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Functionalized Nanomaterial-Based Electrochemical Sensors

Woodhead Publishing Series in Electronic and Optical Materials

Functionalized Nanomaterial-Based Electrochemical Sensors

Principles, Fabrication Methods, and Applications

Chaudhery Mustansar Hussain Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, United States

Jamballi G. Manjunatha Department of Chemistry, FMKMC College, Constituent College of Mangalore University, Madikeri, Karnataka, India

Woodhead Publishing is an imprint of Elsevier

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A catalogue record for this book is available from the British Library

ISBN: 978-0-12-823788-5

ISBN: 978-0-12-824185-1

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Section B Fabrication of functionalized nanomaterial-based

3 Application of hybrid nanomaterials for development of electrochemical sensors

Thiago C. Canevari

3.1 Introduction

3.2 SiO2/MWCNTs, SiO2/MWCNTs/AgNPS, and GO/Sb2O5

3.3 Carbon dots/Fe3O4 and rGO/carbon dots

3.4 rGO/carbon dots/AuNPs

3.5

4 Biofunctionalization of functionalized nanomaterials for electrochemical sensors

Muhammed Bekmezci, Ramazan Bayat, Vildan Erduran, and Fatih Sen

4.1

4.3

5

Sankararao Mutyala, P. Hari Krishna Charan, Rajendran Rajaram, and K. Naga Mahesh

5.1

5.2

5.3

6 Functionalized carbon material-based electrochemical sensors for day-to-day applications

Vildan Erduran, Muhammed Bekmezci, Ramazan Bayat, and Fatih Sen

6.1 Introduction

6.2

6.3

6.4

7

6.5

9

Parisa Nasr-Esfahani and Ali A. Ensafi

7.1

7.2

Balaji Maddiboyina, OmPrakash Sunaapu, Sandeep Chandrashekharappa, and Gandhi Sivaraman

Section

10

A.H. Sneharani

10.1

10.2

10.3

10.4

10.5

10.6

11

Masoud Reza Shishehbore and Mohadeseh Safaei

12

Ramazan Bayat, Muhammed Bekmezci, Vildan Erduran, and Fatih Sen

12.1

12.2

14

15

Hilmi Kaan Kaya, Tahsin Çağlayan, and Filiz Kuralay

S. Nandini, S. Nalini, S. Bindhu, S. Sandeep, C.S. Karthik, K.S. Nithin, P. Mallu, and J.G. Manjunatha

15.1

A. Priyadharsan, S. Shanavas, S. Boobas, Tansir Ahamad, R. Acevedo, P.M. Anbarasan, and R. Ramesh

H.C. Ananda Murthy, Ararso Nagari Wagassa, C.R. Ravikumar, and H.P. Nagaswarupa

17.3

18 Functionalized

Vildan Erduran, Muhammed Bekmezci, Ramazan Bayat, Zübeyde Bayer Altuntaş, and Fatih Sen

18.1

19

Celina M. Miyazaki, Flavio M. Shimizu, and Marystela Ferreira

19.1

19.3

19.5

21

Waleed A. El-Said, Naeem Akhtar, and Mostafa M. Kamal

Álvaro Torrinha, Thiago M.B.F. Oliveira, Francisco W.P. Ribeiro, Simone Morais, Adriana N. Correia, and Pedro de Lima-Neto

21.1

21.2

21.3

Moslehifard, and Farzad Nasirpouri 22.1

22.3

Contributors

R. Acevedo  Faculty of Engineering and Technology, San Sebastian University, Santiago, Chile

Tansir Ahamad Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia

Naeem Akhtar Interdisciplinary Research Center in Biomedical Materials (IRCBM), COMSATS University Islamabad, Lahore, Pakistan

Zübeyde Bayer Altuntaş Sen Research Group, Department of Biochemistry, Dumlupınar University, Kutahya, Turkey

H.C. Ananda Murthy Department of Applied Chemistry, School of Natural Science, Adama Science and Technology University, Adama, Ethiopia

P.M. Anbarasan  Nano and Hybrid Materials Laboratory, Department of Physics, Periyar University, Salem, Tamil Nadu, India

Ramazan Bayat  Sen Research Group, Department of Biochemistry, Dumlupınar University, Kutahya; Department of Materials Science & Engineering, Faculty of Engineering, Dumlupınar University, Kütahya, Turkey

Muhammed Bekmezci  Sen Research Group, Department of Biochemistry, Dumlupınar University, Kutahya; Department of Materials Science & Engineering, Faculty of Engineering, Dumlupınar University, Kütahya, Turkey

S. Bindhu  Department of Chemistry, SJCE, JSS Science and Technology University, Mysuru, Karnataka, India

S. Boobas Department of Physics, Sri Vasavi College, Bhavani, Tamil Nadu, India

Tahsin Çağlayan  Defense Industries Research and Development Institute, The Scientific and Technological Research Council of Turkey, Ankara, Turkey

Thiago C. Canevari Chemistry Course, Engineering School, Mackenzie Presbyterian University, São Paulo, SP, Brazil

Sandeep Chandrashekharappa  Institute for Stem Cell Biology and Regenerative Medicine (InStem), Bangalore, Karnataka, India

Hamed Cheshideh  Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran; Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan

Adriana N. Correia Departamento de Química Analítica e Físico-Química, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, Ceará, Brazil

Pedro de Lima-Neto  Departamento de Química Analítica e Físico-Química, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, Ceará, Brazil

Waleed A. El-Said  Department of Chemistry, Faculty of Science, Assiut University, Assiut, Egypt; Department of Chemistry, College of Science, University of Jeddah, Jeddah, Saudi Arabia

Ali A. Ensafi  Department of Chemistry, Isfahan University of Technology, Isfahan, Iran; Department of Chemistry & Biochemistry, University of Arkansas, Fayetteville, AR, United States

Vildan Erduran  Sen Research Group, Department of Biochemistry, Dumlupınar University, Kutahya; Department of Materials Science & Engineering, Faculty of Engineering, Dumlupınar University, Kütahya, Turkey

Marystela Ferreira  Centre of Science and Technology for Sustainability, Federal University of São Carlos, Sorocaba, São Paulo, Brazil

P. Hari Krishna Charan  Department of Chemistry, Aditya Institute of Technology and Management, Srikakulam, Andhra Pradesh, India

Gururaj Kudur Jayaprakash  School of Advanced Chemical Sciences, Shoolini University, Solan, Himachal Pradesh, India

Shankramma Kalikeri  Division of Nanoscience and Technology, Department of Water and Health (Faculty of Life Sciences), JSS Academy of Higher Education & Research (Deemed to be University), Mysore, Karnataka, India

Mostafa M. Kamal Department of Chemistry, Faculty of Science, Assiut University, Assiut, Egypt

Deepak Kapoor  Department of Pharmaceutical Chemistry, Delhi Pharmaceutical Sciences Research University, New Delhi, India

C.S. Karthik  Department of Chemistry, SJCE, JSS Science and Technology University, Mysuru, Karnataka, India

Hilmi Kaan Kaya Department of Chemistry, Faculty of Science, Hacettepe University, Ankara, Turkey

N. Kazemifard Department of Chemistry, Isfahan University of Technology, Isfahan, Iran

Deepak Kumar  School of Pharmaceutical Sciences, Shoolini University, Solan, Himachal Pradesh, India

Filiz Kuralay  Department of Chemistry, Faculty of Science, Hacettepe University, Ankara, Turkey

Balaji Maddiboyina  Department of Pharmacy, Vishwabharathi College of Pharmaceutical Sciences, Guntur, Andhra Pradesh, India

P. Mallu  Department of Chemistry, SJCE, JSS Science and Technology University, Mysuru, Karnataka, India

J.G. Manjunatha  Department of Chemistry, FMKMC College, Constituent College of Mangalore University, Madikeri, Karnataka, India

Celina M. Miyazaki  Centre of Science and Technology for Sustainability, Federal University of São Carlos, Sorocaba, São Paulo, Brazil

Yaamini Mohan  School of Biosciences and Technology, Vellore Institute of Technology, Vellore, India

Simone Morais  REQUIMTE-LAQV, Instituto Superior de Engenharia do Porto, Instituto Politécnico do Porto, Porto, Portugal

Elnaz Moslehifard  Department of Prosthodontics, Faculty of Dentistry, Tabriz University of Medical Sciences, Tabriz, Iran

Sankararao Mutyala Nanosol Energy Pvt Ltd, Hyderabad, Telangana, India

K. Naga Mahesh Nanosol Energy Pvt Ltd, Hyderabad, Telangana, India

H.P. Nagaswarupa  Department of Studies in Chemistry, Davangere University, Shivagangothri, Davangere, Karnataka, India

S. Nalini  Department of Biochemistry, Bangalore City University, Bengaluru, Karnataka, India

S. Nandini  Department of Biochemistry, Bangalore City University, Bengaluru, Karnataka, India

Farzad Nasirpouri  Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran

Parisa Nasr-Esfahani  Department of Chemistry, Isfahan University of Technology, Isfahan, Iran

K.S. Nithin Department of Chemistry, The National Institute of Engineering, Mysuru, Karnataka, India

Thiago M.B.F. Oliveira  Centro de Ciência e Tecnologia, Universidade Federal do Cariri, Juazeiro do Norte, Ceará, Brazil

Rajat Kumar Pandey  School of Pharmaceutical Sciences, Shoolini University, Solan, Himachal Pradesh, India

A. Priyadharsan  Department of Physics, E.R.K. Arts and Science College, Erumiyampatti, Tamil Nadu, India

Rajendran Rajaram Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai, Tamil Nadu, India

Shashanka Rajendrachari  Department of Metallurgical and Materials Engineering, Bartin University, Bartin, Turkey

Dileep Ramakrishna  Department of Chemistry, School of Engineering, Presidency University, Bangalore, India

R. Ramesh Department of Physics, Periyar University, Salem, Tamil Nadu, India

Srilatha Rao  Department of Chemistry, Nitte Meenakshi Institute of Technology, Bangalore, Karnataka, India

C.R. Ravikumar  Research Centre, Department of Science, East West Institute of Technology, VTU, Bangalore, Karnataka, India

Francisco W.P. Ribeiro  Instituto de Formação de Educadores, Universidade Federal do Cariri, Brejo Santo, Ceará, Brazil

Z. Saberi Department of Chemistry, Isfahan University of Technology, Isfahan, Iran

Mohadeseh Safaei Department of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran

S. Sandeep Department of Chemistry, SJCE, JSS Science and Technology University, Mysuru, Karnataka, India

Fatih Sen Sen Research Group, Department of Biochemistry, Dumlupınar University, Kutahya, Turkey

S. Shanavas  Nano and Hybrid Materials Laboratory, Department of Physics, Periyar University, Salem, Tamil Nadu, India

Flavio M. Shimizu  Department of Applied Physics, “Gleb Wataghin” Institute of Physics (IFGW), University of Campinas (UNICAMP), Campinas, São Paulo, Brazil

Masoud Reza Shishehbore  Department of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran

Gandhi Sivaraman  Department of Chemistry, Gandhigram Rural Institute Deemed University, Dindigul, Tamil Nadu, India

A.H. Sneharani  DoS in Biochemistry, Jnana Kaveri P.G. Center, Mangalore University, Kodagu, India

OmPrakash Sunaapu Department of Chemistry, University College of Engineering, Anna University, Dindigul, Tamil Nadu, India

Puchakayala Swetha  State Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, People’s Republic of China

Rajiv Tonk Department of Pharmaceutical Chemistry, Delhi Pharmaceutical Sciences Research University, New Delhi, India

Álvaro Torrinha  REQUIMTE-LAQV, Instituto Superior de Engenharia do Porto, Instituto Politécnico do Porto, Porto, Portugal

Ararso Nagari Wagassa  Department of Applied Chemistry, School of Natural Science, Adama Science and Technology University, Adama, Ethiopia

Preface

Since the last decade, utility of nanomaterials and functionalized nanostructures has become significant in multidisciplinary fields including biomedical, environmental, food and beverages, textiles, pharmaceutical, cosmetics, agricultural, sensors, energy storage management, electronic materials, etc. Specifically, new methods in the synthesis of functionalized nanomaterials (FNMs) and their applications in different areas of science have been developed. Functionalization of nanomaterials is a method of inserting a particular material onto the surface of the nanomaterial to boost its properties and reduce its toxicity. Functionalized nanomaterials can be synthesized through covalent, noncovalent, grafting, physical methods, etc. They have a great impact on the fabrication of electrochemical sensors and biosensors for the determination of a wide spectrum of molecules, toxic ions, and even disease diagnosis applications. Their real-time applications are extensive due to their unique characteristics like high electrical, thermal, mechanical, and electronic properties and biocompatibility, large surface, etc. Electrochemical sensors and devices are well known for their versatile applications and advantages like simple handling procedure, quick results, high sensitivity and selectivity, low consumption of sample, etc.

This book gives the readers a holistic insight into functionalized nanomaterial-based electrochemical sensors from design to application. This book is categorized into several sections: Section A explains “Modern Perspectives in Electrochemical-Based Sensors: Functionalized Nanomaterials (FNMs)”; Section B deals with “Fabrication of Functionalized Nanomaterial-Based Electrochemical Sensor Platforms”; Section C describes “Functionalized Carbon Nanomaterial-Based Electrochemical Sensors”; Section D provides “Noble Metals, Non-Noble Metal Oxides, and Noncarbon-Based Electrochemical Sensors”; Section E conveys “Functionalized Nanomaterial-Based Electrochemical Sensors for Environmental Applications”; Section F emphasizes on “Functionalized Nanomaterial-Based Electrochemical Sensor Technology for Food and Beverage Applications”; Section G focuses on “Functionalized NanomaterialBased Electrochemical Sensors for Point-of-Care Applications”; Section H deals with “Health, Safety, and Regulation Issues for Functionalized Nanomaterials”; Section I describes “Economics and Commercialization of Functionalized NanomaterialBased Electrochemical Sensors”; and Section J explains “Future of Functionalized Nanomaterial-Based Electrochemical Sensors.”

The goal of this book is to provide a comprehensive insight from the basic level to the application of FNMs for the fabrication of electrochemical sensors and biosensors. I hope this book will be a great asset to electrochemists, material scientists, college and university graduates, chemists, biologists, pharmacists, engineers,

xx Preface physicists, industrial researchers, and analytical scientists. The editor and contributors are eminent researchers and experts from universities and various industries. On behalf of Elsevier, we thank all the authors of this book for their valuable contributions. We are extremely thankful to John Leonard (editorial project manager) at Elsevier for his tremendous support and assistance throughout this assignment.

Section A Modern perspective in electrochemical-based sensors: Functionalized nanomaterials (FNMs)

Functionalized nanomaterial-based electrochemical sensors: A sensitive sensor platform

1

aDepartment of Metallurgical and Materials Engineering, Bartin University, Bartin, Turkey, bDepartment of Chemistry, School of Engineering, Presidency University, Bangalore, India

1.1 Introduction

A great advancement in science and technology as an indispensable technology growth is the use of Nanomaterials and nanotechnology. Nanomaterials are materials that have one of their dimensions less than or equal to 100-nm scale [1–4]. With the advancement in synthetic methodologies, the preparation of a variety of these nanomaterials is permitted with the desired size, surface properties, shape, and other physicochemical properties [5–7]. Moreover, the materials that can be functionalized thus present a great panorama for uniting biological credit and signal transduction mechanisms which lead to the development of novel bioelectronic devices with outstanding sensor properties [8–13]. Nanomaterials usually have a larger surface area and this compliments the improvement in electron-transfer rate [14–17]. Thus, these properties are quite utilized in catalysis, polymer technology, drug delivery, food production, painting, and electrochemical sensing [18]. Electrochemical sensors form a vital subdivision of chemical sensors in which the transduction element is designed from an electrode source [19,20]. It works on the principle of electrochemistry, which is a very influential electroanalytical technique that shows the advantages in terms of high sensitivity, instrument simplicity, portability, easy miniaturization, and is relatively cost-effective [21]. A portable biochemical detection was made possible, very recently, through the use of smartphones assimilated with sensors, such as test trips, sensor chips, and hand-held detectors [22]. The assimilation of these miniaturized devices as sensitive arrays was possible through the application of micro-electro-mechanical systems and of course nanotechnology [23–25]. Meanwhile, some of the properties of sensors are very high sensitivity, selectivity, and stability, researchers have been pushing a lot of effort on refining these properties. In this case, the incorporation of nanomaterials is playing its role as sensors. Generally, nanomaterials exhibit unique properties and functionalities which can create a promising evolution of the new analytical schemes that are easily triggered to detect various biological molecules [26]. These analytical schemes have been used with numerous sensor programs covering a wide range of nanomaterials and fabrication convolution [27]. A nano-level fabrication of the electrode surface is a gifted platform to develop high-performance electrochemical to detect the target

analytes [28]. The design of these types of nano-level electrode materials focuses on the signal amplification through the catalytic activity and conductivity, facile interactions with chemical and biological reagents, and the immobilization of the functional moieties with precisely designed as signal tags which are prominent in highly selective sensing [29]. Therefore, the fabrication of a functionalized nanomaterial-based electrode is recently progressing with high acceleration. This chapter aims to expose researchers to the success recorded in this area while hoping that the article will stimulate further discoveries in the area of electrochemical sensors using nanomaterials.

1.2

Quantum-Dot nanomaterial

Quantum dots are semiconductor nanocrystals in which excitons are confined in all three spatial dimensions. The confinement can be realized by fabricating the semiconductor in a very small size, typically several hundred to thousands of atoms per particle [30,31]. Due to quantum confinement effects, QDs act like artificial atoms, showing controllable discrete energy levels. QDs were first fabricated in the 1980s by Louis E. Brus and the unique properties of these special nano-structures attracted interest from many fields. Quantum-Dot (QD) semiconductor nanocrystals have been reported to be used for the design of multianalyte electrochemical aptamers biosensors with sub picomolar (attomole) detection limit [32].

QDs can be optically excited. When absorbing photons, electrons in QDs gain energy leading to the creation of excitons. An exciton is a bound state of an electron and a quasiparticle called a hole. After relaxation from the excitonic excited state to its lower energy state, the electron and hole recombine (exciton recombination), emitting a photon. The overall process of optical excitation, relaxation of the excited state, recombination of electron and hole, and fluorescent emission is called photoluminescence (PL). The number of photons emitted can be measured as a function of energy, which gives the PL spectrum. Different from many organic dyes, QDs can be excited by many light sources within a large wavelength range, since QDs have continuous and broad absorption spectra. Furthermore, many kinds of QDs can be excited by the same light source and their emission can be easily separated. The emission light spectra of QDs are narrower and more symmetric than conventional organic dyes, making the sensitivity of detection higher than for organic dyes. Due to this property, QDs are attractive fluorophores for biological imaging (biological tagging).

The energy gap of excitons in QDs is strongly size dependent. This size-dependent phenomenon is due to the effect of confinement: The smaller QDs have stronger confinement making the energy gap larger. Similarly, a larger size gives a smaller energy gap. Hence, QDs with different emission colors can be made from the same material by changing their size. Hence for larger (small) sizes, the emission is more toward the red (blue). Colloidal QDs, which are synthesized by relatively inexpensive wet chemistry methods, make it possible to have the desired particle size which makes it easy to find QDs with the energy spectrum we need and high quantum yield (number of photons absorbed over the number of photons emitted), even at room temperature. Currently, CdSe or CdTe QDs with a ZnS shell is commonly used and studied. The

Core/Shell structure diminishes chemical damage to the fluorescence core. ZnS is optically transparent to the emission range; therefore, there are no photon losses associated with the shell with visible light emission. A study, as discussed below, is done to show the application of QDs in biological imaging.

The aptamer is the RNA or DNA ligand to the target molecule and it was typically attained by a methodology called systematic evolution of ligands by exponential fortification (SELEX) [33]. The aptamers can fix powerfully to a target molecule like an antibody and can be custom-made with a higher degree of efficiency. This is as such used as a powerful tool for proteome analysis [34]. Other advantages are its qualified ease of isolation and modifications united with high stability. The nanocrystals play a very important and significant role in electro diversification of the electrical tags which is one of the requirements for multiplexed bioanalysis. Due to the remarkably low (attomole) detection limit, this can be a consequence of the extensive amplification excellence of the nanoparticle-based electrochemical stripping measurements [35]. Since it is a multianalyte biosensor, four different encoding nanomaterials, CdS, ZnS, CuS, and PbS, were used to differentiate the signals of four targeted DNA. For functioning the aptamer/Quantum-Dot-Based dual-analyte biosensor, a single-step displacement assay was utilized as presented in Scheme 1.1.

In the scheme, numerous thiolated aptamers were co-immobilized, along with the binding of similar QD-tagged proteins on the gold substrate (A). This was followed by the addition of sample (B), with the displacement of the tag proteins. This displacement allows the monitoring of remaining nanocrystals through an electrochemical detection source (C). The biosensor was first used for single analyte sensing to evaluate its sensitivity and selectivity. High sensitivity grew from the electrochemical detection is shown in Fig. 1.1A and the calibration plot, presented in Fig. 1.1B represents a rapid drop in the peak current up to 200 ng L 1 which, in the future, maintained a slower decrease (a characteristic of displacement assays). The detection limit of 20 ng L 1 (0.5 pM) was recorded between the 20 and 500 ng L 1 concentration range. Therefore, the biosensor has a considerably lower detection limit (of the order of 3–4) relative to those aptamer biosensors reported previously [36–38]. High reproducibility (relative standard deviation of 5%) was recorded after six consecutive measurements of 100 ng L 1 thrombin.

Dissolution of the QDs (conjugated to the undisplaced protein molecules) was carried out by the addition of HNO3 (100 μL, 0.1 M) and sonication for 1 h. The resulting solution was transferred to a 1 mL electrochemical cell containing 900 μL of acetate buffer (0.1 M, pH 4.6) and 10 ppm mercury (II). Electrochemical stripping detection proceeded after 1 min pretreatment at + 0.6 V, 2 min accumulation at 1.2 V, and scanning the potential to 0.25 V [32].

A multianalyte assignment of the biosensor was validated in Fig. 1.2. Here, the dual-analyte detection of thrombin (a) and lysozyme (b) was shown. Comparable reductions in both the metal peaks were a consequence of the simultaneous addition of both thrombin and lysozyme proteins (Fig. 1.2D). This advises that as much as five or six protein targets can be analyzed simultaneously in a single run if there are nonoverlapping metal peaks within a given potential window. CdS nanoparticle-based (another Quantum-Dot) biosensing of sugars established on their interaction with surface-functionalized lectins was also presented in Scheme 1.2 [39]. This is done

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