhang, J. Wang, B. Tang, X. Tan, R. A. Rupp, L. Pan, Y. Kong, Q. Sun, and J. Xu, Opt. Express 17 (2009) 9981.

M. Esseling, A. Zaltron, C. Sada, and C. Denz, Appl. Phys. Lett. 103 (2013) 061115.

C. Arregui, J.B. Ramiro, A. Alcázar, A. Méndez, J.F. Muñoz-Martínez and M. Carrascosa, J. Eur. Opt. Soc. March 10, (2015). nº15026.

Figures

123 Figure 1: (a, b) Chequered pattern (square side 250 µm) of charged (a) and neutral (b) aluminium NP; (c, d) Particle density profile along a row of the patterns showed in (a) and (b) respectively; (e, f) Simulation of the EP (e) and DEP (f) potential generated by a single square illumination.

Methods of the incorporation of nanoparticles of SiO2 in synthesis of aqueous polyurethane dispersion; evaluation of mechanical properties M.P. Muñoz Muñoz, M.V. Navarro Bañón, A.B. Francés Bueno Technical Research Centre of Furniture and Wood of Region of Murcia (CETEM).

C/ Perales s/n, Yecla, Murcia, Spain, 30510 p.munoz@cetem.es

Waterborne polyurethane dispersions (WPUDs) have a wide applicability in various industrial sectors such as coatings for textiles and leather, wood coatings, adhesives, etc. The properties of the polyurethane obtained will depend on the raw materials used for their synthesis, polyol and isocyanate, and also of the additives added in their formulation.

Nanotechnology offers an opportunity for modifying the properties of polyurethanes. Nanosilicas have been widely used for improving the properties of polyurethane materials but their use mainly has been focused in the incorporation of this nanomaterial after synthesizing the polyurethane dispersion. In this work, the addition of nanosilica during the synthesis process of WPUDs was analyzed. The synthesis of polyurethane was obtained from the reaction between a polyether polyol and IPDI as isocyanate in presence of other additives such as UV-blocking and bactericide blocking agents. The nanosilicas used were: hydrophilic nanosilicas (commercial and generated in situ) and nanosilicas modified with AMPS (aminopropyltriethoxysilane) [1-3].

124

For adding nanosilicas during the synthesis of WPUDs several aspects such as: the step of the reaction, the transfer medium of nanosilicas, and the dispersion method in this medium had to be analyzed and defined.

Ultrasound and mechanical stirring methods (at different shear rate) were analyzed for obtaining a good dispersion of nanosilicas in the selected medium. Once different methods for incorporating silica nanoparticles were studied, a specific analysis of the incorporation of silica nanoparticles in various stages (prepolymer step or aqueous dispersion step) of the synthesis process of WPUDs was analyzed.

The aim of this paper is to show the results obtained during the analysis of the incorporation of silica nanoparticles unmodified and modified during the synthesis process of WPUDs and establish its effect on the final properties of the material obtained. For each type of nanosilica, it has been studied the incorporation procedure and analyzed their influence over the concentration and addition step in the process of synthesis.

The chemical composition of the films obtained was analyzed by FTIR spectroscopy, thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). To assess the physical and mechanical properties, several standardized test methods were carried out: Viscosity Brookfield measurement (UNE EN ISO 2555:2000), tensile strength and elongation at break (ISO 527- 3: 1995), determination of elastic modulus and water vapor permeability of polyurethane films was evaluated according with a defined internal method based on ASTM E96 standard. The results show that there is an influence related with the modification of the nanosilica and the step at which the nanosilica is added in the synthesis process of WPUDs on the final properties of the polyurethane material.

References [1] [2] [3]

López Sanchez, Gonzado. Tesis: Incorporación de micro/nanoesferas en poliésteres degradables y su influencia en procesos de cristalización. Universidad Politécnica de Cataluña. Febrero de 2012 Z. Luo, R.Y. Hong, H.D. Xie, W.G. Feng. Power Technology 218 (2012) 23-30.

Zhijian Wu, Hong Xiang, Taehoon Kim, Myung-Suk Chun, Kangtaek Lee. Journal of Colloid and Interface Science 304 (2006) 119-124.

Graphene interaction with cellular structures and potentiating action on environmental pollutants effects Navas JM, Lammel T, Boisseaux P, Fernández-Cruz ML INIA (National Institute for Agricultural and Food Research and Technology), Dpt. of Environment; Ctra de la Coruña Km 7.5; E-28040 Madrid, Spain jmnavas@inia.es

Monolayered graphene shows a unique structure constituted by one-atom thick two-dimensional crystal of sp2 carbon atoms that is responsible of extraordinary physico-chemical properties. As a consequence, graphene has potential applications in so diverse fields as electronics or aeronautics. In addition, graphene can interact with other substances facilitating their transport to the inner of cells what opens the possibility of interesting applications in medicine, and agriculture and livestock farming. The wide spectrum of graphene applications increases also the possibility of release to the environment where it could cause deleterious effects on organisms. Nevertheless, interplay of graphene with environmental toxicants (pollutants) could modulate their toxicity. Taking all this into account, we performed a series of experiments (see references 1, 2 and 3) with the general objective of determining the mechanisms underlying the toxicity of graphene oxide (GO) platelets to different cell lines in vitro, and describing in detail the interaction of graphene platelets with cellular structures. Finally, we wanted to establish if GO could facilitate the entrance into cells of other substances modulating therefore their potential desired or undesired (toxic) effects. Since liver plays a pivotal role in detoxification processes, two cell lines with liver origin were used: HepG2 (human origin) and PLHC-1 (from the fish Poeciliopsis llucida). Two different GO were used, one of them with a higher number of carboxyl groups that we have named carboxyl-graphene (CXYG). Suspensions of GO and CXYG obtained in cell culture medium were characterized through a variety of techniques including dynamic light scattering (DLS; to determine frequency size distribution), transmission and scanning electron microscopy (TEM and SEM respectively, to establish the platelet shape), and atomic force microscope (AFM, to determine the platelets width). TEM and SEM allowed us also to observe in detail the interaction of GO and CXYG with cell membranes and organelles. Cytotoxicity was assessed by means of AlamarBlue, CFDA-AM (5- carboxyfluorescein diacetate acetoxymethyl ester) and neutral red uptake. Oxidative stress status was determined through reactive oxygen species (ROS) levels, and mitochondrial membrane potential (MMP). Other enzyme activities or expression levels of particular genes informed about effects of interest. Negligible cytotoxicity was observed at concentrations of GO or CXYG lower than 16 µg/ml in both cell lines. Both graphene derivatives interacted with the plasma membrane in both cell lines damaging it. However, at low concentrations (showing barely any decrease in cell viability) GO and CXYG appeared inside cells. Strikingly, in the case of PLHC-1, GO and CXYG accumulations not surrounded by any membrane could be observed, suggesting that internalization occurs through a nonendocytosis mechanism. These results open the door for the use of graphene as carrier of other substances. In parallel, an increase of ROS levels and a reduction of MMP were detected, together with the observation of physical interaction of platelets with mitochondrial membranes.

Therefore, oxidative stress associated with damage of cellular ultrastructure constitutes probably an important cause of toxicity. When cells were first pre-exposed to GO or CXYG or co-exposed to GO or CXYG and some environmental pollutants, all of them inducers of cytochrome P4501A (CYP1A), an enhancement of the expression of this cytochrome was observed at the transcriptional level together with an increase of the CYP1A dependent EROD (ethoxyresorrufin-O-deethylase) enzyme activity. This effect did not occur when cells were post-exposed to graphene derivatives, suggesting that graphene platelets favor the accumulation of pollutants inside the cells possibly by passive diffusion after damaging cell membranes.

125

References [1] [2] [3]

126

Lammel T, Boisseaux P, Fernรกndez-Cruz ML, Navas JM, Particle and Fiber Toxicology, 10 (2013) 27.

Lammel T, Navas JM, Aquatic Toxicology, 150 (2014) 55-65.

Lammel T, Boisseaux P, Navas JM, Environmental Toxicology, 30 (2015) 1192-1204.

Effect of adding oxide ceramic nanoparticles into free-formaldehyde wood adhesive for preparing particleboards Juan José Ortega Gras1, Mª Virtudes Navarro Bañón1, C. del Castillo2, Raquel Fernández2, Arne Schirp3, Maria Brodel3 1

Technical Research Centre of Furniture and Wood of Region of Murcia (CETEM). C/ Perales s/n, Yecla, Murcia, Spain.

2 Tecnologías Avanzadas Inspiralia S.L. C/Estrada 10B, Madrid, Spain, 28034.

3 Fraunhofer Wilhelm-Klauditz-Institut WKI. Bienroder Weg 54E, Braunschweig, Germany, 38108. jj.ortega@cetem.es

Several nanoparticles have been used in several polymeric systems and improvements related with mechanical properties and changes in the curing process of thermo-stable resins have been detected [1-5].

In this work, the use of oxide ceramic nanoparticles (SiO2, TiO2, ZrO2, etc) in wood adhesive for wood panel production was analyzed to determine the effect on its properties and performance as wood adhesive for obtaining particleboards. However, instead of using formaldehyde based wood adhesive which are commonly used in industrial production process of wood panels, a free formaldehyde resin was used.

Despite the toxicity of formaldehyde, dangerous for the human health and environment, the use of resin based on formaldehyde as wood adhesive in the industrial production process of wood panels (particleboard, fiberboard, plywood, etc.) remains due to technical performance and economical reasons.

Great efforts have been carried out for years to find alternative resins free of formaldehyde which could be used instead the conventional ones. Several studies have been carried out to analyze the possibility of reducing or avoiding the use of free-formaldehyde resins using bio-resins such as tannins, lignin and liquefied wood or synthetic resins with a different chemical nature respect to conventional ones such as polyacrylate or polyester resins. Recently, a European regulation Nº 605/2014 was enforced about the new classification of formaldehyde as carcinogenic 1B. This regulation requires compliance with a series of protective measures at industrial scale and the search of alternative materials free of formaldehyde for the same use if it is possible since the technical point of view. Nowadays, there are commercial free formaldehyde resins in the market with high possibilities of being used as wood adhesives.

In this work, a free formaldehyde resin was selected as wood adhesive for particleboard and several oxide ceramic nanoparticles were used to analyze the effect of them in the properties of the resin and finally on the properties of particleboard samples obtained at laboratory scale. The analysis of optimal dispersion methods, the study of nanoparticles dispersion stability, the analysis of the effect of nanoparticles on the curing process of the resin and also on its physical and mechanical properties and finally the effect of nanoparticles on the properties of particleboard samples obtained at laboratory scale were carried out.

These results have been obtained across the Ecopresswood project financially supported by the Seventh Framework Programme of the European Commission.

References [1]

Xiaolin Cai, Bernard Riedl, Hui Wan, S.Y. Zhang, Xiang-Ming Wang. Composites: Part A, 41 (2010) 604-611.

[2] Lei H, Du G., Pizzi A., Celzard A., Fang Q. J. Adhes. Sci. Technol. 24 (2010) 1567-1576.

[3] Veigel S, Rathke J, Weigl M, Gindl-Altmutter W. J Nanomater 8 (2012)1-8.

[4] H.R. Taghiyari and A. Moradiyan. Int. J. Nano Dimens. 5 (4) (2014) 379-386.

[5] Wei Gao, Jinzhen Cao, D. Pascal Kamdem. Maderas. Ciencia y Tecnología 13 (2011) 203-210.

127

Innovative Graphene Applications Alfredo Pacheco Tanaka, Izaskun Bustero and Yolanda R. de Miguel Nanotechnology Cluster, TECNALIA, Mikeletegi 2, San Sebastian, Spain alfredo.pacheco@tecnalia.com

Our approach in the identification of potential innovative graphene applications starts from a societal point of view, by identifying current needs in a wide-range of fields, such as energy, health, industry, construction, etc.

Our sound technological knowledge enables us to identify problems and applications for this new material, which can greatly benefit society.

Once identified, thanks to our state-of-the art laboratories, our objective is to develop prototypes which can solve the identified problems. Finally, a feasible solution is designed and transferred to industry.

Here we present some examples of our R+D activities, which are focused on the following industrial applications of graphene: • • • • •

WATER DESALINATION ENERGY STORAGE PRINTED ELECTRONICS THERMAL MANAGEMENT OF ELECTRONICS SENSING FUNCTIONALITIES IN COMPOSITE STRUCTURES

Single-molecule spintrometry: measuring and tuning the spin states of a molecule with STM J.I. Pascual CIC nanoGUNE, 20018 Donostia – San Sebastián, Spain Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain ji.pascual@nanogune.eu

Molecular electronic spins are the basics of molecular magnetic materials. In an organic molecule they acquire special relevance because the organic ligands sculpt an anisotropic field that minimizes the energy when the spin points along one direction. This magnetic anisotropy is thus a key factor in molecular magnetism. However, it responds strongly to variations of the local environment of the molecule, including deformations, electrical interactions, bonds…

As model systems for molecular magnetism, we investigate transition metal porphyrins on metal surfaces.

In many cases the magnetic state of the free molecule is maintained on the metal. Using scanning tunneling microscopy and spectroscopy we resolve spin-induced spectral fingerprints on individual atoms and molecules [1,2] that allow us to prove the existence of anisotropy in the spin orientation and determine its dependence on local molecular arrangement.

References [1] [2] Figures

B.W. Heinrich, L. Braun, J.I. Pascual, K.F. Franke. Nat. Phys. 9, 765 (2013).

B.W. Heinrich, L. Braun, J.I. Pascual, K.F. Franke. Nanolett 15, 4024 (2015).

129

Enzymatic etching of nonoparticles in biosensing Valery Pavlov, Laura Saa, Ruta Grynite, Marc Coronado-Puchaua, Luis Liz-Marzan CIC Bioma GUNE, Paseo Miramon 182, San Sebastian, Spain vpavlov@cicbiomagune.es

The physical properties of inorganic nanoparticles (NPs) depend on their shape, size and composition.

Noble metal NPs exhibit strong localized surface plasmon resonances (LSPR) in the visible or near-IR wavelength range. Hence, metal and semiconductor NPs of different nature have found broad application in imaging and colorimetric bioanalytical assays. Gold nanorods (AuNRs) and fluorescent semiconductor quantum dots (QDs) can be employed as a highly sensitive platform to probe environmental changes through variations in their size. The longitudinal LSPR frequency demonstrated by Au NRs is highly sensitive to minute changes in the AuNR aspect ratio. The emission spectra of spherical QDs depends on their diameter and concentration. We discovered for the first time that the oxidative enzyme Horseradish Peroxidase is able to produce free radicals which oxidize AuNRs and semiconductor QDs. We introduced novel bio-analytical assays based on enzymatic etching of inorganic nanoparticles. HRP is able to induce a gradual oxidation of the AuNRs in the presence of trace concentrations of H2O2 and halide ions. [1] As a consequence, other enzymatic reactions, carried out by Glucose Oxidase (GOx) can be easily coupled to the HRP activity assay, thereby allowing for the detection of different amounts of glucose.

130

Modification of AuNRs with thiol-containing organic molecules such as glutathione and thiocholine hinders enzymatic etching of AuNR. Higher concentrations of thiol-containing molecules in the reaction mixture gradually decrease the rate of enzymatic etching. Interestingly, the decrease in the rate of AuNR shortening can be easily monitored by UV-Vis spectroscopy, through changes in the longitudinal LSPR band, highly sensitive to variations in AuNR aspect ratio. This effect can be applied to develop the novel optical assays for acetylcholine esterase (AChE) activity (Figure 1). The biocatalytic hydrolysis of acetylthiocholine by AChE yields thiocholine, which prevents enzymatic AuNR etching in the presence of HRP. [2] We also descovered a facile, mild and inexpensive enzymatic etching method for resizing of CdS QDs. It was found out that the biocatalytic process involving bromide, HRP and H2O2 decreased the size of semiconductor CdS QDs. Thus, this phenomenon can be applied to resizing of semiconductor CdS QDs under mild physiological conditions and rapid and sensitive detection of H2O2 and HRP (Figure 2). It was proven that CdS QDs immobilized on polyvinyl chloride microspheres can be etched biocatalytically too.

Thus, we introduced a new platform for optical detection of analytes based on etching of semiconductor NPs. [3]

References [1] [2] [3]

Saa L, Coronado-Puchau M, Pavlov V, Liz-Marzรกn LM, Nanoscale. 6(13) (2014) 7405.

Saa L, Grinyte L, Liz-Marzรกn LM, Pavlov V. manuscript in preparation.

Grinyte R, Saa L, Garai-Ibabe G, Pavlov V, Chem. Commun., 51, (2015),17152.

Figures

Figure 1: Protective effect of thiol molecules (R-SH) against biocatalytic oxidative etching of AuNRs.

Figure 2: Enzymatic etching of CdS QDs.

131

Additive Free, Single Layer Graphene in Water Alain Pénicaud1, George Bepete1, Eric Anglaret2 & Carlos Drummond1 1

Centre de recherche Paul Pascal - CNRS, Université de Bordeaux, France Laboratoire Charles Coulomb, Université de Montpellier - CNRS, France penicaud@crpp-bordeaux.cnrs.fr

2

Full exfoliation of graphite to form thermodynamically stable, negatively charged, graphene (graphenide) flakes in solution can be achieved by dissolution of graphite intercalation compounds (GICs) in low boiling point aprotic organic solvents under inert atmosphere. [1,2] We now report that, under certain conditions, graphenide can be transferred to water as single layer graphene. The organic solvent can then be evaporated to remain with an aqueous graphene suspension of ca 0.15 mg/ml concentration under ambient atmosphere. The Raman spectra (2.33 eV laser) collected in situ on such dispersions show bands at 1343, 1586, 1620 and 2681 cm-1 corresponding to the D, G, D’ and 2D bands of graphene respectively.

The 2D band at 2681 cm-1 is well fitted with a sharp lorentzian line (∼28 cm-1) which is a hallmark of single layer graphene. [3] We have thus succeeded in preparing air stable, bulk suspensions of single layer graphene in water. [4] Upscaling towards industrial production of this graphene waters is underway.

References

132

[1] [2] [3] [4]

A. Catheline et al. Soft Matter, 12, 7882, (2012).

A. Pénicaud & C. Drummond, Acc. Chem. Res. 46, 129 (2013).

Y.Y. Wang et al. J. Phys. Chem. C., 112(29), 10637, (2008).

G. Bepete, C. Drummond, A. Pénicaud, European patent, June 12, 2014, EP14172164.

Synthesis of iron based nanoparticles in presence of nanocellulose for contaminant removal Uxua Pérez de Larraya1,2, Houssine Sehaqui2, Juncal Estella1, Tanja Zimmermann2 1

CEMITEC, Centro multidisciplinar de tecnologías para la industria, Polígono Mocholí – Plaza Cein, 4, 31110 Noain, Spain EMPA, Materials Science and Technology, App. Wood Materials Lab., Überlandstrasse 129, 8600 Dübendorf, Switzerland uperezdelarraya@cemitec.com

2

Nanocelluloses are natural biopolymers having a diameter in the nano scale. They have recently attracted great research and industrial attention as a multifunctional material to be used in a wide range of applications including packaging, medical and automotive applications, electronics, photonic devices and environmental remediation [1].

Due to their good biodegradability, biocompatibility, non toxicity, porosity, and rich surface in hydroxyl groups, nanocelluloses are promising materials to be used as template for various synthesis reactions [2].

In parallel, iron-based nanoparticles have shown great potential in the last decade for in situ soil remediation and water decontamination. However, the poor chemical stability, mechanical strength and aggregation tendency of iron-based nanoparticles makes it relevant to investigate new approaches to enhance their performance over time [3].

The in-situ synthesis of iron nanoparticles in the presence of nanocellulose is an interesting strategy to generate a biobased composite with enhanced stability and higher contaminant adsorption capacity, due to the additional cellulose functionality. Furthermore, such composite is easy to recover from treated effluents through the action of magnets.

In the present work, the synthesis of iron nanoparticles was carried out in the presence of nanocelluloses with the aim to obtain a novel material for contaminant removal. Since iron salts bind to hydroxyl groups of nanocellulose via electrostatic interaction, this forms oxyhydroxides that act as nucleation points for the growing of iron nanoparticles via reduction. Subsequently, the aggregation of these iron nanoparticles is avoided allowing a better and more homogeneous size distribution (Figure).

Different nanocellulose derivatives and different synthesis conditions were tested. The resulting material was characterized with X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller analysis (BET), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Finally, the decontamination ability of the iron nanoparticles/nanocellulose composite was evaluated and revealed the high efficiency of the novel material.

References [1] [2] [3]

Shatkin J.A, Wegner T.H, Bilek, E.M, Cowie J., Tappi Journal, 3 (2014) 9-16.

Menchaca-Nal S., Londoño-calderón C.L., Cerrutti P., Foresti M.L., Pampillo L., Bilovol V., Candal R., Martínez-García R., Carbohydrate Polymers, 5 (2016) 726-731.

Zhang, W.X., Journal of Nanoparticle Research, 5 (2003) 323-332.

133

Figures

Figure 1: Iron based nanoparticles synthesized onto nanocelluloses.

134

Silver and copper selenide: New approach in manufacture of highly efficient thermoelectric Jaime Andrés Pérez Taborda, Fernando Briones Fernández-Pola, Marisol Martin-González Instituto de Microelectrónica de Madrid (IMM-CSIC), C/ Isaac Newton 8, Tres Cantos, 28760 Madrid, Spain jaimeandres.perez@csic.es

The current interest in thermoelectric materials (TE) focuses on its ability to transform a temperature difference in a voltage difference (Seebeck effect). Similarly to the creation of a temperature difference due to an electric voltage (Peltier effect), it is possible to use them as heat sources and sinks in industrial applications as an alternative cooling medium and cooling. [1] The main advantages of thermoelectric devices over other cooling systems - compression systems - is a more reliable usage time by not having moving parts, non-use of greenhouse gases and the absence of vibration due they are solid state devices with reduced size becoming very efficient in local applications.

Increasing the efficiency of a thermoelectric material necessitates increasing the figure of merit, usually called zT. The zT is composed of three material’s parameters as well as the absolute temperature T. zT =( S2σ )κ -1 in which S is the Seebeck coefficient, σ is the electrical conductivity, and κ =κe + κp is the thermal conductivity ( κe and κp are the electron and phonon contributions respectively.[2] The TE performance is maximized by realizing excellent electrical transport and poor heat conduction in solid materials.

The n-type Ag2+xSe and p-type Cu2+xSe has promising thermoelectric properties. Previous investigations on Ag2Se report that it has high electrical conductivity and low thermal conductivity and that it zT approaches 1 at room temperature. [3] The reported zT increases as temperature increases from 70 K to room temperature. This is especially encouraging because Ag2Se becomes a superionic conductor around 407 K, as does Cu2Se, which has been reported to have a zT that increases with temperature to 1.5 at 1000 K. [4] Report a new approach in manufacture of highly efficient thermoelectric via reactive sputtering. This new manufacturing technology allows to control the stoichiometry of the samples, the crystallographic orientation and thermoelectric properties. It is fully reproducible and scalable to the industry today. In Figure 1 it is shown as morphology is influenced depending these stoichiometries changes.

References [1] [2] [3] [4]

D. M. Rowe, Thermoelectrics handbook: macro to nano (CRC press, 2005).

T. M. Tritt, Thermal conductivity: theory, properties, and applications (Springer Science, 2004).

T. Day, F. Drymiotis, T. Zhang, D. Rhodes, X. Shi, L. Chen, and G. J. Snyder, Journal of Materials Chemistry C 1, 7568 (2013).

H. Liu et al., Nature materials 11, 422 (2012).

135

Figures

Figure 1: The low-Seebeck phase is composed of well-densified plate-like grains with sizes about a micron, while the highSeebeck phase shows small grains of tenths-of-micron size.

136

Metrology for Graphene and 2-D Materials: Characterisation and Standardisation for an Emerging Industry Andrew J. Pollard National Physical Laboratory, Teddington, TW11 0LW, United Kingdom Andrew.pollard@npl.co.uk

Graphene has already demonstrated that it can be used to the benefit of metrology as a new quantum standard for resistance [1]. However, there are many application areas where graphene and other 2-D materials may be disruptive; areas such as flexible electronics, nanocomposites, sensing, filtration membranes and energy storage [2]. Applying metrology to the area of graphene is now paramount to enable the emerging global graphene industry and bridge the gap between academia and industry.

Measurement capabilities and expertise for a wide range of scientific areas are required to address this challenge. The combined and complementary approach of varied characterisation methods for structural, chemical and electrical properties, will allow the real-world issues of commercialising graphene and other 2-D materials, such as determining the suitability and realistic performance enhancement of grapheneenabled products for the many different types of graphene, to be addressed.

Examples of metrology challenges that have been overcome through cross-disciplinary research, newly developed measurement techniques and collaboration with both academia and industry will be discussed, for specific consumer application areas, using both established and emerging measurement techniques such as Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS) and secondary ion mass spectrometry (SIMS).

We will discuss the quantitative determination of the lattice disorder present in graphene layers through studying the evolution of Raman spectra with defect size and density, for vacancy defects created via carefully controlled ion bombardment, and explore how this enables an accurate determination of the phase-breaking length of graphene. This is further extended to other 2-D materials such as MoS2 and we investigate the application of Raman spectroscopy for quantification of defects in these systems. We will further discuss understanding the measurement of real-world graphene samples, and the application of routine industry ready techniques, such as controlled mass-selected argon cluster cleaning to remove polymer residues present on the transferred graphene surface, which minimise damage to the underlying graphene. The application of SIMS measurements in these studies will be discussed, and further details of how it can be applied to the understanding of the growth mechanisms of graphene and other 2-D materials on metal catalysts will be explored. Other more novel applications of SIMS in relation to the characterisation of dispersed graphene materials in polymer composites for flexible device technologies, and how it can aid in identifying contamination and the degree of dispersion of different graphene products will also be presented. In addition, how these metrology investigations ultimately lead to the development of international graphene standards will also be described.

References [1] [2]

T.J.B.M. Janssen et al. Rep. Prog. Phys. 76 (2013) 104501.

K.S. Novoselov et al. Nature, 490 (2012) 192.

137

The Quest for Charge Transport in single Adsorbed Long DNA-Based Based Molecules

Danny Porath Institute of Chemistry and Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, 91904 Israel danny.porath@mail.huji.ac.il

138

DNA and DNA-based based polymers have been at the focus of molecular electronics owing to their programmable structural versatility. The variability in the measured molecules and experimental setups, caused largely by the contact problem, has produced a wide range ge of partial or seemingly contradictory results, highlighting the challenge to transport significant current through individual DNA DNA-based molecules.

A well-controlled controlled experiment that would provide clear insight into the charge transport mechanism through a single long molecule deposited on a hard substrate has never been accomplished. In this lecture I will report on detailed and reproducible charge transport in G4-DNA, DNA, adsorbed on a mica substrate. Using a novel benchmark process for testing molecular conductance ductance in single polymer wires, we observed currents of tens to over 100 pA in many G4-DNA DNA molecules over distances ranging from tens to over 100 nm, compatible with a long-range thermal hopping between multi-tetrad tetrad segments. With this report, we answer a long-standing standing question about the ability of individual polymers to transport significant current over long distances when adsorbed a hard substrate, and its mechanism. These results may re re-ignite the interest in DNA-based wires and devices towards a practical tical implementation of these wires in programmable circuits.

Keywords: Molecular electronics, Single molecules characterization, DNA-based based Nanotechnology References [1] [2]

"Direct measurement of electrical transport through DNA molecules", Danny Porath, Alexey Bezryadin,Simon de Vries and Cees Dekker, Nature 403, 635 (2000). Cited 1312 times times.

"Charge Transport in DNA-based based Devices", Danny Porath, Rosa Di Felice and Gianaurelio Cuniberti, Topics in Current Chemistry Vol. 237, pp. 183-228 228 Ed. Gary Shuster. Springer Verlag 2004. Cited 193 times.

[3]

[4]

[5] [6]

[7] [8] [9] [10] [11]

[12] [13]

[14]

“Direct Measurement of Electrical Transport Through Single DNA Molecules of Complex Sequence”, Hezy Cohen, Claude Nogues, Ron Naaman and Danny Porath, PNAS 102, 11589 (2005). Cited 201 times.

“Long Monomolecular G4-DNA Nanowires”, Alexander Kotlyar, Nataly Borovok, Tatiana Molotsky, Hezy Cohen, Errez Shapir and Danny Porath, Advanced Materials 17, 1901 (2005).

Cited 70 times.

“Electrical characterization of self-assembled single- and double-stranded DNA monolayers using conductive AFM”, Hezy Cohen et al., Faraday Discussions 131, 367 (2006). Cited 42 times.

“High-Resolution STM Imaging of Novel Poly(G)-Poly(C)DNA Molecules”, Errez Shapir, Hezy Cohen, Natalia Borovok, Alexander B. Kotlyar and Danny Porath, J. Phys. Chem. B 110, 4430 (2006). Cited 24 times.

"Polarizability of G4-DNA Observed by Electrostatic Force Microscopy Measurements", Hezy Cohen et al., Nano Letters 7(4), 981 (2007). Cited 56 times.

“Electronic structure of single DNA molecules resolved by transverse scanning tunneling spectroscopy”, Errez Shapir et al., Nature Materials 7, 68 (2008). Cited 93 times.

“A DNA sequence scanned”, Danny Porath, Nature Nanotechnology 4, 476 (2009).

“The Electronic Structure of G4-DNA by Scanning Tunneling Spectroscopy”, Errez Shapir, et.al., J. Phys. Chem. C 114, 22079 (2010).

“Energy gap reduction in DNA by complexation with metal ions”, Errez Shapir, G. Brancolini, Tatiana Molotsky, Alexander B. Kotlyar, Rosa Di Felice, and Danny Porath, Advanced Maerials 23, 4290 (2011).

"Quasi 3D imaging of DNA-gold nanoparticle tetrahedral structures", Avigail Stern, Dvir Rotem, Inna Popov and Danny Porath, J. Phys. Cond. Mat. 24, 164203 (2012).

"Comparative electrostatic force microscopy of tetra- and intra-molecular G4-DNA", Gideon I. Livshits, Jamal Ghabboun, Natalia Borovok, Alexander B. Kotlyar, Danny Porath, Advanced materials 26, 4981 (2014).

"Long-range charge transport in single G4-DNA molecules", Gideon I. Livshits et. al., Nature Nanotechnology 9, 1040 (2014).

139

Electrical Characterization of polymer matrix graphene composites Imanol Recio1,2, Julio Gomez1 and Elvira Villaro3,4 1 AVANZARE, Avda. Lentiscares 4-6, Navarrete, Spain Departamento de Químicas. Universidad de La Rioja, Madre de Dios, 53 Logroño, Spain 3 Instituto de Tecnologías Químicas Emergentes de La Rioja; San Francisco, 11 Navarrete, Spain 4 Departamento de Química Inorgánica y Técnica, UNED. Senda del Rey, 9, Madrid, Spain. irecio@avanzare.es 2

Nanocomposites are high performance materials that exhibit unusual properties and thus are of high interest in material science. Carbon based materials have been widely used as reinforcements in polymers.

Several authors have used graphene as filler in different polymer matrix (olefin, acrylic, styrene, polyurethane and vinyl) showing important improvements in electrical, thermal and mechanical properties. Factors as processing technique, dispersion and compatibility between graphene and matrix have an extremely high importance in the results.

This poster deals on the electrical characterization of 2D nanocomposites. Some reduce graphene oxide has been prepared and characterize. The reduce graphene oxides, with different lateral size, thickness and defects, have been combined with different polymer matrices (PVC-plastisol, epoxy-resin, Polyamide 6 and TPU) to obtain a series of nanocomposites. Electric impedance spectroscopy (EIS) is the technique used to characterize electrically these nanocomposites and analyse the dielectric relaxations of these composites.

140

Very low percolation loads have been reached appreciating conductivity in composites with load as low as 0,13%w. in TPU composites or 0,3%w in epoxy-resin composites. The effect of temperature has been studied seeing a very high increase of the electrical conductivity with the temperature. The conductivity mechanism and the effect of the humidity in function of the temperature has been also studies.

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement no. 642890 www.thelinkproject.eu References [1]

[2]

[3]

[4]

Cunningham G, Lotva M, McEvoy N, Duesberg GS, Van Der Schoot P and Coleman JN. 2012.

Percolation scaling in composites of exfoliated MoS2 filled with nanotubes and graphene.

Nanoscale, 4, 6260-6264.

Khanam P N, Ponnamma D and AL-Madeed M A 2015 Electrical Properties of Graphene Polymer Nanocomposites Graphene-Based Polymer Nanocomposites in Electronics (Springer Series on Polymer and Composite Materials DOI 10.1007/978-3-319-13875-6) pp 25–47.

Galindo B, Gil Alcolea S, Gómez J, Navas A, Ortega Murguialday A, Pérez Fernandez M and Puelles R C 2014 Effect of the number of layers of graphene on the electrical properties of TPU polymers IOP Conf. Ser.: Mater. Sci. Eng. 64 012008 http://dx.doi.org/10.1088/1757899X/64/1/012008.

Liao K H, Qian Y, Macosko C W 2012 Ultralow percolation graphene/polyurethane acrylate nanocomposites Polymer 53 3756–61.

Patchy nanoparticles at the air-liquid liquid interface: contact angles and adsorption energies measured by neutron reflectivityl Javier Reguera1,2, Evgeniy Ponomarev1 ,Thomas Geue4 ,Francesco Francesco Stellacci1 , 5 Fernando Bresme , Mauro Moglianetti6 1

CIC BiomaGUNE, Paseo de Miramón 182C, 20009 Donostia-San San Sebastian, Spain 2 Ikerbasque, Basque Foundation for Science, 48011 Bilbao, Spain 3 Institute of Materials, École Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland 4 Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, 5232 Villigen, Switzerland 5 Department of Chemistry, Imperial College, SW7 2AZ, London, United Kingdom 6 Center for Biomolecular Nanotechnologies (CBN), Istituto Italiano di Tecnologia, 73010 Arnesano, Italy jreguera@cicbiomagune.es

The properties of nanoparticles (NPs) at the air-liquid, liquid-liquid, liquid, and solid solid-liquid interfaces have attracted strong interest in the last years for their scientific and technological importance importance.[1] A better understanding of these interfacial systems is crucial to shed light on complex physical processes like heterogeneous catalysis, electron transfer, biological surface activity, biosensing and self self-assembly. The control of the interfacial properties will help to design better systems for controlled trolled emulsions with long stability, improved 2D supracrystals for catalysis, or plasmonic surfaces for SERS among others.

We present here a novel experimental approach based on neutron reflectivity (NR) that allows the in situ measurement of the contactt angles, energy of absorption and interfacial energies of nanoparticles adsorbed at fluid interfaces.2 Because our method provides a route to quantify the adsorption and interfacial energies of the nanoparticles in situ,, it circumvents problems associated to existing indirect methods, which rely on the transport of the monolayers to substrates for further analysis. We illustrate the method by measuring the contact angle of hydrophobic nanoparticles coated by octanethiol (d (d-OT) and the more hydrophilic patchy NPs coated with a mixture of d-OT OT and mercaptohexanol (MHol), respectively.[2] The contact angles were also calculated via atomistic molecular dynamics (MD) computations, showing excellent agreement with the experimental data. Our method opens the route to quantify the adsorption of complex nanoparticle structures adsorbed at fluids interfaces featuring different chemical compositions.

References [1] [2]

Figures

A. Maestro, E. Guzmán, F. Ortega and R. G. Rubio, Curr. Opin. Colloid Interface Sci., 19 (2014), 355.

J. Reguera, E. Pnomarev, T. Geue, F. Stellacci, F. Bresme and M. Moglianetti, Nanoscale, 7 (2015) 5665.

141

Fabrication and molecular scale characterization of selenium nanoparticles produced by Stenotrophomonas sp. BII-R7 Ruiz-Fresneda MA, SĂĄnchez-Castro I, Merroun ML University of Granada, Faculty of Sciences, Department of Microbiology, Campus Fuentenueva 18071, Granada, Spain mafres@ugr.es

The main objective of the present work is to characterize the structure and size of selenium nanoparticles (Se NPs) produced by the bacterial strain Stenotrophomonas sp. BII-R7, using a combination of microbiological, spectroscopic and microscopic techniques. There are several microorganisms described for their ability to interact with selenium (Se), reducing toxic forms [selenite or Se(IV)] to less toxic forms [elemental selenium or Se(0)] [1]. This is the case of the strain Stenotrophomonas sp. BII-R7, in which the reduced Se(0) produced, was accumulated in form of nanoparticles. Preliminary BII-R7 draft genome analysis revealed the presence of glutathione-related enzymes, NADH-dependent enzymes or thioredoxin reductase described for their ability to reduce Se(IV) to Se(0).

142

The Se NPs obtained were analyzed using X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), high resolution STEM (Scanning-Transmission Electron Microscopy) equipped with HAADF (HighAngle Annular Dark Field) detector and EDX (Energy Dispersive X-ray Spectrometry). XRD analysis indicated the small average size (15 nm) and crystalline hexagonal structure of the Se NPs produced by this bacterial strain. In addition, using this technique, the Se NPs production procedure was optimized by studying the effects of different physicochemical parameters (Se initial concentration, incubation time, type of washing agents used, etc.) on diffraction patterns. On the other hand, STEM-HAADF and EDX microanalysis showed the presence, in addition to small sized Se NPs, of very few extracellular and intracellular amorphous Se NPs around 200 nm of diameter. Finally, the effects of selenium toxicity on cellular viability and consequently, on Se NPs production by Stenotrophomonas sp. BII-R7 were also determined using Flow Cytometry. Definitely, this work describes a microbiological method to produce Se biogenic NPs of different size and morphology, with potential industrial and medical applications.

References [1]

Antonioli P, Lampis S, Chesini I, Vallini G, Rinalducci S, Zolla L, Righetti PG, Appl Environ Microbiol, Stenotrophomonas maltophilia SeITE02, a New Bacterial Strain Suitable for Bioremediation of Selenite-Contaminated Environmental Matrices (2007) 73(21): 6854â&#x20AC;&#x201C;6863.

Nanotoxicology for safe development of nanomaterials: light and shadows E. Sabbioni CeSI- Aging Research Center, â&#x20AC;&#x153;G. dâ&#x20AC;&#x2122;Annunzioâ&#x20AC;? University Foundation, 66100 Chieti, Italy enrico.sabbioni@alice.it

The nanotech tsunami of engineered nanomaterials (NM) raises the issue of their impact on environmental and human health, being more and more widespread in industrial and biomedical applications, as well as in everyday life. Since emerging evidence that even at the cellular level NM behave differently from the corresponding bulk materials, the protection of public health, consumers and workers in this sector is now a topic of enormous interest that is taken into serious consideration by the competent authorities in charge in environmental and health safety. In this context, it is a decade since nanotoxicology is recognized as a sub-discipline of toxicology with the aim of: obtaining information on adverse effects of NM and the possible ways of contact with humans and the ecosystem; developing appropriate research guidelines; providing a scientific basis to reduce the uncertainty of the risk assessment. Unfortunately, although hazard assessment of NM has made a significant progress, the nanotoxicology has not produced the desired results in terms of scientific knowledge relevant for the risk assessment. This is mainly due to a poor collaboration/communication between the various projects, despite a substantial EU Framework Programme funding in this matter. In particular, although in the last decade some biological effects of NM have been documented we still lack a fundamental understanding about modes of action and mechanisms leading to toxicity and aspects of biokinetics and its impact on toxicity. Moreover, significant uncertainties on methodological framework (incomplete physicochemical characterization, unrealistic doses, different biological models, absence of validated methods) and vague and fragmentary data on NM in consumer products equalize the nanotoxicology to a "fishing trip in the sea of uncertainty", making difficult to support research and regulation.

Herein we discuss: (i) the biological effects of NM as emerged from nanotoxicology research by in vivo and in vitro biological models (ii) key factors concerning the modes of action of NM in relation to their toxicity (physicochemical characterization, interaction with biological fluids, uptake, intracellular trafficking); (iii) concerns about the potential risk as consequence of human exposure to nanoparticles via food and cosmetics; (iv) strategic priorities for future nanotoxicology research, i.e. its evolution from being an observational into a predictive discipline. In this context, the crucial need is to clarify NM toxicity pathways which lead to understanding the molecular fundamentals in groups of NM with marked similarities. This in order to include the mechanistic knowledge in the technology development, to help in the safe design of new NM, and to be into the development of a rational testing approach. In addition, most of the current nanotoxicology research deals with the 1 st generation NM. However, 2 nd and 3rd generation NM will appear soon on markets and appropriate testing for such NM should be developed. Nanotoxicology must keep away from two extremes: on one side, to generate superficial information to draw the attention of the media or the public, or to arouse distrust towards nanotechnology for ideological but not scientific reasons; on the other side, to remain silent in front of the conduct of industrial operators more interested in marketing consumer products that have not received the necessary controls. In this context, only a close cooperation between producers, users and researchers in the area of nanosafety will lead to a sustainable and safe development of nanotechnology. In any case, nanotoxicology will play a central role in prevention science if it can give a sound scientific basis and establish itself in the global context as a responsible and independent discipline.

143

The Application of Permanent Magnets Materials in Electrical motors Nawal Sabri, ghoutia naima sabri University of Abou Bakr Belkaid, Tlemcen, University of Tahri Mohamed, Bechar, Algeria sabri_nm@yahoo.fr

This study concerns the permanent magnets and their applications in the electric motors. It treats the losses in these materials: losses in normal mode "loss of hysteresis" and in sinusoidal mode by using the formula of Steinmetz. This enabled us to know which are the desirable qualities of the permanent magnets to make them suitable for high power applications, such as motors, generators and power transformers.

These magnetic materials have a great importance because they reduced the size of motors considerably and allow stepping motors to be developed with very high rotational accuracy which form the back bone of hard drives in computers.

The magnetic losses of ferrite PM are discussed for different samples. To minimize the losses in such materials, the choice of the frequency of operation is indispensable for two reasons:The fact that these losses depend of the frequencyand each sample of material has its own frequency band where it works with less loss.

References [1]

144 [2] [3] [4] [5]

H. Lewis, F. J.Villacorta, “Perspectives on permanent magnetic materials for energy conversion and power generation”, The Minerals, Metals & Materials Society and ASM International, vol44A, pp. 2-20, Jan 2013.

G.N.Sabri et al., “Magnetic materials for clean environment energy applications”, AWER Procedia Advences in Applied Sciences, Vol 1, pp. 989-995, 2013. Özgür et al., Microwave Ferrites, Part 1: Fundamental properties, Journal of Materials Science: Materials in Electronics, pp.14-15, 2009.

Valenzuela, R. Novel Applications of Ferrites, Hindawi Publishing Corporation, Physics Research International, Volume 2012, p 2, 2012.

M .Verite, « Etude de dépôts de ferrite pour dispositifs intégrés micro-ondes non réciproques », Thèse de Doctorat à l’université de Limoges, France, Soutenue le 14 novembre 2002, p.p 10-33.

Figures

Figure 1: The magnetic losses versus frequency (3C85) at T=100°C.

Figure 2: The magnetic losses versus frequency (3C90) at T=100°C.

INL next decade - a general perspective and a specific look at INLâ&#x20AC;&#x2122;s energy research Sascha Sadewasser and Lars Montelius INL - International Iberian Nanotechnology Laboratory, 4715-330 Braga, Portugal

The decision to create an International Research Laboratory, taken by the Spanish and Portuguese Governments in 2005 led to the International Iberian Nanotechnology Laboratory (INL), which started operations in 2011 in Braga, Portugal. With the first four years dedicated to the installation of equipment and building up the research and administrative personnel, INL enters now into the next decade with ~100 scientists and technicians dedicated to perform world class research and development in four research areas, health, food and environment, information and communications technology, and energy. In the future, a strong portfolio in these research areas will be developed. In addition, INL will provide services to the international community through its six competence centers: nanofabrication, nanosynthesis, highresolution imaging, bio-photonics, life-science characterization, and sensor&systems centers.

The presentation will give a more detailed insight on the different research and development activities in the energy research area. Here, materials research is developed in the field of renewable energy harvesting from the sunlight. Two approaches are followed in-depth, solar water splitting and photovoltaic energy conversion. In both activities a special focus is given to the potential of incorporating nanomaterials o nanostructures into power conversion devices. The recent progress in these areas is presented in several specific examples.

145

From basic Nanowire research to real-world applications Lars Samuelson Lund University, NanoLund/Solid State Physics Box 118, S-221 00 Lund, Sweden

Semiconductor nanowires are ‘needle’-like structures with unique materials, electronic and optical properties that renders them promising for next-generation applications in fields like opto/electronics, energy systems and life sciences. An intensive and world-wide research effort in the field of nanowires was launched in the late 1990s, about ten years after the pioneering work by Dr. Hiruma at Hitachi, Japan. In my research group we spent the first five years on fundamental studies of the materials growth and the materials physics of nanowires, especially heterostructure systems [1], while in parallel also developing novel methods that combined top-down patterning with bottom-up self-assembly, to enable the reproducible fabrication of perfectly ordered nanowire arrays [2], [3].

From around 2005 it became evident that this blue-sky materials research [4], [5] offered significant advantages and opportunities for various applications, primarily in enabling high-speed [6] and optoelectronics devices by monolithic integration of III-V nanowires with silicon [7]. We have also explored ways in which these nanostructures can be used for energy scavenging [8] and in applications that enable energy conservation [9].

146

In this talk I will also present my perspective of broader materials research considerations related to semiconductor nanowires, what the state-of-the-art is, what the key challenges are and focus particularly on the opportunities that these nanostructures present in terms of realizing the nextgeneration of highperformance optoelectronics devices such as solar cells and light-emitting diodes, at a low cost and with low materials consumption [10].

References [1] [2] [3] [4] [5] [6] [7] [8] [9]

M.T. Björk et al., “One-dimensional steeple-chase for electrons…”, Nano Lett 2 (2002) 87.

T. Mårtensson et al., “Fabrication of individually seeded NW…”, Nanotechn. 14 (2003) 1255.

T. Mårtensson et al., “Nanowire arrays defined by nanoimprint litho..”, Nano Lett 4 (2004) 699.

A.I. Persson et al., “Solid-phase diffusion mechanisms for…”, Nature Materials 3 (2004) 677.

K.A. Dick et al., “Synthesis of branched ‘nanotrees’ by…”, Nature Materials 3 (2004) 380.

C. Thelander et al., “Nanowire-based one-dim. electronics”, Materials Today 9 (2006) 28.

T. Mårtensson et al., “Epitaxial III-V nanowires on silicon”, Nano Lett 4 (2004) 1987.

J. Wallentin et al., “InP nanowire array solar cells achieving 13.8%...”, Science 339 (2013) 1057.

B. Monemar et al., “NW-based visible LEDs..”, Semicond. & Semimet Acad. Press/Elsevier (2015).

[10] M. Heurlin et al., “Continuous gas-phase synthesis of nanowires…”, Nature 492 (2012) 90.

Molecular photoswitches as solar energy storage devices Eduardo Santamaría-Aranda, Elena Contreras-García, Raúl Losantos, David Martínez-López, Diego Sampedro, Pedro J. Campos Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja, Madre de Dios 53, 26006 Logroño, La Rioja, Spain edsantam@unirioja.es

In recent years, the use of molecular switches to control diverse properties has become increasingly popular. Among the different types of reported switches, photoswitches have received considerable attention due to practical advantages such as high temporal and spatial resolution and lack of wastage products. The use of these photoswitches has led to a number of amazing applications on the photocontrol of different properties from polymers to liquid crystals or peptide conformations. [1] Most of these applications rely on the use of light to interconvert the system between two different states.

Additionally, the switch could be used also to provide a potential use in its own as energy storage.

Specifically, the energy of a photon could be absorbed and stored in a molecular photoswitch and the difference in energy between the two states could be released once an energy barrier for the backreaction is surmounted. If the absorbed light is solar energy, the switch turns into a solar energy storage. This concept is called Molecular Solar Thermal system (MOST) and it has gained some attention in the last years as an alternative to other energy conversion systems due to its functioning as a closed cycle and lack of emissions. Herein we report how a well-known type of molecular switch could be tuned to act as a part of a MOST system. [2]

147 References [1] [2]

Garcia-Iriepa, C.; Marazzi, M.; Frutos, L. M.; Sampedro, D. RSC Advances 2013, 3, 6241-6266.

Blanco-Lomas, M.; Martínez-López, D.; Campos, P. J.; Sampedro D. Tetrahedron Lett. 2014, 55, 3361-3364.

Figures

Figure 1: Tuning of the properties of Rhodopsin-based molecular switches.

Hollow Mesoporous Silica Nanostructures: Synthesis and inclusion in rubber compounds Sábel Santibáñez1,2, José M. López-de-Luzuriaga1, Miguel Monge1, Jorge García-Barrasa2 1

Departamento de Química. Centro de Investigación en Síntesis Química (CISQ). Universidad de La Rioja. Complejo Científico Tecnológico, Madre de Dios 51, 26006 - Logroño (LA RIOJA) - Spain.

2 Centro Tecnológico del Calzado de La Rioja (CTCR), Calle Raposal, 65, 26580-Arnedo (LA RIOJA.) - Spain ssantibanez@ctcr.es

Hollow mesoporous silica nanostructures (HMSN) have attracted much attention due to their interesting properties such as large surface area, low density, excellent mechanical and thermal stability, low toxicity, high biocompatibility and high drug loading capacity. For all this, HMSN have been used in many areas for the design of applications in catalysis, drug storage and release, reinforcing of polymers, etc.

HMSN can been obtained through two main strategies namely, hard-template and softtemplate methods.

The hard-template method consists of the fabrication of a sacrificial template followed by the deposition of a mesoporous silica shell and final removal of the core template. On the other hand, in the softtemplate method emulsion droplets act as template for silica growth. In this context, we have systematically developed the synthesis of different HMSN through, the above mentioned methods, employing tetraethyl orthosilicate (TEOS) as the silica source and hexadecyltrimethylammonium bromide (CTAB) as surfactant. We have studied how several changes of the reaction conditions, such as concentration of reagents, solvents, catalyst or temperature, affects to the morphology and properties of HMSN.

148

The synthesized HMSN, have been integrated in rubber compounds as reinforcing agents, providing clear advantages in tear strength, abrasion, heat resistance, hardness, high modulus, etc. .

Figures

Synthesis and characterization of alloy nanoparticles Neelotpol Sarkar, Vipul Sharma, Venkata Krishnanz Amity Institute of Nanotechnology, Amity University Uttar Pradesh, Sector 125, Noida, India Indian Institute of Technology, Mandi neelotpol@gmail.com

Present work involves synthesis of alloy nanoparticles by wet chemical method. Firstly alloy nanoparticles were prepared and later subjected to annealing thereby enhancing diffusion forming modified nanoparticles. CTAB is used as a template, at high concentration they form micelle with an aqueous chamber in a polar solvent here water was used. In the aqueous cavity nanoparticle formation takes place after the addition of sodium borohydrite. Alloy nanoparticle is the formed inside it as conformed by UV-vis spectroscopy and Energy Dispersive spectroscopy. These alloy nanoparticle have been viewed under Transmission Electron Microscopy, conforming that the dimensionality of the particles is in the nanorange. Spherical nanoparticles of size 4-5nm were formed that had given rise to nano network congestion.

These nanoparticles were used in mercury sensing and were also used to synthesize spider silk-alloy hybrid nano-composite. In the near future these nanoparticles will open new field of research in Forensic Nanotechnology.

References [1] [2] [3] [4] [5]

[6] [7]

Marco Lattauda, T. Alan Hatton “Synthesis, properties and application of janus nanoparticles”, Nano Today (2011) 6, 286-308.

Yang song et al “AuAg bimetallic janus nanoparticles and their electrocatalytic activity for oxygen reduction in alkaline media”, Langimur 2012, 28, 1714317152.

Alfredo Sanchez et al “Janus mesoporus Au-mesoporous silica nanoparticles as electrochemical bioregognition-signalling system”, Electrochemistry Communications 30 (2013) 51-54.

David L. Cheung et al, “Stability of janus nanoparticles at fluid interfaces” Soft matter, 2009, 5, 3969-3976.

Lei Jia et al, “Janus nanoparticle magic: selective asymmetric modification of Au–Ni nanoparticles for its controllable assembly onto attapulgite nanorods” Chem. Commun., 2012, 48, 12112–12114.

Serena Biella et al, “Gas phase oxidation of alcohols to aldehydes or ketones by supported gold” Chem. commun. , 2003, 378–379.

Samit Guha, et al, “Fluorescent Au@Ag core shell nanoparticles with controlled shell thickness and Hg(II) sensing” Langmuir, 2011, 27, 13198–13205.

149

Figures

Figure 1: TEM image of alloy nanoparticle.

150

Broadening of FIB applications using Xe plasma FIB Aleksei Savenko, Rene Dobbe, Daniel Phifer FEI Company, Achtseweg Noord 5, 5651GG, Eindhoven, The Netherlands aleksei.savenko@fei.com

Development of FIB-SEM (also known as “DualBeam™”) equipment has undergone significant progress during recent years. Conventional Gallium FIB is still unsurpassed in precision of milling/deposition for features in the range of 10 nm - 30 µm. Meanwhile the release of Xe+ plasma FIB (PFIB) made it possible to combine comparable precision with much higher milling productivity [1]. Due to significantly larger beam currents and marginally higher sputter rate, it is possible to mill structures of up to several hundred microns within a reasonable time or to increase significantly the throughput for traditional structures.

Moreover, the milling with Xe PFIB produces better quality of surface.

The following new applications have become available due to the higher milling rate of the Xenon based PFIB and are being adopted to extend the capabilities to larger structure sizes as compared to the Gallium based FIB-SEM: - Tomography and 3D EBSD/EDS characterization of volumes up to (100 µm)3 - TEM lamella preparation of large areas or multiple places within shortest amount of time - Large area cross-section; larger than 100x100 µm size - Patterning of extended area of surface for optical and technological applications - Sample preparation for techniques such as micro-CT and micro-size compression/tensile testing - Through wafer milling, as well as inspections of TSVs (through silicon vias) and wire bonding Minimizing of surface defects during milling is critical for a number of applications. Amorphization and penetration depth of ions is less for Xe+ versus Ga+ in the same conditions [2]. Some applications are not possible due to the creation of Ga FIB milling artifacts, such as droplets liberation during InGaAs milling, eutectic formation with In, Al, Zn, Pb metals [3], or segregation of Ga at the grain boundary of Al TEM lamellas. In these cases, Xe is an inert element and is showing promise to investigate these materials without the challenges of Ga. FIB alone allows removing material faster, but it is the combination with high resolution SEM that makes the Helios PFIB DualBeam a powerful instrument for imaging and for analytical investigation. Significant precision and throughput are achievable in 3D imaging, EBSD and EDS applications. Fully automated routines such as 3D EDS and EBSD as well as SEM imaging 3D software are available to collect serial image stacks through areas of interest. TEM sample preparation and manufacturing of designed structures can be done at high level of automation as well, making the Xe FIB-SEM a useful tool to characterize the 2D and 3D material structure, properties and ultimately relate these to functionality.

An expanded, continuous range of length-scales is now accessible for 3D characterization by variety of microscopy and tomography correlative methods. It spans from sub-nanometer TEM resolution to mesoscale range of micro-CT. Plasma FIB covers the intermediate range in-between, i.e. µm-mm range.

Combination of several such methods allows achieving comprehensive and complementary studies of the object of interest. As the next step, the 3D-data treatment, analysis and versatile visualization can be done by 3D reconstruction & visualization software suites such as FEI Avizo.

Combining SEM with Xe+ or Ga+ ion beam, the proper system can be specified for certain applications to gain significant advantage from Xe or Ga, whereas in other cases performance is comparable and

151

interchangeable. In summary, Xe Plasma FIB/SEM technology enables dramatically improved material removal rates compared to traditional methods - while maintaining exceptional surface quality, highcontrast and ultra-high resolution imaging performance. Ga FIB allows the fabrication of smaller precise structures. Both techniques have applications in materials science where they enable better material characterization.

References [1] [2] [3]

152

T.L. Burnett, R. Kelley, B. Winiarski, et al., Ultramicroscopy, 161 (2016) 119–129.

R.D. Kelley, K. Song, B. Van Leer, et al., Microscopy and Microanalysis, 19 (S2) (2013) 862–863.

J. Mayer, L.A. Giannuzzi, T. Kamino, J. Michael, MRS Bulletin, V 32 (2007) 400–407.

Optical spectroscopy of metallic icosahedral nanoparticles: classical versus atomistic description M. Urbieta1,2,3, Y. Zhang1, M. Barbry1, P. Koval1,2, D. Sánchez-Portal1,2, N. Zabala1,2,3 and J. Aizpurua1,2 1

CFM-MPC, Centro Mixto CSIC-UPV/EHU, Paseo Manuel de Lardizabal 5, San Sebastian, Spain Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, San Sebastian, Spain 3 Department of Electricity and Electronics, FCT/ZTF, UPV/EHU, 48940 Leioa, Spain murbieta008@ikasle.ehu.es

2

Progress in nanotechnology has allowed control of metallic nanoparticles at the nanometer and even subnanometer scale. Some of the most fascinating properties and applications of plasmonic nanoparticles are based on the tunability of their optical response and their ability to localize the electromagnetic fields around tips or at inter particle gaps. The near-fields are commonly addressed theoretically within classical frameworks. However, in some situations the atomic structure needs to be considered to correctly determine the response of the nanosystem [1].

In this work we study the far- and near-field response of metallic nanoparticles and compare three different models. i) First, we use a classical modeling within a boundary element method (MNPBEM) [2-3], which considers abrupt boundaries between media with homogeneous and isotropic dielectric functions to solve Maxwell's equations. Because the mean free path of the electrons is comparable to the size of the particles considered, the billiard model is used to approach surface scattering effects [4-5], with the resulting increase of damping in the dielectric function. ii) Secondly, we consider a discrete dipole approximation (DDA), in which each atom of the nanoparticle is described as a dipole [6] and the atomistic structure is preserved. iii) Finally, our results are compared with atomistic ab-initio time-dependent density functional theory (TDDFT) calculations [1].

We show that the general patterns of subnanometric localization and enhancement of fields can effectively be approached by classical means. The presence of tips and sharp endings in the geometry of the particle introduces a major enhancement and localization of the near-fields. Nevertheless, for the case of close particle dimers, differences arise due to the lack of quantum tunneling effects in the classical descriptions. In Figure 1) we show the near-field enhancement and the absorption cross section for a dimer of sodium icosahedral particles of radius 1.6 nm, as calculated in the classical BEM model.

References [1] [2] [3] [4] [5] [6]

M. Barbry, P. Koval, F. Marchesin, R. Esteban, A. G. Borisov, J. Aizpurua, D. Sánchez-Portal, Nano Lett., 15 (2015) 3410-3419.

U. Hohenester, A. Trügler, Comput. Phys. Commun, 183 (2012) 370-381.

F. J. García de Abajo, A. Howie, Phys. Rev. B, 65 (2002) 115418.

U. Kreibig, C. Fragstein, Z. Phys., 224 (1969) 307-323.

A. Moroz, J. Phys. Chem. C, 112 (2008) 10641-10652.

E. M. Purcell, C. R. Pennypacker, Astrophys. J., 186 (1973) 705–714.

153

Figures

Figure 1: a) Absorption cross section of a facet-to-facet configuration of a Na icosahedral dimer for varying separation distances. The circumscribed radius of the icosahedral particles is r = 1.6 nm and the polarization of the external field parallel to the dimer axis. b) Field enhancement for a separation distance of dsep = 1 nm at energy corresponding to the bonding dimer plasmon (BDP) shown in plane a).

154

Aberration corrected views into the nano-world María Varela Universidad Complutense de Madrid. Madrid 28040, Spain mvarela@ucm.es

Harnessing the next generation of functional materials requires understanding structural, physical, electronic and even magnetic properties at the nano-scale, in real space. Aberration corrected scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS) can probe structural, chemical, and electronic properties with atomic-level resolution, and now they can also provide magnetic information at this length scale in exquisite detail [1-3]. This talk will review a few examples of applications of STEM-EELS to complex oxide low dimensional systems such as interfaces or nanostructures. Avenues to explore magnetism in low dimensional materials will be discussed, including imaging modes sensitive to magnetic properties such as orbital moment or spin [2]. Through the use of electron magnetic circular dichroism (EMCD) [1], we will show how sub-nanometer real-space characterization of magnetism is possible. In magnetite Fe3O4 iron-oxide nanoparticles capped with organic acids we not only find that the surface of the nanoparticles is ferromagnetic but, combining the results with densityfunctional calculations, we establish how magnetization is restored in the surface layer.

The bond to the organic acid prevents further oxidation to Fe2O3 and results in O-Fe atomic configuration and distances close to the bulk values [3]. Other examples will include explaining the origin of the unexpected ferromagnetism in ultrathin LaCoO3-x (LCO) films. Bulk LCO is non-magnetic and fully stoichiometric, but in thin films, epitaxial strain is released through local lattice expansion at ordered oxygen-deficient atomic planes. The vacancies lead to excess electrons in the Co d-states, resulting in ferromagnetic ordering. The ensuing electron doping should result in metallic behavior but, on the contrary, the films are insulating. The vacancy superstructures disrupt the band structure causing the appearance of Peierls-like minigaps. On strain relaxation, these minigaps trigger a nonlinear rupture of the energy bands, resulting in the observed insulating behavior [4]. We conclude that oxygen vacancies complement strain as a major controllable degree of freedom that can be used to engineer novel behavior in complex-oxide films.

Acknowledgements This work was possible thanks to the collaboration of J. Gazquez, N. Biskup, J. Salafranca, M. P. Oxley, W. Luo, S. T. Pantelides, M. Chisholm, S. J. Pennycook, X. Battle, A. Labarta, Y. Suzuki, V. Mehta, G. SanchezSantolino, M. Cabero, C. Leon and J. Santamaría, amongst others. Research at UCM sponsored by Fundación BBVA and Spanish MINECO MAT2015-66888-C3-3-R. Research at Oak Ridge National Laboratory supported by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division, and through a user project supported by ORNL’s Shared Research Equipment (ShaRE) User Program, which is also sponsored by DOE-BES. References [1] [2] [3] [4]

P. Schattschneider et al., Nature 441 (2006) 486.

J. Gazquez et al. Nano letters 11 (2011) 973.

J. Salafranca et al., Nano Letters 12 (2012) 2499.

N. Biskup et al., Phys. Rev. Lett. 112 (2014) 087202.

155

Atomic layer deposition in biomedical applications Mercedes Vila JuĂĄrez CTECHnano. Tolosa Hiribidea 76, E-20018 San Sebastian, Spain m.vila@ctechnano.com

Different from chemical vapor deposition (CVD) and physical vapor deposition (PVD), atomic layer deposition (ALD) is based on saturated surface reactions. In this case, the thin films are grown in a layerby-layer fashion allowing sub-nanometer thickness control, low temperature depositions, good uniformity and superior step coverage on high specific surface area components compared to CVD and PVD. These advantages of ALD over other thin film deposition processes have been conventionally applied mainly in semiconductor electronic industry on the preparation of layers of outstanding High-K dielectric materials.

But, due to the advances in tool design and recipe development, the importance of ALD is rapidly expanding for producing innovative nanoscale materials.

ALD potential applications are highly multidisciplinar and specially, innovations brought by nanotechnology to biosciences, are proving to be good candidates to benefit from these potentialities.

Applications of ALD in biomedicine cover from biosensors to tissue engineering and implantable devices.

References

156

[1]

R. J. Narayan et al. Phil. Trans. R. Soc. A (2010) 368, 2033â&#x20AC;&#x201C;2064.

Caco-2 cells as an in vitro model to determine detrimental effects on the intestinal barrier. Studies with SiO2- and ZnO-NPs at sub-toxic doses Laura Vila, Alba García, Ricard Marcos, Alba Hernández Grup de Mutagènesi, Departament de Genètica i de Microbiologia, Facultat de Biociències, Universitat Autònoma de Barcelona, Bellaterra, Spain; CIBER Epidemiología y Salud Pública, ISCIII, Spain. laura.vila@uab.es

Engineered nanoparticles (NPs) are used in many commercial products due to their desirable characteristics for many industrial applications. In addition, some of them are being used as additives in food and packaging, increasing human exposure [1],[2],[3]. This increased use of NPs and the lack of complete knowledge on their potential hazard in the gastrointestinal tract, as a main protection barrier, require further investigations.

ZnO-NPs are already used in food packaging products due to their antimicrobial and UV-absorbent properties [4] . Furthermore, amorphous SiO2-NPs are used as food additive and as a component in milk powders, instant soups, etc. to improve flow-ability [4] [5] [6].

The human Caco-2 cell line is derived from colonic epithelial adenocarcinoma cells. This cell line has the capability to differentiate into small intestine enterocyte after reaching confluence, when it is grown under normal cell culture conditions. After 21 days of differentiation the cells become to be polarized and acquire tight junctions, microvilli and membrane transporters [7] [8]. This is considered a very useful model to observe uptake of nutrients and pharmaceuticals and, for these reasons, differentiated Caco-2 cells have become a model for in vitro studies related with the uptake and transport through barriers.

Intestinal cell toxicity of ZnO and SiO2-NPs were evaluated in differentiated Caco-2 cells. Moreover, intestinal integrity and paracellular permeability were also evaluated after 24 hours of NPs incubation at sub-toxic doses in order to mimic a realistic environmental exposure. The nanomaterials were characterized for their morphology and size by TEM (Fig. 1) and DLS/LDV. The analysis of cytotoxicity show non-toxic effects of amorphous silica in differentiated Caco-2 cells, while ZnO-NPs led to significant reduction of Caco-2 cells viability. The use of sub-toxic doses of both NPs demonstrates that the integrity and permeability remain properly after 24 hours of exposure (Fig. 2- 3).

Hence, neither of these two NPs at sub-toxic doses were able to damage our system of differentiated Caco-2 model.

References [1]

[2] [3] [4]

[5]

Borm PJA, Robbins D, Haubold S, Kuhlbusch T, Fissan H, Donaldson K, Schins RPF, Stone V, Kreyling W, Lademann J. Krutmann J, Warheit D, Oberdorster E., Part Fibre Toxicol., The potential risks of nanomaterials: a review carried out for ECETOC (2006), 3:11.

Nel A, Xia T, Madler L, Li N., Science, Toxic potential of nanomaterials at the nanolevel (2006). 311:622-627.

Di Pasqua AJ, Sharma KK, Shi YL, Toms BB, Ouellette W, Dabrowiak JC, Asefa T. J, Inorg Biochem, Cytotoxicity of mesoporous silica nanomaterials (2008), 102:1416-1423.

Chaudhry Q, Scotter M, Blackburn J, Ross B, Boxall A, Castle L, Aitken R, Watkins R., Food Addit Contam Part A Chem Anal Control Expo Risk Assess, Applications and implications of nanotechnologies for the food sector (2008), 25:241-258.

Schmid K, Riediker M., Environ Sci Technol, Use of nanoparticles in Swiss Industry: a targeted survey (2008), 42:2253-2260.

157

[6] [7]

[8]

Dekkers S, Krystek P, Peters RJ, Lankveld DX, Bokkers BG, van Hoeven-Arentzen PH, Bouwmeester H, Oomen Ag., Nanotoxicol, Presence and risks of nanosilica in food products (2011) 5:393-405.

Chantret I, Barbat A, Dussaulx E, Brattain MG, Zweibaum A., Cancer Res., Epithelial polarity, villin expression, and enterocytic differentiation of cultured human colon carcinoma cells: a survey of twenty cell lines (1988), 48:1936-1942.

Chopra DP, Dombkowski AA, Stemmer PM, Parker GC., Stem Cells Dev., Intestinal epithelial cells in vitro (2010), 19:131-142.

Figures

Figure 1: TEM images of SiO2-NPs (A) and ZnO-NPs (B) in dried form.

158

Figure 2: Integrity and permeability analysis of SiO2-NPs. Integrity was evaluated using trans epithelial electrical resistance (TEER; A). Permeability was evaluated analyzing the concentration of paracellular compost named Lucifer Yellow (LY) in basolateral medium (B).

.

Figure 3: Integrity and permeability analysis of ZnO-NPs. Integrity was evaluated using trans epithelial electrical resistance (TEER; A). Permeability was evaluated analyzing the concentration of paracellular compost named Lucifer Yellow (LY) in basolateral medium (B).

Manufacturing and characterization of high electrical conductivity structural epoxy graphene composites Elvira Villaro Ábalos1,2, Julio Gómez Cordón3 1

Instituto de Tecnologías Químicas Emergentes de La Rioja; San Francisco, 11, 26370 Navarrete, La Rioja, Spain.

2 Departamento de Química Inorgánica y Técnica, UNED. Senda del Rey, 9, Madrid, Spain 3 Avanzare Innovación Tecnologica S.L. Avda Lentiscares 4-6 Navarrete, La Rioja, Spain evillaro@interquimica.org

Glass and carbon fiber fabrics reinforced composites are emerging technologies in last three decades (carbon fiber first emerged in the aviator sector in the 1980s) with structural applications, being an alternative to metallic parts. Structural functions of these types of hierarchical composites are well known and are nowadays used in important sectors, as wind-energy, sports aeronautic and automotive. [1] Thermosetting carbon fiber fabrics reinforced composites show high electrical conductivity in plane (X-Y directions) while are insulators in through plane (Z-direction). On the other side, glass fiber composites (the 85% of the market) do not have electrical conductivity at any case.

This research aims the preparation of high electrical conductivity, both in plane and through plane, structural thermosetting composites; employing carbon fiber (CF) and glass fiber (GF) fabrics with Highly Reduced Graphene Oxide (HRGO).

We have prepared HRGO-epoxy dispersions and employed them to make glass and carbon fiber fabrics reinforced composites. The fabrics were impregnated with the HRGO-epoxy dispersions and the prototypes were prepared by wet lay-up technique, curing at vacuum conditions. This method constitutes a simple process giving the possibility of obtain structural materials with high electrical conductivity, and take a great advantage in the preparation of many final industrial applications.

Using GF fabrics, more than 1S/m of electrical conductivity is obtained in XY-plane with the addition of 1%w of HRGO in the composite. In Z-axis the percolation limit is achieved with less than 0.6%w.

In case of CF Reinforced Composites (CFRC), with own high electrical conductivity in XY-plane size (5S/m), the inclusion of 0.5%w of HRGO increases the electrical conductivity more than three orders of magnitude.

And what is more, the percolation limit of the conductivity in Z-axis is obtained with 0.25%w of loading.

More than 0.1S/m is obtained through plane with 0.5%w of HRGO in the composite; while MWCNT need more than 1%w to obtain similar results. [2] Applications of these structural composites can go between automotive [3] and aerospace industries; since the obtained values cover the electrical conductivity requirements, and provide structural parts able to act as antistatic or high electrical conductivity pieces in the body, according to the HRGO content. It is also important highlight the easy and appropriate features for the industrialisation of the method of preparation of these high electrical conductivity reinforced composites.

References [1] [2] [3]

Sanjay M.R, Arpitha G.R., B.Yogesha, Materials Today: Proceedings 2 (2015) 2959 – 2967 Xu H, Tong X, Zhang Y, Li Q, Lu W, Composites Science and Technology, (2016) Carbon Fiber to Go Mainstream in Automobile by 2025-Lux Research.

159

iGCAuto: Innovative Graphene-Based Polymer Composite Materials for Automotive Applications Elvira Villaro Ábalos1,2, Marta Pérez1, Ahmed Elmarakbi3 1

Instituto de Tecnologías Químicas Emergentes de La Rioja; San Francisco, 11, 26370 Navarrete, La Rioja, Spain.

2 Departamento de Química Inorgánica y Técnica, UNED. Senda del Rey, 9, Madrid, Spain 3 Department of Computing, Engineering and Technology, University of Sunderland evillaro@interquimica.org

The global automotive industry is currently facing great challenges as responsibility for increasing CO2 emissions, lack of strong decarbonisation targets, fuel consumption, and safety. It is widely viewed as being the industry in which the greatest volume of advanced composite materials will be used in the future to produce light vehicles. However, in recent decades, cars have become larger and heavier with new generations. The main drivers of the weight increase are the improved safety and comfort requirements. Striving for reduced weight as the only objective will not necessarily result in a reduced environmental impact of the future vehicles: Another two key drivers need to be pursued at the same time, namely affordability and life cycle impact minimisation.

160

iGCAuto is part of the Graphene Flagship WP10, dedicated to nanocomposites, and specially focused on automotive applications of graphene. The project is researching in the field of the Graphene Related Materials (GRM) science and technology in a unique direction for large scale automotive applications towards safer, greener and energy efficient vehicles. Main target is provide Europe’s automotive industry with highly competitive innovative lightweight graphene-based material solutions and the necessary capabilities to design, simulate, manufacture and assemble very lightweight, CO2 and energy efficient and safe vehicles (EESVs). The development of novel graphene composites materials and their potential applications in automotive industry has been investigated and discussed in this project, towards safer and greener transport.

To achieve the objective, there have been prepared and characterized GRM thermosetting and thermoplastic composites, after the optimization of their processing methods. These hierarquical composites can be used as components in the vehicle body. Apart from their structural functions; proved with the enhancement of the mechanical properties, we have also obtained great improvements in thermal and electrical conductivity; showing the opportunities of obtaining, in industrial way, new multifunctional materials, not only with structural capabilities but also electrical and thermal conductors.1.

References [1]

Progress in polymer science 36 (2011) 638-670.

Structure and Spectroscopy of Helium Nanodroplets Doped with Molecular Impurities at Low Temperatures Pablo Villarreal, Rocío Rodríguez-Cantano, Tomás González-Lezana, Rita Prosmiti and Gerardo Delgado-Barrio Instituto de Física Fundamental-CSIC, Serrano 123, 28006 Madrid, Spain p.villarreal@csic.es

We review in this talk some theoretical studies carried out in our group involving molecular species immersed in (or attached to) He clusters at very low temperatures. Using a quantum chemistry-like methodology, superfluidity of boson 4He (in contrast with fermion 3He) clusters is demonstrated for dopants residing inside the droplet by spectroscopic IR or Raman simulations depending on their polar or non-polar nature [1-4]. In addition, Path Integral Monte Carlo calculations are used to determine the energy and structure for different atomic, molecular and ionic species frequently placed at the surface of boson He droplets [5-8].

References [1] [2] [3] [4] [5] [6] [7] [8]

D. López-Durán, M. P. de Lara-Castells, G. Delgado-Barrio, P. Villarreal, C. Di Paola, F. A. Gianturco, and J. Jellinek, Phys. Rev. Lett.. 93 (2004) 053401.

M. P. de Lara-Castells, D. López-Durán, G. Delgado-Barrio, P. Villarreal, C. Di Paola, F. A. Gianturco, and J. Jellinek, Phys. Rev. A 71 (2005) 033203.

M. P. de Lara-Castells, P. Villarreal, G. Delgado-Barrio, and A. O. Mitrushchenkov, J. Chem. Phys.

131 (2009) 194101.

N. F. Aguirre, P. Villarreal, G. Delgado-Barrio, A. O. Mitrushchenkov, and M. P. de Lara-Castells, Phys. Chem. Chem. Phys. 15 (2013) 10126.

R. Pérez de Tudela, D. López-Durán, T. González-Lezana, G. Delgado-Barrio, P. Villarreal, F. A. Gianturco, and E. Yurtsever, J. Phys, Chem. A 115 (2011) 6892.

R. Rodríguez-Cantano, T. González-Lezana, P. Villarreal, and F. A. Gianturco, J. Chem. Phys. 142 (2015) 104303.

P. Villarreal, R. Rodríguez-Cantano, T. González-Lezana, R. Prosmiti, G. Delgado-Barrio, and F. A. Gianturco, J. Phys. Chem. A 119 (2015) 11574.

R. Rodríguez-Cantano, T. González-Lezana, and P. Villarreal, Int. Rev. Phys. Chem. 35 (2016) 37.

161

Figures

Figure 1: Evolution of S branches in the Raman spectra of Br2 embedded in different mixtures of 3He/4He clusters at T=0.5 K[1].

162

Figure 2:Snapshot from the PIMC simulation for He32 â&#x20AC;&#x201C;He*â&#x2C6;&#x2019; at T = 0.4K. A bipyramid structure can be seen in a dimple at the top[8].

Epitaxial growth of semiconductor nanostructures on graphene: Generic model and a potential first device application Helge Weman Professor, Norwegian University of Science and Technology, 7491 Trondheim, Norway Founder and CTO, CrayoNano AS, 7052 Trondheim, Norway helge.weman@ntnu.no

We have recently developed a generic atomic model which describes the epitaxial growth of semiconductor nanostructures on graphene that is applicable to all conventional semiconductor materials [1, 2], as shown in Fig. 1. The model has been verified by crosssectional transmission electron microscopy studies of GaAs nanowires that grow epitaxially and dislocation-free on graphene, in spite of a lattice mismatch of 6.3 % [1]. We have also fabricated a prototype of a single GaAs nanowire photodetector, which demonstrated a high-quality material [1]. The epitaxial growth of semiconductor nanostructures on graphene is thus very appealing for device applications since graphene can function not only as a replacement of the semiconductor substrate but in addition as a transparent and flexible electrode for e.g. solar cells and LEDs. For deep ultraviolet AlGaN based LEDs in huge need for various disinfection and sterilization purposes, the concept offers a real advantage over present thin film based technology. Such thin film UV LEDs are today very expensive and inefficient due to the lack of a good transparent electrode (ITO is absorbing in deep UV), the high dislocation density in the active thin film layers, low light extraction efficiency, and the use of very expensive semiconductor substrates (e.g. AlN). The spinoff company CrayoNano are now developing LEDs based on the selective-area growth of AlGaN nanostructures on mask-patterned graphene, which potentially can overcome all these problems, as will be further discussed in my talk.

References [1] [2]

M.A. Munshi, D.L. Dheeraj, V.T. Fauske, D.C. Kim, A.T.J. van Helvoort, B.O. Fimland, and H. Weman, Nano Letters 12, 4570 (2012).

A.M. Munshi and H. Weman, Phys. Status Solidi RRL 7, 713 (2013). (Review article)

163

Figures

164

Figure 1: (a-d) Relative orientation and arrangement when semiconductor atoms are adsorbed on H- and/or B-sites. (e) Generic model describing the semiconductor bandgaps vs. lattice constants together with lattice constants for the latticematched atom arrangements on graphene [1].

Conductive Coordination Polymers at the Nanoscale Félix Zamora1,2, Cristina Hermosa1,3, Cristina Gómez-Navarro3 , Pablo Ares3 and Julio Gómez-Herrero3 1

Universidad Autónoma de Madrid. Facultad de Ciencias Departamento de Química Inorgánica and Condensed Matter Physics Center (IFIMAC). E-28049 Madrid, Spain www.nanomater.es 2 IMDEA-Nanoscience. C/ Faraday 9, Campus Cantoblanco-UAM, E-28049 Madrid, Spain 3 Universidad Autónoma de Madrid. Facultad de Ciencias Departamento de Física de la Materia Condensada and Condensed Matter Physics Center (IFIMAC). E-28049 Madrid, Spain felix.zamora@uam.es

The suitable combination of metal entities with organic molecules, named as ligands, lead to the formation of coordination polymers (CPs). These metal-organic systems can originate a large variety of architectures with interesting physico-chemical properties.

In this talk I will pay attention to a particular type of linear coordination polymers known as MMX chains which consist of the combination of two simple building blocks a dimetal subunit with halides. I will describe several experiments that have allowed us to form small nanostructures, composed of few molecules, on insulating surfaces using a rather unusual deposition method named as direct sublimation.

[1] I will present several experiments of their electrical characterization. [2,3] These experiments have confirmed their intrinsic metallic character and excellent electrical conductivity. Finally, I will discuss on very recent results obtained on MMX produced on mica and SiO2 by simple drop-casting from solution and the electrical measurements carried out on a single molecule. These results show the high potential of MMX as molecular wires.

165 References [1] [2] [3]

Figures

Welte, L. et al. Adv Mater 21 (2009) 2025.

L. Welte, A. Calzolari, R. Di Felice, F. Zamora, J. Gómez-Herrero. Nat. Nanotech. 5 (2010) 110.

C. Hermosa, J. V. Álvarez, M.-R. Azani, C. J. Gómez-García, M. Fritz, J. M. Soler, J. GómezHerrero, C. Gómez-Navarro, F. Zamora. Nat. Commun., 4 (2013) 1709.

Cover image: HD-KFM image on Graphene Credit: Nicolas F. Martinez (ScienTec Iberica, Spain)

Edited by Phantoms Foundation Alfonso Gomez 17 28037 Madrid - Spain info@phantomsnet.net www.phantomsnet.net

www.nanospainconf.org

Edited by

Phantoms Foundation Alfonso Gomez 17 28037 Madrid - Spain info@phantomsnet.net www.phantomsnet.net