Frontiers of surface-enhanced raman scattering : single-nanoparticles and single cells

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List of Contributors xi <
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Preface xv <
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1. Calculation of Surface-Enhanced Raman Spectra IncludingOrientational and Stokes Effects Using TDDFT/Mie Theory QM/EDMethod 1 George C. Schatz and Nicholas A. Valley <
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1.1 Introduction: Combined Quantum Mechanics/ElectrodynamicsMethods 1 <
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1.2 Computational Details 3 <
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1.3 Summary of Model Systems 4 <
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1.4 Azimuthal Averaging 5 <
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1.5 SERS of Pyridine: Models G, A, B, S, and V 6 <
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1.6 Orientation Effects in SERS of Phthalocyanines 11 <
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1.7 Two Particle QM/ED Calculations 13 <
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1.8 Summary 15 <
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Acknowledgment 16 <
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References 16 <
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2. Non-resonant SERS Using the Hottest Hot Spots of PlasmonicNanoaggregates 19 Katrin Kneipp and Harald Kneipp <
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2.1 Introduction 19 <
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2.2 Aggregates of Silver and Gold Nanoparticles and Their HotSpots 21 <
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2.2.1 Evaluation of Plasmonic Nanoaggregates by VibrationalPumping due to a Non-resonant SERS Process 21 <
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2.2.2 Probing Plasmonic Nanoaggregates by Electron Energy LossSpectroscopy 24 <
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2.2.3 Probing Local Fields in Hot Spots by SERS and SEHRS 25 <
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2.3 SERS Using Hot Silver Nanoaggregates and Non-resonant NIRExcitation 26 <
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2.3.1 SERS Signal vs. Concentration of the Target Molecule26 <
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2.3.2 Spectroscopic Potential of Non-resonant SERS Using theHottest Hot Spots 30 <
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2.4 Summary and Conclusions 31 <
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References 32 <
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3. Effect of Nanoparticle Symmetry on Plasmonic Fields:Implications for Single-Molecule Raman Scattering 37 Lev Chuntonov and Gilad Haran <
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3.1 Introduction 37 <
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3.2 Methodology 38 <
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3.3 Plasmon Mode Structure of Nanoparticle Clusters 39 <
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3.3.1 Dimers 39 <
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3.3.2 Trimers 40 <
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3.4 Effect of Plasmon Modes on SMSERS 47 <
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3.4.1 Effect of the Spectral Lineshape 47 <
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3.4.2 Effect of Multiple Normal Modes 49 <
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3.5 Conclusions 54 <
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Acknowledgment 54 <
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References 54 <
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4. Experimental Demonstration of Electromagnetic Mechanism ofSERS and Quantitative Analysis of SERS Fluctuation Based on theMechanism 59 Tamitake Itoh <
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4.1 Experimental Demonstration of the EM Mechanism of SERS59 <
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4.1.1 Introduction 59 <
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4.1.2 Observations of the EM Mechanism in SERS SpectralVariations 60 <
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4.1.3 Observations of the EM Mechanism in the Refractive IndexDependence of SERS Spectra 62 <
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4.1.4 Quantitative Evaluation of the EM Mechanism of SERS 64 <
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4.1.5 Summary 72 <
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4.2 Quantitative Analysis of SERS Fluctuation Based on the EMMechanism 72 <
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4.2.1 Introduction 72 <
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4.2.2 Intensity and Spectral Fluctuation in SERS and SEF 73 <
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4.2.3 Framework for Analysis of Fluctuation in SERS and SEF73 <
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4.2.4 Analysis of Intensity Fluctuation in SERS and SEF 76 <
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4.2.5 Analysis of Spectral Fluctuation in SERS and SEF 78 <
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4.2.6 Summary 82 <
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4.3 Conclusion 82 <
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Acknowledgments 83 <
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References 83 <
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5. Single-Molecule Surface-Enhanced Raman Scattering as aProbe for Adsorption Dynamics on Metal Surfaces 89 Mai Takase, Fumika Nagasawa, Hideki Nabika and KeiMurakoshi <
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5.1 Introduction 89 <
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5.2 Simultaneous Measurements of Conductance and SERS of aSingle-Molecule Junction 90 <
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5.3 SERS Observation Using Heterometallic Nanodimers at theSingle-Molecule Level 96 <
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5.4 Conclusion 101 <
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Acknowledgments 101 <
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References 101 <
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6. Analysis of Blinking SERS by a Power Law with anExponential Function 107 Yasutaka Kitahama and Yukihiro Ozaki <
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6.1 Introduction 107 <
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6.2 Materials and Methods 110 <
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6.3 Power Law Analysis 110 <
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6.4 Plasmon Resonance Wavelength Dependence 117 <
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6.4.1 Power Law Exponents for the Bright and Dark Events 117 <
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6.4.2 Truncation Time for the Dark Events 123 <
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6.5 Energy Density Dependence 123 <
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6.5.1 Power Law Exponents for the Bright and Dark Events 123 <
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6.5.2 Truncation Time for the Dark Events 125 <
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6.5.3 Comparison with Other Analysis 126 <
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6.6 Temperature Dependence 129 <
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6.6.1 Power Law Exponents for the Bright and Dark Events 129 <
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6.6.2 Truncation Time for the Dark Events 129 <
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6.6.3 Comparison with Other Analysis 130 <
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6.7 Summary 132 <
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Acknowledgments 132 <
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References 133 <
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7. Tip-Enhanced Raman Spectroscopy (TERS) for NanoscaleImaging and Analysis 139 Taka-aki Yano and Satoshi Kawata <
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7.1 Crucial Difference between TERS and SERS 139 <
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7.2 TERS-Specific Spectral Change as a Function ofTip   Sample Distance 141 <
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7.3 Mechanical Effect in TERS 143 <
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7.4 Application to Analytical Nano-Imaging 144 <
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7.5 Metallic Probe Tip: Design and Fabrication 149 <
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7.6 Spatial Resolution 154 <
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7.7 Real-Time and 3D Imaging: Perspectives 155 <
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References 156 <
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8. Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy(SHINERS) 163 Jian-Feng Li and Zhong-Qun Tian <
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8.1 Introduction 163 <
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8.2 Synthesis of Various Shell-Isolated Nanoparticles (SHINs)167 <
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8.3 Characterizations of SHINs 169 <
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8.3.1 Correlation of the SHINERS Intensity and Shell Thickness169 <
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8.3.2 Characterization of the Ultra-Thin Uniform Silica Shell171 <
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8.3.3 Influence of the SHINs on the Surface 172 <
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8.4 Applications of SHINERS 173 <
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8.4.1 Single-Crystal Electrode Surface 173 <
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8.4.2 Non-Metallic Material Surfaces 175 <
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8.4.3 Single Particle SHINERS 178 <
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8.5 Different Strategies of SHINERS Compared to Previous SERSWorks Using Core   Shell or Overlayer Structures 178 <
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8.6 Advantages of Isolated Mode over Contact Mode 180 <
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8.7 Concluding Discussion 184 <
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8.8 Outlook 185 <
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Acknowledgments 186 <
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References 186 <
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9. Applying Super-Resolution Imaging Techniques to Problemsin Single-Molecule SERS 193 Eric J. Titus and Katherine A. Willets <
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9.1 Introduction 193 <
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9.1.1 Single-Molecule Surface-Enhanced Raman Scattering(SM-SERS) 193 <
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9.1.2 Super-Resolution Imaging 194 <
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9.2 Experimental Considerations for Super-Resolution SM-SERS195 <
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9.2.1 Sample Preparation 195 <
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9.2.2 Instrument Set-up 196 <
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9.2.3 Camera Pixels and Theoretical Uncertainties 197 <
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9.2.4 Correlated Imaging and Spectroscopy in Super-ResolutionSM-SERS 198 <
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9.2.5 Correlated Optical and Structural Data 199 <
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9.3 Super-Resolution SM-SERS Analysis 200 <
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9.3.1 Mechanical Drift Correction 201 <
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9.3.2 Analysis of Background Nanoparticle Luminescence 202 <
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9.3.3 Calculating the SM-SERS Centroid Position 202 <
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9.4 Super-Resolution SM-SERS Examples 204 <
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9.4.1 Mapping SM-SERS Hot Spots 204 <
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9.4.2 The Role of Plasmon-Enhanced Electromagnetic Fields:Structure Correlation Studies 206 <
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9.4.3 The Role of the Molecule: Isotope-Edited Studies 210 <
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9.5 Conclusions 214 <
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References 214 <
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10. Lithographically-Fabricated SERS Substrates: DoubleResonances, Nanogaps, and Beamed Emission 219 Kenneth B. Crozier, Wenqi Zhu, Yizhuo Chu, Dongxing Wang andMohamad Banaee <
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10.1 Introduction 219 <
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10.2 Double Resonance SERS Substrates 220 <
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10.3 Lithographically-Fabricated Nanogap Dimers 226 <
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10.4 Beamed Raman Scattering 229 <
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10.5 Conclusions 238 <
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References 239 <
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11. Plasmon-Enhanced Scattering and Fluorescence Used forUltrasensitive Detection in Langmuir   Blodgett Monolayers243 Diogo Volpati, Aisha Alsaleh, Carlos J. L. Constantino andRicardo F. Aroca <
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11.1 Introduction 243 <
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11.2 Surface-Enhanced Resonance Raman Scattering of TaggedPhospholipids 245 <
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11.2.1 Experimental Details 245 <
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11.2.2 Langmuir and LB films 246 <
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11.2.3 Electronic Absorption 247 <
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11.2.4 Characteristic Vibrational Modes of the TaggedPhospholipid 248 <
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11.2.5 Single Molecule Detection 250 <
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11.3 Shell-Isolated Nanoparticle Enhanced Fluorescence (SHINEF)251 <
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11.3.1 Tuning the Enhancement Factor in SHINEF 251 <
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11.3.2 SHINEF of Fluorescein-DHPE 253 <
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11.4 Conclusions 254 <
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Acknowledgments 255 <
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References 255 <
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12. SERS Analysis of Bacteria, Human Blood, and Cancer Cells:a Metabolomic and Diagnostic Tool 257 W. Ranjith Premasiri, Paul Lemler, Ying Chen, YosephGebregziabher and Lawrence D. Ziegler <
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12.1 Introduction 257 <
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12.2 SERS of Bacterial Cells: Methodology and Diagnostics258 <
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12.3 Characteristics of SERS Spectra of Bacteria 261 <
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12.4 PCA Barcode Analysis 263 <
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12.5 Biological Origins of Bacterial SERS Signatures 265 <
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12.6 SERS Bacterial Identification in Human Body Fluids:Bacteremia and UTI Diagnostics 266 <
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12.7 Red Blood Cells and Hemoglobin: Blood Aging and DiseaseDetection 267 <
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12.8 SERS of Whole Blood 269 <
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12.9 SERS of RBCs 271 <
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12.10 Malaria Detection 273 <
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12.11 Cancer Cell Detection: Metabolic Profiling by SERS 273 <
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12.12 Conclusions 276 <
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Acknowledgment 277 <
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References 277 <
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13. SERS in Cells: from Concepts to Practical Applications285 Janina Kneipp and Daniela Drescher <
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13.1 Introduction 285 <
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13.2 SERS Labels and SERS Nanoprobes: Different Approaches toObtain Different Information 286 <
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13.2.1 Highlighting Cellular Substructures with SERS Labels286 <
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13.2.2 Probing Intrinsic Cellular Biochemistry with SERSNanoprobes 288 <
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13.3 Consequences of Endocytotic Uptake and Processing forIntrinsic SERS Probing in Cells 289 <
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13.4 Quantification of Metal Nanoparticles in Cells 292 <
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13.5 Toxicity Considerations 295 <
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13.6 Applications 298 <
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13.6.1 pH Nanosensors for Studies in Live Cells 298 <
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13.6.2 Following Cell Division with SERS 299 <
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Acknowledgment 301 <
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References 301 <
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Index 309