Surface-enhanced Raman Scattering

by Kneipp, Katrin; Moskovits, Martin; Kneipp, Harald

• ISBN13: 9783540335665
• ISBN10: 3540335668
• Format: Hardcover
• Copyright: 2006-09-13
• Publisher: Springer Verlag

Summary

Almost 30 years after the first reports on surface-enhanced Raman signals, the phenomenon of surface-enhanced Raman scattering (SERS) is now well established. Yet, explaining the enhancement of a spectroscopic signal by fouteen orders of magnitude continues to attract the attention of physicists and chemists alike. And, at the same time and rapidly growing, SERS is becoming a very useful spectroscopic tool with exciting applications in many fields. SERS gained particular interest after single-molecule Raman spectroscopy had been demonstrated. This bookl summarizes and discusses present theoretical approaches that explain the phenomenon of SERS and reports on new and exciting experiments and applications of the fascinating spectroscopic effect.

Table of Contents

Surface-Enhanced Raman Spectroscopy: a Brief Perspective
Martin Moskovits	1	(18)
1 Introduction	1	(1)
2 The Electromagnetic Theory of SERS	2	(5)
3 Assemblies of Interacting Nanostructures: The Ubiquitous SERS-Active Systems	7	(5)
4 Possible Extensions of the Electromagnetic Model	12	(1)
5 Conclusions	13	(1)
References	14	(3)
Index	17	(2)
Electromagnetic Mechanism of SERS
George C. Schatz, Matthew A. Young, Richard P. Van Duyne	19	(28)
1 Introduction	19	(2)
2 Electromagnetic Mechanism of SERS	21	(1)
3 Numerical Methods for Calculating Electromagnetic Enhancement Factors	22	(1)
4 Results of EM Calculations	23	(2)
5 Long-Range Hectromagnetic Enhancement Effects	25	(3)
6 Electronic-Structure Studies	28	(2)
7 SERS Excitation Spectroscopy as a Probe of the Electromagnetic Mechanism	30	(9)
8 Conclusions	39	(1)
References	40	(5)
Index	45	(2)
Electromagnetic Theory of SERS
Mark I. Stockman	47	(20)
1 Introduction	47	(2)
2 Spectral Theory of SERS Enhancement	49	(7)
2.1 Spectral Expansion of Local Fields and Green's Function	49	(5)
2.2 SERS Enhancement Factor in Green's Function Theory	54	(2)
3 Numerical Computations and Results	56	(7)
3.1 SERS Enhancement in Fractals in Dipolar Approximation	57	(1)
3.2 Single-Molecule SERS in Random Systems	58	(3)
3.3 Single-Molecule SERS in Nanosphere Nanolens	61	(2)
References	63	(2)
Index	65	(2)
Coupled Plasmonic Plasmon/Photonic Resonance Effects in SERS
Shengli Zou and George C. Schatz	67	(20)
1 Introduction	67	(1)
2 Methods	68	(3)
3 Single Nanoparticles and Dimers	71	(4)
4 Particle Arrays	75	(7)
4.1 Chains Perpendicular to the Wavevector	76	(3)
4.2 Chains Parallel to the Wavevector	79	(2)
4.3 Configurations that Combine Parallel and Perpendicular Chains	81	(1)
5 Conclusion	82	(1)
References	83	(2)
Index	85	(2)
Estimating SERS Properties of Silver-Particle Aggregates through Generalized Mie Theory
Hongxing Xu, Mikael Käll	87	(18)
1 Introduction	87	(3)
1.1 Electromagnetic Enhancement	87	(2)
1.2 Generalized Mie Theory	89	(1)
2 The Recursive Order-of-Scattering Method	90	(2)
3 Examples of GMT Calculations for Ag-Particle Aggregates	92	(9)
3.1 "Hot Sites" Between Metal Particles	92	(2)
3.2 Polarization Anisotropy	94	(2)
3.3 Comparisons between Near-Field and Far-Field Spectra	96	(2)
3.4 Including Molecular Quantum Dynamics into the EM SERS Theory	98	(1)
3.5 Optical Forces	99	(2)
4 Summary	101	(1)
References	102	(1)
Index	103	(2)
Studying SERS from Metal Nanoparticles and Nanoparticles Aggregates with Continuum Models
Stefano Corni, Jacopo Tomasi	105	(20)
1 Introduction	105	(1)
2 Description of the Model: A Molecule Close to a Complex-Shaped Nanoparticle	106	(4)
2.1 The Calculation of Surface-Enhanced Raman Spectra	107	(3)
2.1.1 Enhanced Scattering Cross Section	108	(2)
3 Extending the Model to Metal-Particle Aggregates	110	(5)
3.1 Decomposition of the Total Enhancement	112	(1)
3.2 Hot Spots and Aggregate Size	113	(2)
4 Beyond SERS	115	(5)
4.1 SEIRA	116	(3)
4.2 Molecular Fluorescence	119	(1)
5 Summary and Perspectives	120	(2)
References	122	(1)
Index	123	(2)
SERS From Transition Metals and Excited by Ultraviolet Light
Zhong-Qun Tian, Zhi-Lin Yang, Bin Ren, De-Yin Wu	125	(22)
1 Introduction	125	(3)
2 The Physics behind SERS of Transition Metals	128	(9)
2.1 The Electronic Structure and Dielectric Constants of Transition Metals	128	(2)
2.2 Theoretical Simulation of the Local Electric Field by the Finite Difference Time-Domain Method	130	(2)
2.3 3D-FDTD Simulation of the Electromagnetic Field Distribution over a Cauliflower-Like Nanostructure	132	(2)
2.4 3D-FDTD Simulation of the Electromagnetic Field Distribution over a Nanocube Dimer	134	(1)
2.5 3D-FDTD Simulation of Electromagnetic-Field Enhancement of Core-Shell Nanoparticles	135	(2)
3 SERS From Transition Metals with Ultraviolet Excitation	137	(5)
3.1 Potential-Dependent UV-Raman Spectra from Transition Metals	138	(2)
3.2 Confirmation of UV-SERS Effect on Transition Metals	140	(2)
4 Conclusion	142	(1)
References	142	(4)
Index	146	(1)
Electronic Mechanisms of SERS
Andreas Otto and Masayuki Futamata	147	(1)
1 Introduction	147	(1)
2 Long-Range Electromagnetic (em)-Enhancement Gem and "Chemical", "First-Layer"-Enhancement Gfirst layer of Various Ag Samples	148	(5)
3 The Electronic Origin of the "First-Layer Effect" of SERS	153	(1)
4 The Raman-Continuum of Electron- Hole-Pair Excitations	154	(3)
5 SERS-Active Sites	157	(4)
6 Theory of SERS-Active Sites	161	(3)
7 The Story of "Missing NO"	164	(3)
8 EM Enhancement in Single-Molecule SERS of Dyes in Langmuir—Blodgett Films	167	(2)
9 Conjectures on SM SERS in Junction Sites	169	(3)
10 Special Examples of SERS at Low Coverage of Small Silver Aggregates	172	(6)
References	178	(4)
Index	182	(1)
Two-Photon Excited Surface-Enhanced Raman Scattering
Katrin Kneipp, Harald Kneipp	183	(14)
1 Introduction	183	(1)
2 Surface-Enhanced Anti-Stokes Raman Scattering	184	(6)
2.1 SERS Vibrational Pumping	184	(4)
2.2 Pumped Anti-Stokes SERS — A Two-Photon Raman Effect	188	(2)
3 Surface-Enhanced Hyper-Raman Scattering (SEHRS)	190	(3)
3.1 SEHRS Enhancement Factors	190	(1)
3.2 Resonant and Nonresonant Surface-Enhanced Hyper-Raman Scattering	191	(2)
4 Summary and Conclusion	193	(1)
References	194	(2)
Index	196	(1)
Applications of the Enhancement of Resonance Raman Scattering and Fluorescence by Strongly Coupled Metallic Nanostructures
Nicholas P.W. Pieczonka, Paul J.G. Goulet, Ricardo F. Aroca	197	(20)
1 Introduction	197	(4)
2 Applications	201	(12)
2.1 SERRS of Thin Solid Films and Langmuir—Blodgett Monolayers	201	(5)
2.1.1 Spatial Spectroscopic Tuning	203	(1)
2.1.2 SERRS Mapping and Imaging	204	(2)
2.1.3 Single-Molecule SERRS from Langmuir—Blodgett Monolayers	206	(1)
2.2 SERRS from Colloids and Nanocomposite Films	206	(6)
2.2.1 SERRS from Ag and Au Metal Colloids	208	(2)
2.2.2 SERRS from Silver Nanowire Layer-by-Layer Film Substrates	210	(2)
2.3 SEF of LB	212	(1)
3 Conclusion	213	(1)
References	214	(2)
Index	216	(1)
Tip-Enhanced Raman Spectroscopy (TERS)
Bruno Pettinger	217	(24)
1 Introduction	217	(3)
2 TERS Results	220	(17)
2.1 Remarks on SERRS	220	(1)
2.2 Initial Steps in TERS	221	(8)
2.3 Towards Higher Efficiencies in TERS	229	(8)
3 Conclusion/Outlook	237	(1)
References	238	(2)
Index	240	(1)
Tip-Enhanced Near-Field Raman Scattering: Fundamentals and New Aspects for Molecular Nanoanalysis/Identification
Prabhat Verma, Yasushi Inouye, Satoshi Kawata	241	(20)
1 Introduction	241	(1)
2 Localized Surface-Plasmon Polaritons at the Tip	241	(1)
3 Instrumentation	242	(1)
4 TERS from Single-Wall Carbon Nanotube	243	(4)
5 TERS Measurements on Rhodamine 6G	247	(3)
6 Tip Force on DNA-Based Adenine Molecules	250	(3)
6.1 TERS from Adenine	250	(1)
6.2 TERS from Tip-Pressurized Adenine Molecules	251	(2)
7 Tip-Enhanced Coherent Anti-Stokes Raman Scattering	253	(6)
References	259	(1)
Index	260	(1)
Single-Molecule SERS Spectroscopy
Katrin Kneipp, Harald Kneipp, Henrik G. Bohr	261	(18)
1 Introduction	261	(2)
2 Single-Molecule SERS Experiments	263	(7)
2.1 Single-Molecule SERS on Silver and Gold Nanoclusters in Solution	264	(3)
2.2 Single-Molecule SERS on Fixed Fractal Silver and Gold Cluster Structures	267	(3)
3 SERS as a Single-Molecule Analytical Tool – Comparison between SERS and Fluorescence	270	(3)
3.1 Potential Applications of Single-Molecule Raman Spectroscopy	271	(2)
4 Conclusion	273	(1)
References	274	(3)
Index	277	(2)
Temporal Fluctuations in Single-Molecule SERS Spectra
Anna Rita Bizzarri, Salvatore Cannistraro	279	(18)
1 Introduction	279	(1)
2 Materials and Methods	280	(2)
3 Results and Discussion	282	(11)
3.1 Fluctuations in SM SERS Spectra	282	(1)
3.2 Statistical Analysis of Intensity Fluctuations in SM SERS Spectra	283	(4)
3.3 ET in SM SERS Spectra of FePP	287	(3)
3.4 Levy Statistics in SM SERS Spectra of FePP	290	(3)
4 Conclusions and Perspectives	293	(1)
References	293	(3)
Index	296	(1)
Single-Molecule Surface-Enhanced Resonance Raman Spectroscopy of the Enhanced Green Fluorescent Protein EGFP
Satoshi Habuchi, Johan Hofkens	297	(16)
1 Introduction	297	(1)
2 Experimental Section	298	(2)
2.1 Purification of EGFP	298	(1)
2.2 Sample Preparation for SM-SERRS Measurements	298	(1)
2.3 Experimental Setup	298	(1)
2.4 Autocorrelation Analysis	299	(1)
3 Results and Discussion	300	(10)
3.1 Single EGFP Molecules Detected by SERRS	300	(1)
3.2 SM-SERRS Spectra of EGFP	301	(4)
3.3 Discussion on the Spectral Jumps Observed in the SM-SERRS Spectra of EGFP	305	(1)
3.4 The Relation between the Fluorescence and SERRS Intensity Trajectories of EGFP	306	(4)
4 Summary	310	(1)
References	310	(2)
Index	312	(1)
Surface-Enhanced Vibrational Spectroelectrochemistry: Electric-Field Effects on Redox and Redox-Coupled Processes of Heme Proteins
Daniel Murgida, Peter Hildebrandt	313	(22)
1 Introduction	313	(1)
2 Strategy and Methodological Approach	314	(7)
2.1 Protein Immobilization on SER/SEIRA Active Metal Electrodes	314	(2)
2.2 Surface-Enhanced Vibrational Spectroelectrochemistry of Heme Proteins	316	(3)
2.3 Theoretical Description and Experimental Determination of the Electric-Field	319	(2)
3 Electric-Field Effects on the Interfacial Processes of Heme Proteins	321	(10)
3.1 Conformational Changes of Cytochrome c	321	(2)
3.2 Modulation of Redox Potentials	323	(2)
3.3 Electron-Transfer Dynamics of Cytochrome c and Other Soluble Electron Carriers	325	(2)
3.4 Electric-Field Effects on the Electroprotonic Energy Transduction of Heme-Cu Oxidases	327	(4)
4 Concluding Remarks	331	(1)
References	332	(2)
Index	334	(1)
Nanosensors Based on SERS for Applications in Living Cells
Janina Kneipp	335	(16)
1 Reasons for Intracellular SERS Approaches	335	(3)
1.1 Raman Spectra from Biological Samples	335	(1)
1.2 Advantages of SERS for Studies in Cells	336	(2)
2 SERS Nanosensors for Probing of Intrinsic Cellular Chemistry	338	(4)
2.1 Requirements of Cellular Systems	338	(1)
2.2 SERS Nanosensors in Endosomal Structures	338	(3)
2.3 Gold Nanoparticles and the Cellular Environment	341	(1)
3 A Labeled Nanosensor Based on the SERS Signal of Indocyanine Green	342	(3)
3.1 Characterization of the SERS Label	342	(1)
3.2 Application of ICG-SERS Nanoprobes in Living Cells	343	(2)
4 Conclusions and Outlook	345	(3)
References	348	(1)
Index	349	(2)
Biomolecule Sensing with Adaptive Plasmonic Nanostructures
Vladimir P. Drachev, Vladimir M. Shalaev	351	(16)
1 Introduction	351	(1)
2 Adaptive Plasmonic Nanostructures	352	(2)
3 SERS Features of Conformational States: Insulin	354	(4)
3.1 SERS Versus Normal Raman	355	(2)
3.2 Human Insulin Versus Insulin Lispro	357	(1)
4 Ebola Virus after Pseudotyping	358	(1)
5 Tag-Free Antibody—Antigen Binding Detection	359	(3)
6 Protein-Binding Detection with Dye Displacement	362	(1)
7 Summary	363	(1)
References	364	(2)
Index	366	(1)
Glucose Sensing with Surface-Enhanced Raman Spectroscopy
Chanda Ranjit Yonzon, Olga Lyandres, Nilam C. Shah, Jon A. Dieringer, Richard P. Van Duyne	367	(14)
1 Introduction	367	(3)
2 SERS of Glucose	370	(1)
3 Reversibility and Real-Time Glucose Sensing	371	(3)
4 Quantitative Aspects of Glucose Sensing with SERS	374	(2)
5 Temporal Stability of the SERS Glucose Sensor	376	(1)
6 Conclusions	376	(1)
References	377	(2)
Index	379	(2)
Quantitative Surface-Enhanced Resonance Raman Spectroscopy for Analysis
W.E. Smith, K. Faulds, and D. Graham	381	(16)
1 Introduction	381	(2)
2 Experimental Approach	383	(6)
2.1 Choice of Wavelength	383	(2)
2.2 Types of Assay	385	(1)
2.3 Choice of Analytes	386	(2)
2.4 Choice of Substrates	388	(1)
3 Examples of Analytical Methods	389	(5)
3.1 DNA	389	(3)
3.2 Mitoxantrone	392	(1)
3.3 Drugs of Abuse	393	(1)
3.4 Glucose	393	(1)
3.5 Derivatization Assays	393	(1)
4 Analysis Using Individual Nanoparticles	394	(1)
5 Summary	395	(1)
References	395	(1)
Index	396	(1)
Rapid Analysis of Microbiological Systems Using SERS
Roger Jarvis, Sarah Clarke, Royston Goodacre	397	(12)
1 Introduction	397	(1)
2 Spectroscopic Characterization of Micro-Organisms	398	(2)
3 Introduction to Multivariate Cluster Analysis	400	(2)
4 Identification of Micro-Organisms Using SERS	402	(1)
5 Monitoring Industrial Bioprocesses	403	(1)
6 Gene-Function Analysis	404	(2)
7 Concluding Remarks	406	(1)
References	406	(2)
Index	408	(1)
Surface-Enhanced Raman Scattering for Biomedical Diagnostics and Molecular Imaging
Tuan Vo-Dinh, Fei Yam Musundi B. Wabuyele	409	(18)
1 Introduction	409	(1)
2 Methods and Instrumentation	410	(4)
2.1 Silver Nanoparticle Island Films for Biomedical Diagnostics	410	(2)
2.2 Silver Nanoparticles for Cellular Imaging	412	(1)
2.3 SERS Instrumentation	413	(1)
3 SERS Applications	414	(9)
3.1 SERS Gene Probe for Medical Diagnostics	414	(3)
3.2 Hyperspectral Imaging of Raman Dye-Labeled Silver Nanoparticles in Single Cells	417	(1)
3.3 SERS Near-Field Scanning Optical Microscopy (SERS-NSOM)	418	(3)
3.4 SERS Molecular Sentinels	421	(2)
4 Conclusion	423	(2)
References	425	(1)
Index	426	(1)
Ultrasensitive Immunoassays Based on Surface-Enhanced Raman Scattering by Immunogold Labels
Hye-Young Park, Jeremy D. Driskell, Karen M. Kwarta, Robert J. Lipert, Marc D. Porter, Christian Schoen, John D. Neill, Julia F. Ridpath	427	(20)
1 Introduction	427	(2)
2 Assay Design	429	(5)
2.1 Preparation of Capture Antibody Substrates	429	(2)
2.2 ERL Preparation	431	(2)
2.3 Immunoassay Protocols	433	(1)
3 Spectroscopic Instrumentation	434	(1)
4 Maximization of Signal Strength	434	(3)
5 Assays	437	(3)
5.1 Early Disease Detection	437	(2)
5.2 Assay of Erwinia Herbicola (BW Stimulant)	439	(1)
6 Showcasing Performance	440	(3)
6.1 Single E. coli 0157:H7 SERS	440	(1)
6.2 Assay of PPV	441	(2)
7 Conclusions	443	(1)
References	444	(2)
Index	446	(1)
Detecting Chemical Agents and Their Hydrolysis Products in Water
Stuart Farquharson, Frank E. Inscore, Steve Christesen	447	(14)
1 Introduction	447	(1)
2 Experimental	448	(1)
3 Results and Discussion	449	(8)
3.1 Cyanide	449	(2)
3.2 HD and GEES	451	(3)
3.3 GB	454	(1)
3.4 VX	455	(2)
4 Conclusions	457	(1)
References	458	(2)
Index	460	(1)
Index	461