Nanofabrication for smart nanosensor applications (micro and nano technologies) 1st edition kaushik

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NanofabricationforSmart NanosensorApplications

NanofabricationforSmart NanosensorApplications

InternationalandInterUniversityCentreforNanoscienceandNanotechnology(IIUCN), SchoolofEnergyMaterials,MahatmaGandhiUniversity,Kottayam,Kerala,India; WuhanUniversity,WuchangDistrict,Wuhan,HubeiProvince,RepublicofChina

FernandoGomes

MacromoleculeInstituteProfessorEloisaMano;CivilEngineeringProgram,COPPE, TechnologyCenter-UniversityCity,FederalUniversityofRiodeJaneiro,RiodeJaneiro,Brazil

Elsevier

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Contributors

M.M.Abdullah PromisingCentreforSensorsandElectronicDevices(PCSED),Departmentof Physics,FacultyofScienceandArts,NajranUniversity,Najran,SaudiArabia

MostafaG.Aboelkheir MacromoleculeInstituteProfessorEloisaMano,TechnologyCenterUniversityCity,FederalUniversityofRiodeJaneiro,RiodeJaneiro,Brazil

GulzarAhmad DepartmentofPhysics,UniversityofAgriculture,Faisalabad,Pakistan

MazharS.AlZoubi DepartmentofBasicMedicalStudies,YarmoukUniversity,Irbid,Jordan

KhalidM.Al-Batanyeh DepartmentofBiologicalSciences,YarmoukUniversity,Irbid,Jordan

NormaAlias CenterforSustainableNanomaterials,IbnuSinaInstituteforScientificandIndustrial Research,UniversitiTeknologiMalaysia,Skudai,Malaysia

AlaaA.A.Aljabali DepartmentofPharmaceuticsandPharmaceuticalTechnology,Facultyof Pharmacy,YarmoukUniversity,Irbid,Jordan

LorcaAlzoubi DepartmentofPharmaceuticsandPharmaceuticalTechnology;MedicinalChemistry andPharmacognosyDepartment,FacultyofPharmacy,YarmoukUniversity,Irbid,Jordan

NidhiAsthana NationalCentreofExperimentalMineralogyandPetrology,UniversityofAllahabad, Allahabad,India

MurthyChavali ShreeVelagapudiRamaKrishnaMemorialCollege(PGStudies),Affiliatedto AcharyaNagarjunaUniversity,Nagaram;PGDepartmentofChemistry,DharmaAppaRaoCollege, AffiliatedtoKrishnaUniversity,Nuzvid;NTRC,MCETRC,Tenali,AndhraPradesh,India

RamchanderChepyala FPC@DCU – FraunhoferProjectCentreforEmbeddedBioanalytical SystemsatDublinCityUniversity,DublinCityUniversity,Dublin,Ireland

ShipluRoyChowdhury TissueEngineeringCentre,FacultyofMedicine,UniversitiKebangsaan Malaysia,KualaLumpur,Malaysia

Vı´torCorr^ eadaCosta MacromoleculeInstituteProfessorEloisaMano,TechnologyCenterUniversityCity,FederalUniversityofRiodeJaneiro,RiodeJaneiro,Brazil

MichaelK.Danquah ChemicalEngineeringDepartment,UniversityofTennessee,Chattanooga,TN, UnitedStates

KrishnaChitanyaEtika DepartmentofChemicalEngineering,BirlaInstituteofTechnologyand Science,Pilani,Rajasthan,India

IreneS.Fahim IndustrialEngineeringDepartment,SmartEngineeringSystemsResearchCenter (SESC),NileUniversity,Giza,Egypt

RomildoDiasToledoFilho CivilEngineeringProgram,COPPE,TechnologyCenter-University City,FederalUniversityofRiodeJaneiro,RiodeJaneiro,Brazil

SanjeevGautam NetajiSubhasUniversityofTechnology,Delhi,India

GaneshGollavelli CentreofExcellenceofNanotechnology;DepartmentofIndustrialChemistry, CollegeofAppliedSciences,AddisAbabaScienceandTechnologyUniversity,AddisAbaba,Ethiopia

HazidatulAkmaHamlan CenterforSustainableNanomaterials,IbnuSinaInstituteforScientificand IndustrialResearch,UniversitiTeknologiMalaysia,Skudai,Malaysia

AhmedM.Hassanein NanoelectronicsIntegratedSystemsCenter(NISC),NileUniversity,Giza, Egypt

MdEnamulHoque DepartmentofBiomedicalEngineering,MilitaryInstituteofScienceand Technology(MIST),Dhaka,Bangladesh

SaiqaIkram Bio/PolymerResearchLaboratory,DepartmentofChemistry,JamiaMilliaIslamia,New Delhi,India

PurnimaJain NetajiSubhasUniversityofTechnology,Delhi,India

YasirJaved DepartmentofPhysics,UniversityofAgriculture,Faisalabad,Pakistan

JaisonJeevanandam DepartmentofChemicalEngineering,CurtinUniversity,Miri,Sarawak, Malaysia

RocktotpalKonwarh DepartmentofBiotechnology,CollegeofBiologicalandChemical Engineering;CentreofExcellenceofNanotechnology,AddisAbabaScienceandTechnology University,AddisAbaba,Ethiopia

SamoKralj FacultyofNaturalSciencesandMathematics,UniversityofMaribor,Maribor,Slovenia

AmitKumar DyalSinghCollege,UniversityofDelhi,Delhi,India

EnamalaManojKumar BioserveBiotechnologies(India)PrivateLtd.,Hyderabad,Telangana,India

AhmedH.Madian NanoelectronicsIntegratedSystemsCenter(NISC),NileUniversity,Giza; RadiationEngineeringDepartment,NCRRT,EgyptianAtomicEnergyAuthority,Cairo,Egypt

TariqMahbub DepartmentofMechanicalEngineering,MilitaryInstituteofScienceand Technology,Dhaka,Bangladesh

ZaidBinMahbub DepartmentofMathematicsandPhysics,NorthSouthUniversity,Dhaka, Bangladesh

AhmedNawaz DepartmentofPhysics,UniversityofAgriculture,Faisalabad,Pakistan

SomiaNawaz DepartmentofPhysics,UniversityofAgriculture,Faisalabad,Pakistan

MohammadA.Obeid DepartmentofPharmaceuticsandPharmaceuticalTechnology,Facultyof Pharmacy,YarmoukUniversity,Irbid,Jordan

KaushikPal InternationalandInterUniversityCentreforNanoscienceandNanotechnology(IIUCN), SchoolofEnergyMaterials,MahatmaGandhiUniversity,Kottayam,Kerala,India;WuhanUniversity, WuchangDistrict,Wuhan,HubeiProvince,RepublicofChina

PeriasamyPalanisamy DepartmentofPhysics,GnanamaniCollegeofEngineering,Namakkal, TamilNadu,India

SureshBabuPalanisamy DepartmentofBiotechnology,CollegeofBiologicalandChemical Engineering,AddisAbabaScienceandTechnologyUniversity,AddisAbaba,Ethiopia

MamunRabbani DepartmentofBiomedicalPhysicsandTechnology,UniversityofDhaka,Dhaka, Bangladesh

LobnaA.Said NanoelectronicsIntegratedSystemsCenter(NISC),NileUniversity,Giza,Egypt

M.MunirSajid DepartmentofPhysics,GovernmentCollegeUniversity,Faisalabad,Pakistan

NaveedAkhtarShad DepartmentofPhysics,GovernmentCollegeUniversity,Faisalabad,Pakistan

BhashaSharma NetajiSubhasUniversityofTechnology,Delhi,India

ShreyaSharma NetajiSubhasUniversityofTechnology,Delhi,India

ZayedBinZakirShawon DepartmentofMathematicsandNaturalSciences,BRACUniversity, Dhaka,Bangladesh

ShashankShekhar NetajiSubhasUniversityofTechnology,Delhi,India

AsiyaS.I. BharathInstituteofHigherEducationandResearch(BIHER),BharathUniversity,Chennai, TamilNadu,India

PreetiSingh Bio/PolymerResearchLaboratory,DepartmentofChemistry,JamiaMilliaIslamia,New Delhi,India

FernandoGomes MacromoleculeInstituteProfessorEloisaMano;CivilEngineeringProgram, COPPE,TechnologyCenter-UniversityCity,FederalUniversityofRiodeJaneiro,RiodeJaneiro, Brazil

MurtazaM.Tambwala SAADCentreforPharmacyandDiabetes,SchoolofPharmacyand PharmaceuticalScienceUlsterUniversity,Coleraine,UnitedKingdom

SabuThomas InternationalandInterUniversityCentreforNanoscienceandNanotechnology (IIUCN),SchoolofChemicalSciences,MahatmaGandhiUniversity,Kottayam,Kerala,India

Editors’biography

Professor(Dr.)KaushikPal isanIndiancitizen.Hedidhis PH.D.inPhysics(e.g.Nanotechnology,Multidisciplinary Sciences,AdvancedMaterialsScience,Spectroscopy)from UniversityofKalyani,West-Bengal,India.Mostrecentlyhe awardedwithhonorable DOCTOROFSCIENCE(D.SC.) from HigherNationalYouthSkillInstitute,Sepang, Selangor,Malaysia.Heisthe“DistinguishResearchProfessor” at FederalUniversityofRiodeJaneiro,Brazil andactingas “ChairProfessorandGroupLeader,(Chief-Scientist&Faculty Fellow)”positionin WuhanUniversity,WuchangDist.,Hubei Province,RepublicofChina.Mostrecently,hehasbeena visitingprofessorworkingandcontributingattheInternationalandInterUniversityCentrefor NanoscienceandNanotechnology(IIUCN),SchoolofEnergyMaterials,MahatmaGandhi University,Kottayam,Kerala.Heawardedinternationalprestigiousawardse.g.awardedthe Marie-CurieExperiencedResearcher(PostdoctoralFellow)bytheEuropeanCommission NetworkinGreece,andreceivedtheBrainKorea(BK-21)NationalResearchFoundation VisitingScientistFellowshipinSouthKorea.HewasappointedSeniorPostdoctoralFellowat WuhanUniversity,ChinaandwithinayearachievedtheprestigiouspositionofChief-Scientist andFaculty(CAS)FellowbytheChineseAcademyofScience.Heservedasresearchprofessor (GroupLeaderandIndependentScientist),atBharathUniversity(BIHER),Researchand Development,Chennai.Hiscurrentresearchspansarefocusingone.g.MolecularNanoscience andnanofabrication,functionalmaterials,condensedmatterphysics(expt.),CNTs/graphene, liquidcrystal,polymericnanocomposite,switchabledevice,electronmicroscopyand spectroscopy,bioinspiredmaterials,drugdelivery,integration,switchabledevicemodulation, stretchableelectronics,supercapacitors,optoelectronics,greenchemistry,andbiosensor applications.Hesupervisesasignificantnumberofbachelor’s,master’s,PhD,andpostdoctoral scholar’stheses,andhisresearchhasbeenpublishedinseveralinternationaltop-tierjournals frompublisherse.g.RoyalChemicalSociety,Elsevier,Springer,IEEE,andInTech.Hehas edited25bookchapterswithsignificantpublishers,contributed10reviewarticles,andhas editedseveralbooksforElsevier,AppleAcademicPress,andInTech.Dr.Palisanexpertgroup leaderandtheassociatememberofvariousscientificsocieties,organizations,andprofessional bodies.Inhisacademicandprofessionalresearch,hehasreceivedanumberofsignificant

awardsandprizes.Hehasbeenthechairpersonof30nationalandinternationalevents, symposia,conferences,andworkshops,andhascontributedto10plenary,28keynote,and30 invitedlecturesworldwide.

ProfessorFernandoGomes graduatedinchemistryfromthe FederalUniversityofEspı´ritoSanto(1999),andreceiveda MasterinEngineeringandMaterialsSciencefromtheState UniversityoftheNorthFluminenseDarcyRibeiro(2002),aPhD inScienceandTechnologyofPolymersfromtheFederal UniversityofRiodeJaneiro(2006),andapostdoctorateinthe chemicalengineeringprogramatCOPPE/UFRJ,Brazil.Heis currentlyAssociateProfessorattheMacromoleculesInstituteat UFRJ,CollaboratedProfessorattheCivilEngineeringProgram atCOPPE/UFRJandYoungScientistintheStateofRiode Janeiro(FAPERJ-2015).Hemainlyworkswithpolymeric nanocompositesobtainedfromrenewableresourcesinthree mainlines:(I)inthefieldofenvironmentalrecovery,coordinatingresearchprojectsfocusedon theuseofrenewableresourcesfortheremovalofoilinspills;(II)inthefieldofhumanhealth, coordinatingprojectsthatseekkineticandspatialcontrolofthedrugreleaseprocess;and(III)in thefieldofsensors,wherehecoordinatesprojectsthatseektoobtainplantfibersthatconduct electricityfortheiruseinsensorsforintelligentdevices.Supervisorof 103 undergraduate students; 28 M.Sc.students, 8 Ph.D.studentsand 5 PostDoc.NowadaysIamthesupervisorof 4 undergraduatestudents; 2 M.Sc.students, 14 Ph.D.studentsand 2 PostDoc.Memberofthe editorialboardofCurrentAppliedPolymerScience(ISSN2452-2716),AssociateEditorofthe MedCraveOnlineJournal(MOJ)PolymerScience(ISSN:2574-9773),andEditorofthe AcademicJournalofPolymerScience.HealsoawardedYoungScientistofRiodeJaneiroState (FAPERJ2011and2014),memberofPostGraduatePrograminScienceandTechnologyof PolymersoftheFederalUniversityofRiodeJaneirosince2008.

Introductiontonanomaterialsand nanomanufacturingfornanosensors

aDepartmentofMechanicalEngineering,MilitaryInstituteofScienceandTechnology, Dhaka,Bangladesh

bDepartmentofBiomedicalEngineering,MilitaryInstituteofScienceandTechnology(MIST), Dhaka,Bangladesh

1.1Nanosensors

Sensorsaredevicesusedtodetectthepresenceofaspecificsubstanceortomeasureaphysical propertysuchastemperature,mass,orelectricaloropticalcharacteristicsandproducea signalforrecordingorfurtherpostprocessing.Thehistoryofsensorsisalongone.Thefirst thermostatcameintoexistenceinthe1880s,andthefirstinfraredsensorwasdevelopedin 1940.Nanosensorsaresimilartomacrolevelsensorsbuthaveatleastonedimensionin nanoscaleandcanbeusedtomeasuresignalsavailableatthatscale.Nanotechnology,withits rapiddevelopmentsinrecentyears,hasshowngreatpotentialinalmostallindustries. Variouselectronicsindustrieshavefueledthesedevelopmentstosatisfytheirneedfor miniaturization,andthenanosensorfieldhastakenadvantageoftheseadvancesforitsown development.Alargevolumeofresearchhasbeenconductedoverthelasttwodecadesin theareaofnanomaterialsforwiderapplications,includingnanosensors [1–10].Since nanosensorscandealwithsignalsproducedatthenanoscale,thesamplequantitiesneededare quitesmallanddetectionisveryrapid.Allofthesequalitieshavehelpedtheapplications ofvarioustypesofnanosensorsindifferentfields,especiallyinthemedicalandhomeland securityfields.Gainingaclearerunderstandingofthespecialpropertiesofferedatthe nanoscalebynanomaterials,evolutionofthevarioustechniquesfornanomaterialproduction, andexploitationofthespecialpropertiesofnanomaterialshavealladvancednanosensor development.

1.1.1Typesofnanosensors

Duringtheshorthistoryofnanosensors,thistechnologyhasexperiencedsubstantial developments.Sinceavarietyofnanosensorsareavailabletoday,classificationcanbe somewhatdifficult.However,nanosensorscanbeclassifiedbasedontwogeneral factors:(1)structureand(2)application.

Basedonstructure,nanosensorscanbefurtherclassifiedintotwogroups: Opticalnanosensors: Opticalnanosensorsusethesensitivityoffluorescenceforqualitative andquantitativemeasurement.

Electrochemicalnanosensors: Thisclassofnanosensormainlydetectselectronicorchemical propertiesofarespectivesubstanceandtransducesasignal.Recently,majordevelopments havetakenplaceinthistypeofnanosensortechnology.

Basedonapplication,nanosensorscanbeclassifiedintochemicalnanosensors,nanoscale electrometers,nanobiosensors,deployablesensors,andsoon.

1.1.2Applicationsofnanosensors

Nanosensorsaregraduallyassumingrolesinalmosteveryaspectofhumanlife.Anumberof sensorscandetectthepresenceofhazardousmaterialsormicroorganismsinfood,water,and air.Thesesensorsaresavinglivesindifferentcornersoftheworld.Inthemedicalfield nanosensorsarehavingahugeimpact:forexample,avarietyofnanosensorsarebeingusedin cancerdetection,DNAandproteindetection,andtargeteddrugdelivery.Deployablesensors havefoundapplicationsinhomelandsecurity.Variouschemicalsensorsarenowaddedto unmannedaerialvehiclestodetectthepresenceofpoisonousgasonthebattlefield,tosavethe livesofsoldiers.VarioustaggingsystemsemployRFIDchips,whicharealsoanapplicationof nanosensors.

1.2Nanomaterialsfornanosensors

Forcenturiesthebeautyofthe400CELycurgusCupandthestrengthandbeautyofa Damascussteelbladehaveamazedpeople,butithasbeenonlydecadessincewediscoveredthe secretbehindtheseextraordinaryancientartifacts:nanomaterials [11,12].Nanomaterials aredefinedasthosenanoparticles(NPs)thathaveatleastonedimensioninnanometerscaleand thatexhibitsomespecialpropertythatisnotavailableinthebulkformofthesame material.Thoughunknowinglyusedinseveralancientartifacts,themodern-dayextensive research,informedfabrication,andutilizationofnanomaterialsbeganin1857,whenMichael Faradayreportedthesynthesisofso-called“activatedgold,”whichwasacolloidalsolution

ofAuNPs [13].Sincethattime,theuseofnanomaterialshasslowlybutsurelyspread, duetotheirextraordinarypropertiesassociatedwiththeirsize.Nanomaterialsshow extraordinarypropertiesdifferentthantheirbulksizebecauseoftheirnanoscaledimension. Thesurface-to-volumeratioofnanomaterialsisveryhigh,whichresultsinvariationsin chemical,mechanical,optical,andmagneticnature [14].Toexplorethepropertiesand applicationsofnanomaterialsproperly,itisjudicioustoclassifythem.However,severalfactors canbeconsideredinclassifyingnanomaterials,suchasphysicalandchemicalproperties, manufacturingprocess,dimensionality,uniformity,composition,andsoforth [15].Fromthe pointofviewofthischapter,weclassifynanomaterialsintofourclassesbasedontheir chemicalcomposition:(1)carbon-based,(2)organic-based,(3)inorganic-based,and(4) composite-basednanomaterials.Inthefollowingsections,wediscussdifferentnanomaterials thatfallwithinthesefourcategoriesandtheirapplications,especiallyasnanosensors.

Atthispoint,abriefintroductiontonanosensorsmaybeveryhelpfulforthosenewtothis field.Asensorisadevicethatdetectsandrespondstoanychangeinitsenvironment. Dailylifeisfullofsensors,suchaslightsensors,rainsensors,laneassistinautomobiles, smokeandfirealarmsensors,electricalsensors,andsoforth.Na nosensorsperformthe samefunction,butonamuchsmallerscale(1– 100nm),capableofsensingpathogens, viruses,molecules,orevenasinglechemicalelement.Themainadvantagesofnanosensors aretheminutesamplequantitiesrequired, speed,portability,andlowcostinmass production,amongothers.

Thehistoryofnanosensorsisonlydecadesold.Sincethebeginningofthecurrentcentury,the worldhasexperiencedarapidescalationofproductionanduseofnanosensorsasaconsequence oftwofactors.First,nanosensors,duetotheirexcellentperformance,haveconvincedthe worldthattheycanbesuccessfullyusedindifferentapplicationsvaryingfromthefood industry,fireandhazardousgasdetection,tovariouscriticalfieldslikemilitaryandadvanced medicalapplications.Secondly,thereisatremendousadvancementofdifferent manufacturingprocessesusedformanufacturingnanosensors,increasedavailability,and developmentofnewnanomaterialsandmoreclearunderstandingofnanoscale phenomena [16].

1.2.1Propertiesofnanomaterialsfornanosensors

Nanomaterials,duetohighsurface-to-volumeratioandthemanufacturingprocess,offersome extraordinarypropertiesthatcanbeexploredtoproducevariousapplicationsindrug manufacturing,environmentalsensingandprotection,materialsandmanufacturingindustries, electronics,energyharvesting,etc.Afewpropertiesthatarerelevanttonanosensorsarebriefly describedinthefollowingsections.

1.2.1.1Opticalproperties

Nanomaterialsoffersomeexcellentopticalproperties,suchaslightabsorption,color,light emission,andmagnetoopticalpropertiesduetotheirsizes;thesepropertiesarequitedifferent fromtheirbulkpropertiesandmakenanomaterialsagoodchoiceforopticalnanosensors.One ofthefirstnanosensorsdevisedtomeasureinhomogeneouspHdistributioninthreedimensionalresolutionwasfluorescein-based,usingapolyacrylamidenanoparticle incorporatedwithpH-sensitivefluorescein-acrylamide [17].Fluorescentnanosensorscan respondtosomespecificstimuliprovidedbythesurroundingenvironmentandtransducea fluorescencesignaltothedetectortosenseenvironmentalchanges.Thesenanosensorsareused tomakeoxygensensors [18] andtemperaturesensors.Thelocalizedsurfaceplasmon(LSP) effectofthenoblemetalnanoparticleisacurrentactivefieldofresearchformaking nanosensors(Fig.1.1).Whenananoparticleconfinessurfaceplasmon,duetoitsdimension, comparabletothewavelengthoflight,thefreeelectronofthenanoparticleparticipatesin thecollectiveoscillation.Thisphenomenoniscalledlocalizedsurfaceplasmon(LSP) [19]. TheLSPeffectgreatlyenhancestheelectricfieldnearthenanoparticlesurfaceandatthe plasmonresonantfrequencytheparticleshowsmaximumopticalextinction.Anumberofgas sensors [20,21] andpHsensors [22,23] aremanufacturedusingLSP.

1.2.1.2Electronicproperties

Nanomaterialscanofferquiteexceptionalelectronicpropertiesthatoriginatefromtheshape andstructureofthenanomaterial.Whentalkingaboutexceptionalelectronicproperties,the namethatcomestomindfirstisgraphene.Graphenehasasingle-layer2Dhoneycomb structureinwhichbothsurfacesareavailableformoleculeabsorption.Thestructurecausesthe electronseemlytobemassless [24] andtheelectronmovesatanaveragespeedwhichis 300timeslessthanthespeedoflightatvacuum.Thisallowsmanyrelativisticeventstobe

Schematicdiagramoflocalizedsurfaceplasmoneffect.

observablewithoutaparticleaccelerator [15].Thecarbonnanotube(CNT)inwhichgraphene actsasabuildingblockalsoofferssomeexcellentelectronicproperties.The sp 2 hybridization ofthecarbonorbitalsintheCNTleavesfreeelectronsatthesurfaceofthetubes,which yieldstheseexcellentproperties.CNTcanshowmetallic,semiconducting,orinsulating behavior,whichcanbecontrolledbycontrollingthediameter,chiralityoftheCNT,andany functionalizationordopingdoneonCNT [25].Nanosensorsusingthesepropertiesdetectusing twomethods:(a)currentenhancement,and(b)currentinhibition.Variouselectrochemical sensorshavebeendevelopedfordifferentpurposes,suchasdetectingdopamine [26],histamine [27],bacteria [28],glucose [29],andsoforth,usingtheelectronicpropertiesofnanomaterials.

1.2.1.3Magneticproperties

Duetotheunevenarrangementandorientationofelectronsinnanomaterials,andtheirsize, nanomaterialsexhibitexcellentmagneticpropertiestoo.Magneticpropertiesofnanomaterials arebecomingacenterofinterestindifferentbranchesofengineering,includingbutnotlimited todifferenttypesofcatalysis,biomedicineforcancertreatment,magneticfluids,nuclear magneticresonanceimaging(NMR),magneticresonanceimaging(MRI),andenvironmental remediation [30].Magneticnanosensorsusedifferenttechniquestoperformdetection,likethe effectmagneticparticlesexertonwaterprotonrelaxationrates,bydeterminingtherelaxation ofthemagneticmomentwithinthemagneticparticle,bydetectingthepresenceofamagnetic particleusingmagnetoresistivity,etc.Kohetal.explaindifferentbiosensorsusingthe previouslymentionedmethods.Thefollowingfiguresshowschematicrepresentationsofthe threeprocedures [31]. Fig.1.2Arepresentshowmagneticnanoparticlesdephasetheprotonsof waterforabetterMRIscan.Magneticparticlesgenerallystaydispersedinaliquidsolvent.But whenatargetanalyte(trianglein Fig.1.2A)appears,thedispersednanoparticlesproducean aggregatearounditandeventuallythisaggregatedephasesthespinsofwaterprotonsmore efficientlythanthedispersedstate.Thisreducesthespin-spinrelaxationtimeT2 toproducea betterMRIimage. Fig.1.2Bshowstheapplicationofmagneticmomentrelaxationwithina magneticnanoparticleforbacterialdetection.ThetypeofrelaxationusedhereisNeel relaxation.IntheupperfigureA,amagneticfieldisappliedtothenanoparticlesandtheyorient themselvesalongtheappliedfield.Someofthenanoparticlesarebondedwiththetarget bacteria.Later,infigureB,thefieldisremovedandmanyoftheparticlesexperienceBrownian relaxationandrandomlyorientinadifferentdirection.Butthenanoparticlesbondedtothe bacteriacannotundergoBrownianrelaxationandrathershowNeelrelaxation,whichis comparativelysloweranddetectable.Thesuperconductingquantuminterferencedevices (SQUIDs)detecttheslowerNeelrelaxationandbacterialdetectionisperformed. Fig.1.2C showstheoperationofamagnetoresistivesensor.Thebasicprinciplethatamagnetoresistive sensorappliesisthatthemagneticparticlebondstothesurfaceofthesensorandeventually altersitsmagneticfield.Thiscausesachangeinsensorcurrentandthedetectionisperformed. Therearetwomechanismsthroughwhichmagneticparticlesbindtothesensorsurface:(i)direct labeling,and(ii)indirectlabeling.Inthecaseofdirectlabeling,magneticnanoparticlesdirectly

Sensor functionalization

antibody BSA

Linker incubation

Analyte incubation

Nanotag-based quantification

Capture antibodyBSAAnalyteBiotinylated antibody

Streptavidin-coated magnetic nanotag

Magnetoresistive Sensor

(A)Magneticpropertyofnanomaterialsusedforsensingapplications [31].(B)Magneticpropertyofnanomaterialsusedforsensing applications(workingprincipleofSQUID) [31].(C)Schematicdiagramofgiantmagnetoresistivesensorapplication [31].

Fig.1.2

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Henry Adams: History of the United States, 3444 (3328).

See maps between pages 3342-3343 (3326-3327).

6. FEDERALIST SECESSION MOVEMENT (A. D. 1804):

T. M. Cooley:

The Acquisition of Louisiana, 3444 (3328).

C. F. Robertson:

The Louisiana Purchase, 3445 (3329).

"The purchase, according to the Federal view of the Constitution, was perfectly legitimate. … But the Federalists in general took narrow and partisan views, and in order to embarrass the administration resorted to quibbles which were altogether unworthy the party which had boasted of Washington as its chief and Hamilton as the exponent of its doctrines. … The Federal leaders did not stop at cavils; they insisted that the unconstitutional extension of territory was in effect a dissolution of the Union, so that they were at liberty to contemplate and plan for a final disruption."

JUDGE T. M. COOLEY.

7. THE BRITISH IMPRESSMENT OF SEAMEN:

G. Tucker: History of the United States 3444 (3328).

Henry Adams: History of the United States, 3444 (3328).

Goldwin Smith: The United States, 3444-3445 (3328-3329).

8. THE IMPEACHMENT OF JUDGE CHASE (A. D. 1804-1805):

Henry Adams: John Randolph, 3445-3446 (3330).

J. Q. Adams: Memoirs, 3446 (3330).

J. Schouler: History of the United States, 3446-3447 (3331).

9. THE LEWIS AND CLARK EXPEDITION (A. D. 1804-1805):

The Nation: Review of Dr. Coues’ History, 3447-3448 (3331-3332).

10. AARON BURR’S FILIBUSTERING SCHEME (A. D. 1806-1807):

J. D. Hammond: History of Political Parties, 3450-3451 (3334-3335). {790}

11. THE QUESTION OF THE SLAVE TRADE:

W. F. Poole: Anti-Slavery Opinions, 3002 (2924).

John Fiske: The Critical Period, 3002-3003 (2924-2925).

C. P. Lucas: The British Colonies, 3003 (2925).

E. Quincy: Life of Josiah Quincy, 3451-3452 (3336).

12. TROUBLES WITH GREAT BRITAIN (A. D. 1804-1810):

J. B. McMaster: History of the United States, 3448-3449 (3332-3333).

S. H. Gay: James Madison, 3449-3450 (3333-3334).

Henry Adams: History of the United States, 3450 (3334).

Henry Adams: History of the United States, 3452-3453 (3336-3337).

Goldwin Smith: The United States, 3453 (3337).

G. L. Rives: Thomas Barclay, 3454 (3338).

13. SIXTH PRESIDENTIAL ELECTION;

JAMES MADISON PRESIDENT (A. D. 1808):

J. Schouler: History of the United States, 3453 (3337).

14. THE THIRD CENSUS (A. D. 1810), 3454 (3338).

15. LOUISIANA ADMITTED TO THE UNION (A. D. 1812):

Waring and Cable: New Orleans, 2095 (2051).

L. Carr: Missouri, 2095 (2051).

J. W. Monette: The Valley of the Mississippi, 2095 (2051).

R. Hildreth: History of the United States, 1182-1183 (1153).

16. BEGINNING OF THE WAR WITH GREAT BRITAIN (A. D. 1812):

C. Schurz: Life of Henry Clay, 3455 (3339).

R. Johnson: The War of 1812,

3456-3457 (3340-3341).

T. W. Higginson: History of the United States, 3457-3458 (3341-3342).

R. Hildreth: History of the United States, 3458 (3342).

J. Schouler: History of the United States, 3458-3459 (3342-3343).

17. CONDITION, AND EARLY SUCCESSES, OF THE NAVY:

J. A. Stevens: Second War with Great Britain, 3459 (3343).

J. R. Soley: Wars of the United States, 3459-3460 (3343-3344).

18. PERRY’S VICTORY ON LAKE ERIE (A. D. 1813):

J. Schouler: History of the United States, 3460-3462 (3344-3346).

T. Roosevelt: The Naval War, 3462 (3346).

19. THE BURNING OF TORONTO, AND BUFFALO (A. D. 1813):

G. Bryce: History of Canada, 3462-3463 (3346-3347).

J. T. Headley: Second War with England, 3463-3464 (3347-3348).

R. Johnson: The War of 1812, 3464-3465 (3348-3349).

20. THE CREEK WAR; JACKSON’S FIRST CAMPAIGN:

A. S. Gatschet: The Creek Indians, 102 (95).

A. Gallatin: Synopsis of Indian Tribes, 102 (95).

W. G. Sumner: Andrew Jackson, 3465 (3349).

21. LUNDY’S LANE, AND LAKE CHAMPLAIN (A. D. 1814):

S. Perkins: History of the Late War, 3466-3467 (3350-3351).

W. Dorsheimer: Buffalo in the War of 1812, 3467-3468 (3351-3352).

T. Roosevelt:

The Naval War of 1812, 3469-3470 (3353-3354).

22. THE CAPTURE OF WASHINGTON; BURNING OF PUBLIC BUILDINGS (A. D. 1814):

A. Johnston:

The United States, 3465 (3349).

C. B. Todd:

The Story of Washington, 3468 (3352).

G. R. Gleig:

Campaigns of the British Army, 3468 (3352).

R. Hildreth:

History of the United States, 3468-3469 (3352-3353).

23. THE LAST BATTLES OF THE WAR:

J. R. Soley:

The Boys of 1812, 3474 (3358).

J. Schouler: History of the United States, 3474-3475 (3358-3359).

24. THE TREATY OF PEACE (A. D. 1814):

J. T. Morse, Jr.:

John Quincy Adams, 3470-3471 (3354-3355).

T. Wilson: The Treaty of Ghent, 3471 (3355).

Full Text of the Treaty, 3471-3474 (3355-3358).

25. INCORPORATION OF THE SECOND BANK OF THE UNITED STATES (A. D. 1817):

D. Kinley: The Treasury of the United States, 2258-2259 (2214-2215).

W. G. Sumner: Andrew Jackson, 2259 (2215).

A. Johnston: History of American Politics, 2259 (2215).

26. THE EIGHTH PRESIDENTIAL ELECTION; JAMES MONROE ELECTED (A. D. 1816):

N. Sargent: Public Men and Events, 3475-3476 (3359-3360).

E. Stanwood:

Presidential Elections, 3476 (3360).

27. THE FIRST MOVE TOWARD "INTERNAL IMPROVEMENTS" (A. D. 1816-1817):

A. B. Hart: Formation of the Union, 3476 (3360).

C. Colton: Life of Henry Clay, 3476 (3360).

28. ADMISSION OF NEW STATES TO THE UNION:

(a) Indiana (A. D. 1816).

T. Donaldson: The Public Domain, 2434-2435 (2382-2383).

J. W. Monette: The Mississippi Valley, 1787-1788 (1748-1749).

(b) Mississippi (A. D. 1817).

J. W. Monette: The Mississippi Valley, 2233 (2189).

T. Donaldson: The Public Domain, 2094 (2050).

J. Schouler:

History of the United States, 2233 (2189).

(c) Illinois (A. D. 1818).

J. Wallace: History of Illinois, 1734 (1695).

B. A. Hinsdale: The Old Northwest, 3379-3380 (3263-3264).

J. B. McMaster: History of the United States, 2430-2431 (2378-2379).

J. W. Monette: The Mississippi Valley, 1787-1788 (1748-1749).

R. G. Thwaites: The Boundaries of Wisconsin, 3776 (3655).

(d) Alabama (A. D. 1819).

W. Brewer: Alabama, 30 (32).

(e) Maine (A. D. 1820).

C. W. Tuttle: Captain John Mason, 2354-2355 (2306-2307).

C. W. Elliott: New England History, 2122-2123 (2079-2080).

G. L. Austin: History of Massachusetts, 2123 (2080).

W. D. Williamson: History of Maine, 2123 (2080).

29. THE SEMINOLE WARS:

A. S. Gatschet: The Creek Indians, 108 (101).

D. G. Brinton: The Floridian Peninsula, 108-109 (101-102).

Bryant and Gay: History of the United States, 1183 (1153).

W. G. Sumner: Andrew Jackson, 1183-1184 (1154).

T. Roosevelt: Life of Benton, 1184 (1154).

30. THE DARTMOUTH COLLEGE CASE (A. D. 1819):

G. T. Curtis: Life of Daniel Webster, 754-755 (3741-3742).

{791}

31. THE BEGINNING OF OCEAN NAVIGATION:

F. E. Chadwick: Development of the Steamship, 3115-3116 (3033-3034).

32. NINTH PRESIDENTIAL ELECTION; THE "ERA OF GOOD FEELING" (A. D. 1820):

J. Schouler: History of the United States, 3478 (3362).

T. W. Higginson: History of the United States, 3478 (3362).

"Monroe like Washington was re-chosen President by a vote practically unanimous. One, however, of the 232 electoral votes cast was wanting to consummate this exceptional honor; for a New Hampshire elector, with a boldness of discretion which, in our days and especially upon a close canvass, would have condemned him to infamy, threw away upon John Quincy Adams the vote which belonged like those of his colleagues to Monroe, determined, so it is said, that no later mortal should stand in Washington’s shoes. Of America’s Presidents elected by virtual acclamation history furnishes but these two examples; and as between the men honored by so unapproachable a tribute of confidence, Monroe entered upon his second term of office with less of real political opposition than

Washington." J. SCHOULER.

33. THE FOURTH CENSUS (A. D. 1820), 3478 (3362).

34. THE FIRST GREAT CONFLICT OVER SLAVERY; THE MISSOURI COMPROMISE (A. D. 1818-1821):

Waring and Cable: New Orleans, 2095 (2051).

L. Carr: Missouri, 2095 (2051).

Carl Schurz: Life of Henry Clay, 3476-3477 (3360-3361).

J. A. Woodburn: The Missouri Compromise, 3477-3478 (3361-3362).

35. THE MONROE DOCTRINE (A. D. 1823):

T. W. Higginson: History of the United States, 3478-3479 (3362-3363).

D. C. Gilman: James Monroe, 3479 (3363).

36.

TARIFF

LEGISLATION;

"THE AMERICAN SYSTEM" (A. D. 1816-1824):

O. L. Elliott: The Tariff Controversy, 3153-3154 (3069-3070).

T. H. Benton: Thirty Years’ View, 3154 (3070).

STUDY XLI.

Page references in first 1895 edition in parentheses.

THE UNITED STATES FROM THE ELECTION OF ADAMS (1825) TO THE COMPROMISE OF 1850.

1. TENTH PRESIDENTIAL ELECTION (A. D. 1824):

J. Quincy: Life of J. Q. Adams, 3479-3480 (3364).

J. P. Kennedy: Life of William Wirt, 3480 (3364).

Goldwin Smith: The United States, 3480-3481 (3364-3365).

2. RECONSTRUCTION OF PARTIES:

T. H. Benton: Thirty Years’ View, 3481 (3365).

A. Johnston: History of American Politics, 3481-3482 (3365-3366).

3. TARIFF CHANGES; "THE BILL OF ABOMINATIONS":

T. H. Benton: Thirty Years' View, 3154 (3070).

H. C. Lodge: Daniel Webster, 3154 (3070).

W. G. Sumner: Andrew Jackson, 3154-3155 (3071).

C. Schurz: Life of Henry Clay, 3155 (3071).

4. ELEVENTH PRESIDENTIAL ELECTION; ANDREW JACKSON (A. D. 1828):

W. G. Sumner: Andrew Jackson, 3482 (3366).

T. H. Benton:

Thirty Years’ View, 3482 (3366).

5. NULLIFICATION AND DISUNION SENTIMENT:

S. H. Gay: James Madison, 3438-3439 (3322-3323).

T. M. Cooley: The Acquisition of Louisiana, 3443-3444 (3327-3328).

A. Johnston: American Politics, 3470 (3354).

H. von Holst: Constitutional History, 3470 (3354).

Texts of Kentucky and Virginia Resolutions, 3435-3438 (3319-3322).

6. NULLIFICATION ORDINANCE OF SOUTH CAROLINA; WEBSTER-HAYNE DEBATE:

G. T. Curtis: Life of Daniel Webster, 3482-3483 (3366-3367).

C. Schurz: Life of Henry Clay, 3483 (3367).

G. Hunt: The Nullification Struggle,

3483-3484 (3367-3368).

Text of Ordinance of Nullification, 3485 (3369).

7. THE BEGINNING OF THE "SPOILS SYSTEM":

John Fiske: Civil Government in the United States, 490.

8. RISE OF THE ABOLITIONISTS:

H. von Holst: Constitutional History, 3005-3006 (2927-2928).

B. Tuckerman: William Jay, 3485-3486 (3369-3370).

Goldwin Smith: William Lloyd Garrison, 3486 (3370).

J. F. Clarke: Anti-Slavery Days, 3487 (3370-3371).

"The ‘Liberator’ was a weekly journal, bearing the names of William Lloyd Garrison and Isaac Knapp as publishers. Its motto was, ‘Our Country is the world, Our Countrymen are Mankind,’ a direct challenge to those whose motto was the Jingo cry of those days, ‘Our Country, right or wrong!’ … The salutatory of the ‘Liberator’ avowed that its editor meant to speak out without restraint. ‘I will be as harsh as truth and as uncompromising as justice. On this subject [Slavery] I do

not wish to think, or speak, or write with moderation. No! No! Tell a man whose house is on fire to give a moderate alarm; tell him to moderately rescue his wife from the hands of the ravisher; tell the mother to gradually extricate her babe from the fire into which it as fallen but urge me not to use moderation in a cause like the present. I am in earnest I will not equivocate I will not excuse I will not retreat a single inch I will be heard.’ This promise was amply kept."

GOLDWIN SMITH.

9. THE FIFTH CENSUS (A. D. 1830).

3487 (3371).

10. THE FIRST RAILROADS:

W. J. M. Rankine:

The Steam Engine, 3111-3112 (3029-3030).

S. Smiles: Life of George Stephenson, 3112 (3030).

C. F. Adams, Jr.: Railroads, 3112-3113 (3030-3031).

11. JACKSON AND THE UNITED STATES BANK:

D. Kinley: The Independent Treasury, 2258-2259 (2214-2215).

W. G. Sumner: Andrew Jackson,

2259 (2215).

A. Johnston: American Politics, 2259 (2215).

J. Parton: Life of Jackson, 3487-3488 (3371-3372).

C. Schurz: Life of Clay, 3488 (3372).

12. BIRTH OF THE WHIG PARTY (A. D. 1834):

E. Stanwood: Presidential Elections, 3488 (3372).

G. T. Curtis: Life of Webster, 3488-3489 (3372-3373).

13. SLAVERY IN THE DISTRICT OF COLUMBIA; THE RIGHT OF PETITION:

N. Sargent: Public Men and Events, 3489 (3373).

J. F. Clarke: Anti-Slavery Days, 3490 (3374), 3494 (3378).

Bryant and Gay:

History of the United States, 3490 (3374).

T. H. Benton: Thirty Years’ View, 3492 (3376).

14. THIRTEENTH PRESIDENTIAL ELECTION (A. D. 1836):

A. D. Morse: Political Influence of Jackson, 3490-3491 (3374-3375).

G. Bancroft: Martin Van Buren, 3491 (3375).

{792}

15. THE FINANCIAL PANIC OF 1837:

A. Johnston: American Politics, 2259 (2215).

E. M. Shepard: Martin Van Buren, 3489 (3373).

A. Johnston: History of the United States, 3774 (3653).

Century Magazine: Cheap Money Experiments, 2259-2260 (2215-2216).

T. M. Cooley: Michigan, 2260 (2216).

E. G. Spaulding: 100 Years of Banking, 2260 (2216).

A. S. Bolles: Financial History, 3491 (3375).

16. ADMISSION OF NEW STATES; ARKANSAS, MICHIGAN:

T. Donaldson: The Public Domain, 2094 (2050).

J. W. Monette: The Mississippi Valley, 140 (133), 1787-1788 (1748-1749).

R. G. Thwaites: The Boundaries of Wisconsin, 2223-2224 (2179-2180).

17. THE SIXTH CENSUS (A. D. 1840).

3493 (3377).

18. THE HARRISON-TYLER ADMINISTRATION (A. D. 1841-1845):

N. Sargent:

Public Men and Events, 3493 (3377).

A. Johnston: American Politics, 3493-3494 (3377-3378).

J. F. Clarke: Anti-Slavery Days, 3494 (3378).

A. S. Bolles: Financial History, 3158 (3074).

J. Schouler: History of the United States, 3494-3495 (3378-3379).

19. THE POLK ADMINISTRATION (A. D. 1845-1849):

W. Wilson: Division and Reunion, 3495 (3379).

E. M. Shepard: Martin Van Buren, 3496 (3380).

20. THE "WALKER TARIFF" (A. D. 1846):

A. L. Perry Political Economy, 3159 (3075).

J. G. Blaine: Twenty Years in Congress, 3159-3160 (3075-3076).

21. ADMISSION OF NEW STATES TO THE UNION; FLORIDA, TEXAS, IOWA, WISCONSIN:

R. Hildreth: History of the United States, 1184 (1154).

T. Roosevelt: Life of Benton, 1184 (1154).

H. Wilson: The Slave Power, 3495-3496 (3379-3380).

J. W. Monette: The Mississippi Valley, 3186 (3101).

C. Schurz: Life of Clay, 3187 (3102).

J. W. Draper: American Civil War, 3187-3188 (3102-3103).

R. G. Thwaites: Boundaries of Wisconsin, 3776 (3655).

See Maps between 3442-3443 (3326-3327).

22. THE WAR WITH MEXICO

(A. D. 1846-1848):

H. Wilson: The Slave Power, 2217 (2173).

J. W. Draper: American Civil War, 2217-2218 (2173-2174).

A. H. Noll: History of Mexico, 2218 (2174).

Bryant and Gay: History of the United States, 2218 (2174).

J. R. Soley: Wars of the United States, 2218-2219 (2174-2175).

H. O. Ladd: War with Mexico, 2219-2220 (2175-2176).

23.

THE FREE SOIL PARTY; SIXTEENTH PRESIDENTIAL ELECTION (A. D. 1848):

E. M. Shepard: Martin Van Buren, 3498 (3382).

C. F. Adams:

Richard Henry Dana, 3498 (3382).

C. Colton: Life of Clay, 3498 (3382).

24. THE SEVENTH CENSUS (A. D. 1850), 3499 (3383).

25. CONQUEST OF CALIFORNIA; DISCOVERY OF GOLD:

J. Royce: California, 358 (348).

E. E. Dunbar: Romance of the Age, 359-360 (349-350).

J. S. Hittell: Discovery of Gold, 360 (350).

J. E. Cairnes: Political Economy, 2261 (2217).

26. AGGRESSION OF THE SLAVE POWER; WEBSTER’S "SEVENTH OF MARCH" SPEECH (A. D. 1850):

J. S. Landon: Constitutional History, 3499 (3883).

F. W. Seward: Seward at Washington, 3499-3500 (3883-3884).

Daniel Webster: Works, 3500-3503 (3384-3387).

H. C. Lodge: Daniel Webster, 3503 (3387).

J. F. Rhodes: History of the United States, 3503 (3387).

H. Wilson: The Slave Power, 1685 (1646).

"When Seward came to the territorial question, his words created a sensation. ‘We hold,’ he said, ‘no arbitrary authority over anything, whether acquired lawfully or seized by usurpation. The Constitution regulates our stewardship; the Constitution devotes the domain (i. e. the territories not formed into States) to union, to justice, to defense, to welfare, and to liberty. But there is a higher law than the Constitution, which regulates our authority over the domain, and devotes it to the same noble purposes. The territory is a part, no inconsiderable part, of the common heritage of mankind, bestowed upon them by the Creator of the Universe. We are His stewards, and must so discharge our trust as to secure in the highest attainable degree their happiness.’ This remark about ‘a higher law’ … was destined to have a transcendent moral influence. A speech which can be condensed into an aphorism is sure to shape convictions."

J. F. RHODES.

27. The Fugitive Slave Law; "Compromise of 1850":

M. G. McDougall: Fugitive Slaves, 3421-3422 (3305-3306)

W. R. Houghton: American Politics, 3503-3504 (3387-3388).

J. F. Rhodes: History of the United States, 3504 (3388)

C. Schurz: Life of Clay, 3504 (3388).

Text of Fugitive Slave Law, 3504-3507 (3388-3391).

STUDY XLII

Page references in first 1895 edition in parentheses.

ENGLAND (GREAT BRITAIN AND IRELAND) FROM THE FALL OF NAPOLEON TO THE DEATH OF QUEEN VICTORIA.

1. ENGLAND AT THE CLOSE OF THE NAPOLEONIC WARS:

J. F. Bright: History of England,

975-976 (948-9).

J. McCarthy: Sir Robert Peel, 977-978 (950-951).

H. Ashworth: Richard Cobden, 3152-3153 (3068-3069).

2. AGITATION FOR PARLIAMENTARY REFORM (A. D. 1816-):

C. Knight: History of England, 976-977 (949-950).

J. McCarthy: Sir Robert Peel, 977-978 (950-951).

3. REMOVAL OF DISABILITIES FROM DISSENTERS (A. D. 1827):

J. R. Green: History of the English People, 923-924 (896-897):

J. Stoughton: Religion in England. 924 (897).

W. E. H. Lecky: History of England, 944-945 (917-918).

S. Walpole:

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