Surface Enhanced Raman Spectroscopy - Anal., Biophys, Life Sci Apps PDF
Preview Surface Enhanced Raman Spectroscopy - Anal., Biophys, Life Sci Apps
Editedby SebastianSchlu¨cker SurfaceEnhancedRaman Spectroscopy Related Titles Andrews,D.L.(ed.) Sasic,S.(ed.) Encyclopedia ofApplied PharmaceuticalApplicationsof Spectroscopy RamanSpectroscopy 2010 2008 ISBN:978-3-527-40773-6 ISBN:978-0-8138-1013-3 Salzer,R.,Siesler,H.W.(eds.) Aroca,R. Infrared andRaman Surface-Enhanced Vibrational Spectroscopic Imaging Spectroscopy 2009 2006 ISBN:978-3-527-31993-0 ISBN:978-0-471-60731-1 Amer,M.S.(ed.) RamanSpectroscopy forSoft MatterApplications 2009 ISBN:978-0-470-45383-4 Wartewig,S. MaterialsCharacterization IntroductiontoMicroscopicand SpectroscopicMethods 2008 ISBN:978-0-470-82298-2 Edited by Sebastian Schlu¨cker Surface Enhanced Raman Spectroscopy Analytical, Biophysical and Life Science Applications TheEditor AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Prof.Dr.SebastianSchlu¨cker editors,andpublisherdonotwarrantthe UniversityofOsnabru¨ck informationcontainedinthesebooks, DepartmentofPhysics includingthisbook,tobefreeoferrors. Barbarastraße7 Readersareadvisedtokeepinmindthat 49076Osnabru¨ck statements,data,illustrations,procedural Germany detailsorotheritemsmayinadvertentlybe inaccurate. LibraryofCongressCardNo.:appliedfor BritishLibraryCataloguing-in-Publication Data Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Bibliographicinformationpublishedbythe DeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de>. 2011WILEY-VCHVerlag&Co.KGaA, Boschstr.12,69469Weinheim,Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form–byphotoprinting,microfilm,orany othermeans–nortransmittedortranslated intoamachinelanguagewithoutwritten permissionfromthepublishers.Registered names,trademarks,etc.usedinthisbook, evenwhennotspecificallymarkedassuch, arenottobeconsideredunprotectedbylaw. Cover AdamDesign,Weinheim Typesetting LaserwordsPrivateLtd., Chennai,India PrintingandBinding FabulousPrintersPte Ltd,Singapore PrintedinSingapore Printedonacid-freepaper ISBN:978-3-527-32567-2 ePDFISBN:978-3-527-63276-3 oBookISBN:978-3-527-63275-6 ePubISBN:978-3-527-63306-7 V Foreword Morethan80yearssincethediscoveryoftheRamaneffecthavepassedandRaman spectroscopyhas becomeoneofthe mostimportant methodswithin the various methodsofanalysisandstructuraldeterminations.Certainly,thediscoveryofthe laser in 1960 has openedup new horizons for Raman spectroscopyand brought severalnewusefultechniques.Oneofthemostinterestingandsignificantfindings in this field is undoubtedly surface-enhanced Raman scattering (SERS) which wasdiscoveredin1977.Withinthisphenomenon,moleculesadsorbedontometal surfaces under certain conditions exhibit an anomalously large interaction cross sectionfor the Raman effect.It might be thought that a subject originated more thanthreedecadesagowouldbevirtuallyexhaustedbynow,butnothingcouldbe fartherfromtruth.The recentdevelopmentsinSERS have ledtolarge increases inthesensitivityofSERSmeasurementsandhaveenablednewphenomenatobe observed and applied. SERS measurements are expected to become increasingly importantinchemistry,biochemistry,andbiophysics. In the 14 chapters of this book, an authoritative, up-to-date account of the principles and fundamentals of SERS is given including many examples for its applications. The book includes the basic theory for SERS; summarizes the various SERS substrates; discusses quantitative SERS methods with empha- sis on reproducibility, stability and sensitivity up to single molecule detection; and describes SERS microscopy, electrochemical SERS, surface enhanced reso- nanceRamanscattering(SERRS),andsurface-enhancedhyperRamanscattering (SEHRS), as well as surface- and tip-enhanced coherent anti-Stokes Raman scattering (SE-CARS, TE-CARS). Applications of SERS include the detection of organic pollutants and pharmaceuticals; studies of electron transfer of proteins at membranemodels;investigations ofmicrofluidics,quantitative DNAanalysis, biomedical applications by means of SERS microscopy, SERS as an intracellular probe;and couplingofSERS withvariousseparationmethods(e.g. liquid orgas chromatography). Theabundantreferencesprovidereadyaccesstotheoriginalresearchliterature. AsthefieldofSERShassufficientlymaturedduringthepastdecades,thedanger of rapid obsolescence for this book is less. The subject matter, however, still offersplentyofopportunityforfurtherexplorationandexploitation.Inmyopinion thisbook,whichclearlyexpressesthecurrentexcitementinthisextremelyactive SurfaceEnhancedRamanSpectroscopy:Analytical,BiophysicalandLifeScienceApplications.EditedbySebastianSchlu¨cker Copyright2011WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim ISBN:978-3-527-32567-2 Openmirrors.com Openmirrors.com VI Foreword research area, will make a substantial contribution to the further growth of an increasinglyimportantsubfieldofvibrationalspectroscopy. Professor Schlu¨cker, editor of this volume, is one of the leading researchers working currently in the SERS field. As chemist at the University of Wu¨rzburg, Germany, and the National Institutes of Health, Bethesda, USA, and now as physicistattheUniversityofOsnabru¨ck,Germany,hehasplayedamajorrolein introducingafewimportantnewexperimentaltechniquesofSERS(e.g.thedirect and label-free SERS detection of solid-phase bound compounds; immuno-SERS microscopywithnanoparticleprobes).Heiswellqualifiedtopresentthisbookto thescientificcommunity. WolfgangKiefer UniversityofWu¨rzburgandEisingen LaboratoryforAppliedRamanSpectroscopy(ELARS) VII Contents Preface XV ListofContributors XVII 1 BasicElectromagneticTheoryofSERS 1 PabloG.EtchegoinandEricC.LeRu 1.1 Introduction 1 1.2 PlasmonResonancesandFieldEnhancements 2 1.2.1 OpticalPropertiesofSimpleMetals 2 1.2.2 PlanarSurfaces 4 1.2.3 TheMetallicCylinder(2D)andSphere(3D) 7 1.2.3.1 TheElectrostaticApproximation 7 1.2.3.2 LocalizedSurfacePlasmonResonancesoftheCylinder 9 1.2.3.3 LocalizedSurfacePlasmonResonancesoftheSphere 10 1.2.3.4 LocalFieldEnhancements 11 1.2.4 SizeEffects 12 1.2.5 ShapeEffects 12 1.2.6 InteractingObjectsandGaps 15 1.2.6.1 CoupledPlasmonResonances 15 1.2.6.2 Tip-EnhancedRamanScattering(TERS) 17 1.2.7 ChoiceofMetal 18 1.2.7.1 GoldversusSilver 18 1.2.7.2 OtherCoinageandTransitionMetals 19 1.3 FieldEnhancementDistributionandLocalization 20 1.3.1 ElectromagneticHotSpots 20 1.3.2 Long-TailDistributionofEnhancements 21 1.4 ElectromagneticModelfortheSERSandFluorescence EnhancementFactors 23 1.4.1 EnhancedAbsorption 23 1.4.2 ComparisonofRamanandFluorescenceProcesses 24 1.4.3 The|E|4ApproximationtoSERSEnhancementFactors 27 1.4.4 FluorescenceQuenchingandEnhancement 28 1.4.5 ComparisonofSERSandFluorescenceEnhancements 29 1.4.6 OtherFormsofEnhancements 31 SurfaceEnhancedRamanSpectroscopy:Analytical,BiophysicalandLifeScienceApplications.EditedbySebastianSchlu¨cker Copyright2011WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim ISBN:978-3-527-32567-2 VIII Contents 1.5 TheMagnitudeoftheSERSEnhancementFactorinTypicalCases 32 1.6 Conclusions 33 References 34 2 NanoparticleSERSSubstrates 39 YulingWangandErkangWang 2.1 Introduction 39 2.2 PreparationandStabilityofMetalNanoparticleColloidalSERS Substrates 40 2.2.1 ColloidalSphericalMetalNanoparticles 41 2.2.1.1 ChemicalReactionforMetalNanoparticlePreparation 41 2.2.1.2 LaserAblationandPhotoreductionforMetalNanoparticle Preparation 44 2.2.1.3 SizeEffectofSERSSignalonMetalNanoparticles 45 2.2.1.4 Near-Infrared(NIR)ExcitationforSERSonMetal Nanoparticles 46 2.2.1.5 StabilityoftheMetalNanoparticleColloids 47 2.2.2 AggregationofMetalNanoparticles 47 2.2.3 BimetallicNanoparticleSERSSubstrate 50 2.2.4 NanoparticleswithVariousShapes 52 2.3 CharacterizationofNanoparticle-BasedSERSSubstrates 57 2.4 NanoparticlesontheUnfunctionalizedSolidSurfaceasSERS Substrates 58 2.5 ConclusionandOutlook 60 References 60 3 QuantitativeSERSMethods 71 StevenE.J.BellandAlanStewart 3.1 Introduction 71 3.2 SERSMedia 71 3.3 StabilityandShelfLife 73 3.4 ReproducibilityandInternalStandards 74 3.5 Selectivity 78 3.6 Conclusion 82 References 83 4 Single-Molecule-andTraceDetectionbySERS 87 NicholasP.W.Pieczonka,GolamMoula,AdamR.Skarbek, andRicardoF.Aroca 4.1 Introduction 87 4.1.1 SERS 87 4.1.2 TheTwoRegimes:EnsembleandTrace/SM 88 4.1.3 RequirementsforSM-SERS 89 4.2 ExperimentsandResults 90 4.2.1 TheLangmuir–BlodgettMethodforSM-SERRS 90 Contents IX 4.2.2 LBSM-SERRStoBiologicallyRelevantSystems 91 4.2.3 ExperimentalDetails 93 4.2.4 Single-MoleculeExamples 94 4.2.4.1 TaggedPhospholipid 94 4.2.4.2 R18,OctadecylRhodamineB 97 4.3 Conclusions 99 References 99 5 DetectionofPersistentOrganicPollutantsbyUsingSERSSensors BasedonOrganicallyFunctionalizedAgNanoparticles 103 LucaGuerrini,PatricioLeyton,MarceloCampos-Vallette, Concepcio´nDomingo,Jose´V.Garcia-Ramos,and SantiagoSanchez-Cortes 5.1 Introduction 103 5.2 InclusionHosts 106 5.2.1 Calixarenes 106 5.2.2 α,ω-AliphaticDiamines 112 5.3 ContactHosts 115 5.3.1 Viologens 115 5.3.2 CarbonNanotubes 118 5.4 OcclusionHosts 120 5.4.1 HumicSubstances 120 5.5 Conclusions 122 Acknowledgements 124 References 124 6 SERSandPharmaceuticals 129 SimonaCˆınta˘PˆınzaruandIoanaE.Pavel 6.1 Introduction 129 6.2 SERSofAntipyreticsandAnalgesics 130 6.3 SERSofAntimalarials 139 6.4 SERSofAnticarcinogenicsandAntimutagenics 142 6.4.1 5-Fluorouracil 142 6.4.2 β-Carotene 150 6.5 ConcludingRemarks 152 References 152 7 SERSandSeparationScience 155 AlisonJ.HobroandBernhardLendl 7.1 Introduction 155 7.2 SERSandCapillaryElectrophoresis(CE) 157 7.3 SERSandLiquidChromatography(LC) 161 7.4 SERSandGasChromatography(GC) 164 7.5 SERSandThinLayerChromatography(TLC) 165 7.6 OtherSeparationMethods 166
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