Frontiers of Surface-Enhanced Raman Scattering

EDITORSYUKIHIRO OZAKI, School of Science & Technology, Kwansei Gakuin University, JapanKATRIN KNEIPP, Department of Physics, Technical University of Denmark, DenmarkRICARDO AROCA, Department of Chemistry & Biochemistry, University of Windsor, Canada

“I believe this book is worth reading by anyone in the field, and I found myself noting a few references throughout each chapter. The book would also be particularly useful for students trying to understand issues in the broader field of current SERS research.”  (Anal Bioanal Chem, 22 August 2014)

• List of Contributors xiPreface xv1. Calculation of Surface-Enhanced Raman Spectra Including Orientational and Stokes Effects Using TDDFT/Mie Theory QM/ED Method 1George C. Schatz and Nicholas A. Valley1.1 Introduction: Combined Quantum Mechanics/Electrodynamics Methods 11.2 Computational Details 31.3 Summary of Model Systems 41.4 Azimuthal Averaging 51.5 SERS of Pyridine: Models G, A, B, S, and V 61.6 Orientation Effects in SERS of Phthalocyanines 111.7 Two Particle QM/ED Calculations 131.8 Summary 15Acknowledgment 16References 162. Non-resonant SERS Using the Hottest Hot Spots of Plasmonic Nanoaggregates 19Katrin Kneipp and Harald Kneipp2.1 Introduction 192.2 Aggregates of Silver and Gold Nanoparticles and Their Hot Spots 212.2.1 Evaluation of Plasmonic Nanoaggregates by Vibrational Pumping due to a Non-resonant SERS Process 212.2.2 Probing Plasmonic Nanoaggregates by Electron Energy Loss Spectroscopy 242.2.3 Probing Local Fields in Hot Spots by SERS and SEHRS 252.3 SERS Using Hot Silver Nanoaggregates and Non-resonant NIR Excitation 262.3.1 SERS Signal vs. Concentration of the Target Molecule 262.3.2 Spectroscopic Potential of Non-resonant SERS Using the Hottest Hot Spots 302.4 Summary and Conclusions 31References 323. Effect of Nanoparticle Symmetry on Plasmonic Fields: Implications for Single-Molecule Raman Scattering 37Lev Chuntonov and Gilad Haran3.1 Introduction 373.2 Methodology 383.3 Plasmon Mode Structure of Nanoparticle Clusters 393.3.1 Dimers 393.3.2 Trimers 403.4 Effect of Plasmon Modes on SMSERS 473.4.1 Effect of the Spectral Lineshape 473.4.2 Effect of Multiple Normal Modes 493.5 Conclusions 54Acknowledgment 54References 544. Experimental Demonstration of Electromagnetic Mechanism of SERS and Quantitative Analysis of SERS Fluctuation Based on the Mechanism 59Tamitake Itoh4.1 Experimental Demonstration of the EM Mechanism of SERS 594.1.1 Introduction 594.1.2 Observations of the EM Mechanism in SERS Spectral Variations 604.1.3 Observations of the EM Mechanism in the Refractive Index Dependence of SERS Spectra 624.1.4 Quantitative Evaluation of the EM Mechanism of SERS 644.1.5 Summary 724.2 Quantitative Analysis of SERS Fluctuation Based on the EM Mechanism 724.2.1 Introduction 724.2.2 Intensity and Spectral Fluctuation in SERS and SEF 734.2.3 Framework for Analysis of Fluctuation in SERS and SEF 734.2.4 Analysis of Intensity Fluctuation in SERS and SEF 764.2.5 Analysis of Spectral Fluctuation in SERS and SEF 784.2.6 Summary 824.3 Conclusion 82Acknowledgments 83References 835. Single-Molecule Surface-Enhanced Raman Scattering as a Probe for Adsorption Dynamics on Metal Surfaces 89Mai Takase, Fumika Nagasawa, Hideki Nabika and Kei Murakoshi5.1 Introduction 895.2 Simultaneous Measurements of Conductance and SERS of a Single-Molecule Junction 905.3 SERS Observation Using Heterometallic Nanodimers at the Single-Molecule Level 965.4 Conclusion 101Acknowledgments 101References 1016. Analysis of Blinking SERS by a Power Law with an Exponential Function 107Yasutaka Kitahama and Yukihiro Ozaki6.1 Introduction 1076.2 Materials and Methods 1106.3 Power Law Analysis 1106.4 Plasmon Resonance Wavelength Dependence 1176.4.1 Power Law Exponents for the Bright and Dark Events 1176.4.2 Truncation Time for the Dark Events 1236.5 Energy Density Dependence 1236.5.1 Power Law Exponents for the Bright and Dark Events 1236.5.2 Truncation Time for the Dark Events 1256.5.3 Comparison with Other Analysis 1266.6 Temperature Dependence 1296.6.1 Power Law Exponents for the Bright and Dark Events 1296.6.2 Truncation Time for the Dark Events 1296.6.3 Comparison with Other Analysis 1306.7 Summary 132Acknowledgments 132References 1337. Tip-Enhanced Raman Spectroscopy (TERS) for Nanoscale Imaging and Analysis 139Taka-aki Yano and Satoshi Kawata7.1 Crucial Difference between TERS and SERS 1397.2 TERS-Specific Spectral Change as a Function of Tip–Sample Distance 1417.3 Mechanical Effect in TERS 1437.4 Application to Analytical Nano-Imaging 1447.5 Metallic Probe Tip: Design and Fabrication 1497.6 Spatial Resolution 1547.7 Real-Time and 3D Imaging: Perspectives 155References 1568. Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy (SHINERS) 163Jian-Feng Li and Zhong-Qun Tian8.1 Introduction 1638.2 Synthesis of Various Shell-Isolated Nanoparticles (SHINs) 1678.3 Characterizations of SHINs 1698.3.1 Correlation of the SHINERS Intensity and Shell Thickness 1698.3.2 Characterization of the Ultra-Thin Uniform Silica Shell 1718.3.3 Influence of the SHINs on the Surface 1728.4 Applications of SHINERS 1738.4.1 Single-Crystal Electrode Surface 1738.4.2 Non-Metallic Material Surfaces 1758.4.3 Single Particle SHINERS 1788.5 Different Strategies of SHINERS Compared to Previous SERS Works Using Core–Shell or Overlayer Structures 1788.6 Advantages of Isolated Mode over Contact Mode 1808.7 Concluding Discussion 1848.8 Outlook 185Acknowledgments 186References 1869. Applying Super-Resolution Imaging Techniques to Problems in Single-Molecule SERS 193Eric J. Titus and Katherine A. Willets9.1 Introduction 1939.1.1 Single-Molecule Surface-Enhanced Raman Scattering (SM-SERS) 1939.1.2 Super-Resolution Imaging 1949.2 Experimental Considerations for Super-Resolution SM-SERS 1959.2.1 Sample Preparation 1959.2.2 Instrument Set-up 1969.2.3 Camera Pixels and Theoretical Uncertainties 1979.2.4 Correlated Imaging and Spectroscopy in Super-Resolution SM-SERS 1989.2.5 Correlated Optical and Structural Data 1999.3 Super-Resolution SM-SERS Analysis 2009.3.1 Mechanical Drift Correction 2019.3.2 Analysis of Background Nanoparticle Luminescence 2029.3.3 Calculating the SM-SERS Centroid Position 2029.4 Super-Resolution SM-SERS Examples 2049.4.1 Mapping SM-SERS Hot Spots 2049.4.2 The Role of Plasmon-Enhanced Electromagnetic Fields: Structure Correlation Studies 2069.4.3 The Role of the Molecule: Isotope-Edited Studies 2109.5 Conclusions 214References 21410. Lithographically-Fabricated SERS Substrates: Double Resonances, Nanogaps, and Beamed Emission 219Kenneth B. Crozier, Wenqi Zhu, Yizhuo Chu, Dongxing Wang and Mohamad Banaee10.1 Introduction 21910.2 Double Resonance SERS Substrates 22010.3 Lithographically-Fabricated Nanogap Dimers 22610.4 Beamed Raman Scattering 22910.5 Conclusions 238References 23911. Plasmon-Enhanced Scattering and Fluorescence Used for Ultrasensitive Detection in Langmuir–Blodgett Monolayers 243Diogo Volpati, Aisha Alsaleh, Carlos J. L. Constantino and Ricardo F. Aroca11.1 Introduction 24311.2 Surface-Enhanced Resonance Raman Scattering of Tagged Phospholipids 24511.2.1 Experimental Details 24511.2.2 Langmuir and LB films 24611.2.3 Electronic Absorption 24711.2.4 Characteristic Vibrational Modes of the Tagged Phospholipid 24811.2.5 Single Molecule Detection 25011.3 Shell-Isolated Nanoparticle Enhanced Fluorescence (SHINEF) 25111.3.1 Tuning the Enhancement Factor in SHINEF 25111.3.2 SHINEF of Fluorescein-DHPE 25311.4 Conclusions 254Acknowledgments 255References 25512. SERS Analysis of Bacteria, Human Blood, and Cancer Cells: a Metabolomic and Diagnostic Tool 257W. Ranjith Premasiri, Paul Lemler, Ying Chen, Yoseph Gebregziabher and Lawrence D. Ziegler12.1 Introduction 25712.2 SERS of Bacterial Cells: Methodology and Diagnostics 25812.3 Characteristics of SERS Spectra of Bacteria 26112.4 PCA Barcode Analysis 26312.5 Biological Origins of Bacterial SERS Signatures 26512.6 SERS Bacterial Identification in Human Body Fluids: Bacteremia and UTI Diagnostics 26612.7 Red Blood Cells and Hemoglobin: Blood Aging and Disease Detection 26712.8 SERS of Whole Blood 26912.9 SERS of RBCs 27112.10 Malaria Detection 27312.11 Cancer Cell Detection: Metabolic Profiling by SERS 27312.12 Conclusions 276Acknowledgment 277References 27713. SERS in Cells: from Concepts to Practical Applications 285Janina Kneipp and Daniela Drescher13.1 Introduction 28513.2 SERS Labels and SERS Nanoprobes: Different Approaches to Obtain Different Information 28613.2.1 Highlighting Cellular Substructures with SERS Labels 28613.2.2 Probing Intrinsic Cellular Biochemistry with SERS Nanoprobes 28813.3 Consequences of Endocytotic Uptake and Processing for Intrinsic SERS Probing in Cells 28913.4 Quantification of Metal Nanoparticles in Cells 29213.5 Toxicity Considerations 29513.6 Applications 29813.6.1 pH Nanosensors for Studies in Live Cells 29813.6.2 Following Cell Division with SERS 299Acknowledgment 301References 301Index 309