Surface Plasmon Enhanced, Coupled and Controlled Fluorescence

Chris D. Geddes, PhD, FRSC, is a professor at the University of Maryland, Baltimore County, USA, where he is the director of the Institute of Fluorescence, and the editor-in-chief of both the Journal of Fluorescence and the Plasmonics journal. With more than 250 papers, 35 books, and >100 patents to his credit, he has extensive expertise in fluorescence spectroscopy, particularly in fluorescence sensing and metal–fluorophore interactions.

List of Contributors xi

Preface xv

1 Plasmonic–Fluorescent and Magnetic–Fluorescent Composite Nanoparticle as Multifunctional Cellular Probe 1
Arindam Saha, SK Basiruddin, and Nikhil Ranjan Jana

1.1 Introduction 1

1.2 Synthesis Design of Composite Nanoparticle 2

1.2.1 Method 1: Polyacrylate Coating–Based Composite of Nanoparticle and Organic Dye 3

1.2.2 Method 2: Polyacrylate Coating–Based Composite of Two Different Nanoparticles 3

1.2.3 Method 3: Ligand Exchange Approach–Based Composite of Two Different Nanoparticles 4

1.3 Property of Composite Nanoparticles 5

1.3.1 Optical Property 5

1.3.2 Fluorophore Lifetime Study 7

1.4 Functionalization and Labeling Application of Composite Nanoparticle 8

1.5 Conclusion 8

2 Compatibility of Metal–Induced Fluorescence Enhancement with Applications in Analytical Chemistry and Biosensing 13
Fang Xie, Wei Deng, and Ewa M. Goldys

2.1 Introduction 13

2.2 Homogeneous Protein Sensing MIFE Substrates 14

2.2.1 Core–Shell Approach 14

2.2.2 Homogeneous Large Au Nanoparticle Substrates 16

2.2.3 Commercial Klarite™ Substrate 18

2.3 Ag Fractal Structures 19

2.3.1 Reasons for High Enhancement Factors in Nanowire Structures 19

2.3.2 Ag Dendritic Structure—Homogeneous Silver Fractal 22

2.4 MIFE with Membranes for Protein Dot Blots 25

2.5 MIFE with Flow Cytometry Beads and Single Particle Imaging 30

3 Plasmonic Enhancement of Molecule–Doped Core–Shell and Nanoshell on Molecular Fluorescence 37
Jiunn–Woei Liaw, Chuan–Li Liu, Chong–Yu Jiang, and Mao–Kuen Kuo

3.1 Introduction 37

3.2 Theory 38

3.2.1 Plane Wave Interacting with an Multilayered Sphere 39

3.2.2 Excited Dipole Interacting with a Multilayered Sphere 40

3.2.3 EF on Fluorescence 40

3.3 Numerical Results and Discussion 41

3.3.1 Core–Shell 41

3.3.2 Nanoshelled Nanocavity 50

3.3.3 NS@SiO2 53

3.4 Conclusion 66

4 Controlling Metal–Enhanced Fluorescence Using Bimetallic Nanoparticles 73
Debosruti Dutta, Sanchari Chowdhury, Chi Ta Yang, Venkat R. Bhethanabotla, and Babu Joseph

4.1 Introduction 73

4.2 Experimental Methods 74

4.2.1 Synthesis 74

4.2.2 Particle Characterization 75

4.2.3 Fluorescence Spectroscopy 76

4.3 Theoretical Modeling 79

4.3.1 Modeling SPR Using Mie Theory 79

4.3.2 Modeling of Metal–Enhanced Fluorescence Modified Gersten–Nitzan Model 81

4.3.3 Modeling MEF Using Finite–Difference Time–Domain (FDTD) Calculations 85

4.4 Conclusion and Future Directions 87

5 Roles of Surface Plasmon Polaritons in Fluorescence Enhancement 91
K. F. Chan, K. C. Hui, J. Li, C. H. Fok, and H. C. Ong

5.1 Introduction 91

5.1.1 Surface Plasmon–Mediated Emission 91

5.1.2 Excitation of Propagating and Localized Surface Plasmon Polaritons in Periodic Metallic Arrays 93

5.1.3 Surface Plasmon–Mediated Emission from Periodic Arrays 95

5.2 Experimental 95

5.2.1 Sample Preparation 95

5.2.2 Optical Characterizations 96

5.3 Result and Discussion 97

5.3.1 The Decay Lifetimes of Metallic Hole Arrays 97

5.3.2 Dependence of Decay Lifetime on Hole Size 98

5.3.3 Comparison between Dispersion Relation and PL Mapping 100

5.3.4 Comparison of the Coupling Rate ΓB of Different SPP Modes 102

5.3.5 Photoluminescence Dependence on Hole Size 104

5.3.6 Dependence of Fluorescence Decay Lifetime on Hole Size 105

5.4 Conclusions 107

6 Fluorescence Excitation, Decay, and Energy Transfer in the Vicinity of Thin Dielectric/Metal/Dielectric Layers near Their Surface Plasmon Polariton Cutoff Frequency 111
Kareem Elsayad and Katrin G. Heinze

6.1 Introduction 111

6.2 Background 111

6.3 Theory 112

6.4 Summary 120

7 Metal–Enhanced Fluorescence in Biosensing Applications 121
Ruoyun Lin, Chenxi Li, Yang Chen, Feng Liu, and Na Li

7.1 Introduction 121

7.2 Substrates 121

7.3 Distance Control 128

7.4 Summary and Outlook 132

8 Long–Range Metal–Enhanced Fluorescence 137
Ofer Kedem

8.1 Introduction 137

8.2 Collective Effects in NP Films 138

8.3 Investigations of Metal–Fluorophore Interactions at Long Separations 138

8.3.1 Distance–Dependent Fluorescence of Tris(bipyridine)ruthenium(II) on Supported Plasmonic Gold NP Ensembles 138

8.3.2 Lifetime 139

8.3.3 Intensity 141

8.3.4 Emission Wavelength and Linewidth 143

8.4 Conclusions 146

9 Evolution, Stabilization, and Tuning of Metal–Enhanced Fluorescence in Aqueous Solution 151
Jayasmita Jana, Mainak Ganguly, and Tarasankar Pal

9.1 Introduction 151

9.1.1 Coinage Metal Nanoparticles in Metal–Enhanced Fluorescence 153

9.2 Metal–Enhanced Fluorescence in Solution Phase 154

9.2.1 Metal–Enhanced Fluorescence from Metal(0) in Solution 154

9.3 Applications of Metal–Enhanced Fluorescence 169

9.3.1 Sensing of Biomolecules 169

9.3.2 Sensing of Toxic Metals 171

9.4 Conclusion 174

10 Distance and Location–Dependent Surface Plasmon Resonance–Enhanced Photoluminescence in Tailored Nanostructures 179
Saji Thomas Kochuveedu and Dong Ha Kim

10.1 Introduction 179

10.2 Effect of SPR in PL 181

10.2.1 Photoluminescence 181

10.2.2 Enhancement of Emission by SPR 182

10.2.3 Quenching of Emission by SPR 184

10.3 Effect of SPR in FRET 185

10.3.1 FRET 185

10.3.2 SPR–Induced Enhanced FRET 188

10.3.3 Effect of the Position, Concentration, and Size of Plasmonic Nanostructures in FRET System 189

10.4 Conclusions and Outlook 191

11 Fluorescence Quenching by Plasmonic Silver Nanoparticles 197
M. Umadevi

11.1 Metal Nanoparticles 197

11.2 Fluorescence Quenching 197

11.3 Mechanism behind Quenching 198

12 AgOx Thin Film for Surface–Enhanced Raman Spectroscopy 203
Ming Lun Tseng, Cheng Hung Chu, Jie Chen, Kuang Sheng Chung, and Din Ping Tsai

12.1 Introduction 203

12.1.1 SERS on the Laser–Treated AgOx Thin Film 203

12.1.2 Annealed AgOx Thin Film for SERS 206

12.2 Conclusion 206

13 Plasmon–Enhanced Two–Photon Excitation Fluorescence and Biomedical Applications 211
Taishi Zhang, Tingting Zhao, Peiyan Yuan, and Qing–Hua Xu

13.1 Introduction 211

13.2 Metal–Chromophore Interactions 212

13.3 Plasmon–Enhanced One–Photon Excitation Fluorescence 214

13.4 Plasmon–Enhanced Two–Photon Excitation Fluorescence 215

13.5 Conclusions and Outlook 220

14 Fluorescence Biosensors Utilizing Grating–Assisted Plasmonic Amplification 227
Koji Toma, Mana Toma, Martin Bauch, Simone Hageneder, and Jakub Dostalek

14.1 Introduction 227

14.2 SPCE in Vicinity to Metallic Surface 227

14.3 SPCE Utilizing SP Waves with Small Losses 230

14.4 Nondiffractive Grating Structures for Angular Control of  SPCE 232

14.5 Diffractive Grating Structures for Angular Control of SPCE 234

14.6 Implementation of Grating–Assisted SPCE to Biosensors 236

14.7 Summary 237

15 Surface Plasmon–Coupled Emission: Emerging Paradigms and Challenges for Bioapplication 241
Shuo–Hui Cao, Yan–Yun Zhai, Kai–Xin Xie, and Yao–Qun Li

15.1 Introduction 241

15.2 Properties of SPCE 242

15.3 Current Developments of SPCE in Bioanalysis 243

15.3.1 New Substrates Designing for Biochip 243

15.3.2 Optical Switch for Biosensing 244

15.3.3 Full–Coupling Effect for Bioapplication 245

15.3.4 Hot–Spot Nanostructure–Based Biosensor 248

15.3.5 Imaging Apparatus for High–Throughput Detection 249

15.3.6 Waveguide Mode SPCE to Widen Detection Region 251

15.4 Perspectives 252

16 Plasmon–Enhanced Luminescence with Shell–Isolated Nanoparticles 257
Sabrina A. Camacho, Pedro H. B. Aoki, Osvaldo N. Oliveira, Jr, Carlos J. L. Constantino, and Ricardo F. Aroca

16.1 Introduction 257

16.2 Synthesis of Shell–Isolated Nanoparticles 259

16.2.1 Nanosphere Au–SHINs 259

16.2.2 Nanorod Au–SHINs 260

16.3 Plasmon–Enhanced Luminescence in Liquid Media 262

16.4 Enhanced Luminescence on Solid Surfaces and Spectral Profile Modification 265

16.4.1 SHINEF on Langmuir–Blodgett Films 266

17 Controlled and Enhanced Fluorescence Using Plasmonic Nanocavities 271
Gleb M. Akselrod, David R. Smith, and Maiken H. Mikkelsen

17.1 Introduction to Plasmonic Nanocavities 271

17.2 Summary of Fabrication 272

17.3 Properties of the Nanocavity 273

17.3.1 Nanocavity Resonances 273

17.3.2 Tuning the Resonance 274

17.3.3 Directional Scattering and Emission 276

17.4 Theory of Emitters Coupled to Nanocavity 277

17.4.1 Simulation of Nanocavity 278

17.4.2 Enhancement in the Spontaneous Emission Rate 278

17.5 Absorption Enhancement 280

17.6 Purcell Enhancement 282

17.7 Ultrafast Spontaneous Emission 286

17.8 Harnessing Multiple Resonances for Fluorescence Enhancement 288

17.9 Conclusions and Outlook 291

18 Plasmonic Enhancement of UV Fluorescence 295
Xiaojin Jiao, Yunshan Wang, and Steve Blair

18.1 Introduction 295

18.2 Plasmonic Enhancement 295

18.3 Analytical Description of PE of Fluorescence 296

18.4 Overview of Research on Plasmon–Enhanced UV Fluorescence 297

18.4.1 Material Selection 297

18.4.2 Structure Choice 301

18.4.3 Experimental Measurement 303

18.5 Summary 306

Index 309