Analysis of the Adsorption Kinetics

1 Protein Adsorption Kinetics:

Influence of Substrate Electric Potential 1

Paul R. Van Tassel

1.1 Introduction 1

1.2 Theoretical Prediction 2

1.3 Experimental Measure 6

1.3.1 OWLS Principles 6

1.3.2 OWLS Experiments 8

1.4 Results 9

1.5 Discussion 17

1.5.1 Surface-Bound Counterions 19

1.5.2 Local pH Effects 20

1.5.3 Solvent Interfacial Structure 20

1.5.4 Protein Charge Heterogeneity 20

1.6 Conclusions 21

References 21

2 From Kinetics to Structure: High Resolution Molecular Microscopy 23

Jeremy J. Ramsden

2.1 Introduction 23

2.2 Optical Waveguide Lightmode Spectroscopy 25

2.2.1 Principles of Optical Biosensing 27

2.2.2 Mode Equations for OWLS 28

2.2.3 The Uniform Thin Film Approximation (UTFA) 30

2.2.4 Optical Invariants 31

2.3 The Practical Determination of Waveguide Parameters 34

2.3.1 Device Fabrication 35

2.3.2 Fluid Handling Arrangements 36

2.4 Static Structure 37

2.5 Kinetic Analysis and Dynamic Structural Inference 37

2.5.1 Particle Transport 37

2.5.2 The Chemical Adsorption Coefficient 40

2.5.3 The Analysis of The Available Area Function 41

2.6 Behaviour of Real Proteins 43

2.6.1 Evaluation of Lateral Diffusivity and 2D Crystal Unit Cell Size 44

2.6.2 Desorption 45

2.6.3 Multilayers 46

2.7 Conclusions 47

References 48

3 Initial Adsorption Kinetics in a Rectangular Thin Channel, and Coverage-Dependent Structural Transition Observed by Streaming Potential 51

Philippe Déjardin, Elena N. Vasina

3.1 Introduction 51

3.2 The Initial Adsorption Constant and its Limit Expressions 56

3.2.1 The Local Initial Adsorption Constant k(x), its Limit Expressions and Approximation 56

3.2.2 The Mean Adsorption Constant, its Limit Expressions and Approximation 59

3.2.3 Experimental Results and Discussion 61

3.3 The Structural Transition with Increasing

Interfacial Concentration 63

3.3.1 Observation by Streaming Potential 64

3.3.2 DifferentModels 66

3.4 Conclusion 67

Appendix 68

References 69

Part II Analysis of the Structure at the Interface

4 Dual Polarisation Interferometry: An Optical Technique to Measure the Orientation and Structure of Proteins at the Solid-Liquid Interface in Real Time 75

Neville Freeman

4.1 Introduction 75

4.2 Experimental Approaches Adopted 79

4.2.1 Typical Approach Adopted 79

4.2.2 Experimental Protocols 79

4.2.3 Advantages 79

4.2.4 Verifying DPI as an Experimental Approach 80

4.3 DPI: Applications 80

4.3.1 Introduction 80

4.3.2 Protein Orientation 81

4.3.3 Bovine Serum Albumin Structures at pH 3 and pH 7 82

4.3.4 Protein Orientation and Subsequent Activity 83

4.3.5 Protein Structure and Small Molecule Interactions 87

4.3.6 Protein Structure and Metal Ion Interactions 90

4.4 Future Developments 91

4.5 Conclusions 93

Appendix 1 DPI: Background 93

A. 1.1 Neutron Reflection 93

A.1.2 Surface Plasmon Resonance 94

Appendix 2 DPI: Theory 95

Appendix3 DPI: Implementation 99

A.3.1 Hardware 99

A.3.2 Data Analysis 101

References 102

5 Total Internal Reflection Ellipsometry:

Monitoring of Proteins on Thin Metal Films 105

Michal Poksinski, Hans Arwin

5.1 Introduction 105

5.2 Total Internal Reflection Ellipsometry 106

5.3 Experimental Setup 110

5.4 Application Examples 113

5.5 Further Possibilities 117

References 118

6 Conformations of Proteins Adsorbed at Liquid-Solid Interfaces 119

Sylvie Noinville, Madeleine Revault

6.1 Introduction 119

6.2 Experimental Techniques 125

6.2.1 High-Resolution Structure of Proteins 125

6.2.2 Secondary Structure of Proteins 126

6.2.3 Orientation, Localised Structural Information 127

6.2.4 Spatial Distribution of Proteins in the Adsorbed Layer 128

6.2.5 Solvation Information 129

6.3 Surface Effects on Both Protein Structure and Solvation by the ATR-FTIR Technique 130

6.3.1 FTIR Spectral Analysis 130

6.3.2 Proteins in Solution 132

6.3.3 Surface-Induced Conformational Changes of a Soft Protein: BSA 134

6.3.4 Surface-Induced Conformational Changes of a Hard Protein: Lysozyme 138

6.3.5 Folding or unfolding of proteins on hydrophobic supports 141

6.4 Conclusion 142

References 142

7 Evaluation of Proteins on Bio-Devices 151

Satoka Aoyagi, Masahiro Kudo

7.1 Introduction 151

7.2 Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) 153

7.2.1 Principles of TOF-SIMS 153

7.2.2 TOF-SIMS Spectra and Secondary-Ion Images 156

7.2.3 Data Analysis 157

7.3 Analysis of Proteins on Bio-Devices 161

7.3.1 Characterization of Proteins on Substrates 161

7.3.2 Investigation of Conformation and Orientation of Proteins on Substrates 164

7.3.3 Imaging of Protein Distribution 165

7.3.4 Other Points and Future Directions 168

7.4 Summary 169

References 169

Part III Some Applications

8 Fibronectin at Polymer Surfaces with Graduated Characteristics 175

Tilo Pompe, Lars Renner, Carsten Werner

8.1 Introduction 175

8.2 Gradated Substrate Physicochemistry 177

8.3 Fibronectin Exchange at a Constant Surface Concentration... 181

8.4 Fibronectin Exchange at Variable Surface Concentrations 188

8.5 Relevance of the Interfacial Constraints of Fibronectin for Cell-Matrix Adhesion 195

References 197

9 Development of Chemical Microreactors by Enzyme Immobilization onto Textiles 199

Christophe Innocent, Patrick Seta

9.1 Introduction 199

9.2 Nonconducting Cellulosic Textiles 201

9.2.1 Pepsin and Trypsin Immobilization on Cotton 201

9.2.2 Immobilization of Uricase and Xanthine Oxidase on Ion-Exchanging Textiles 211

9.2.3 Urease Electrodialysis Coupling 223

9.3 Electron-Conducting Textile 227

9.3.1 Enzyme Immobilization on Carbon Felt 227

9.3.2 Electrocatalysis Coupling with Enzyme-Conducting Textile Catalytic Reactivity 238

References 242

10 Approaches to Protein Resistance on the Polyacrylonitrile-based Membrane Surface: an Overview 245

Ling-Shu Wan, Zhi-KangXu, Xiao-Jun Huang

10.1 Introduction 245

10.2 Copolymerization Procedures 246

10.3 Poly(ethylene glycol) Tethering 252

10.4 Physical Adsorption 257

10.5 Biomacromolecule Immobilization 259

10.6 Biomimetic Modification 263

10.7 Conclusion 266

References 268

11 Modulation of the Adsorption and Activity of Protein/Enzyme on the Polypropylene Microporous Membrane Surface by Surface Modification 271

Qian Yang, Zhi-KangXu, Zheng-Wei Dai

11.1 Surface Modifications for Reducing Nonspecific

Protein Adsorption 271

11.1.1 Plasma treatment 273

11.1.2 Ultraviolet(UV)modification 276

11.1.3 y-Ray-induced modification 282

11.1.4 Ozone Method 285

11.2 Surface-Modified PPMMs for Enzyme Immobilization 286

11.2.1 Physical Adsorption/Entrapment 287

11.2.2 Covalent Binding 289

11.2.3 Site-Specific Immobilization 294

11.3 Conclusions 295

References 295

12 Nonbiofouling Surfaces Generated from Phosphorylcholine-Bearing Polymers 299

Yasuhiko Iwasaki, Nobuo Nakabayashi, Kazuhiko Ishihara

12.1 Introduction 299

12.2 Forces Involved in Protein Adsorption 300

12.3 Design of Phosphorylcholine-Bearing Surfaces 302

12.4 Mechanism of Resistance to Protein Adsorption on the MPC Polymer Surface 303

12.5 Fundamental Interactions Between MPC Polymers and Proteins 310

12.6 Recent Designs of Nonfouling Phosphorylcholine

Surfaces with Well-Defined Structures 312

12.7 Control of Cell-Material Interactions on a Phosphorylcholine Polymer Nonfouling Surface 314

12.7.1 Cell Manipulation on a Well-Defined Phosphorylcholine Polymer Brush 315

12.7.2 Selective Cell Attachment to a Biomimetic Polymer Surface

Through the Recognition of Cell-Surface Tags 318

12.8 Conclusion 321

References 321

Subject Index 327

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