Bioelectrochemistry of Biomembranes and Biomimetic Membranes

Rolando Guidelli obtained his degree in Chemistry at Florence University, Italy, and was appointed by Florence University as a lecturer in Electrochemistry. He was then promoted to full professor of Electrochemistry in the Faculty of Science of Florence University. His scientific interests have been focused on electrode kinetics, structure of the metal/water interface and bioelectrochemistry. He has won several distinguished prizes in the field of electrochemistry and is the author and editor of several book chapters on the topic.  Further, he has served as the organizer of several conferences in the field.

Preface xi 1 Biological Membranes 1

1.1 Introduction 1

1.2 The Biological Membranes 2

1.2.1 The Lipids and the Lipid Bilayer 4

1.2.2 The Membranes of Cells and Organelles 9

1.3 The Proteins 12

1.4 The Membrane Functions 14

1.4.1 Transport 15

1.4.2 Signal Transduction 17

1.4.3 Cell–Cell Recognition 17

1.4.4 Enzymatic Activity 18

1.4.5 Intercellular Joining 18

References 19

2 Electrostatics of Biomembranes 21

2.1 The Electric Field 21

2.2 Electric Field Created by a Uniform, Infinitely Extended Planar Charge Distribution 23

2.3 The Parallel-plate Capacitor 27

2.4 The Dielectric Constant 28

2.5 The Electric Potential Across a Membrane 30

2.6 Poisson–Boltzmann Equation and Gouy–Chapman Theory 33

2.7 Measurement of the Charge Density of the Polar Heads of a Charged Lipid 40

2.8 Electropermeabilization of Lipid Bilayers 44

References 51

3 Thermodynamics 53

3.1 Some Concepts of ChemicalThermodynamics 53

3.2 The Electrochemical Potential 59

3.3 Thermodynamics of Irreversible Processes 61

3.4 Coupling of Primary and Secondary Active Transport in Biomembranes 68

3.4.1 Plasma Membranes of Animal Cells 70

3.4.2 Inner MitochondrialMembrane,Thylakoid Membrane, and Bacterial Plasma Membrane 71

3.4.3 Membranes of Plant and Fungal Cells 74

3.4.4 Membranes of the Vesicular System 76

References 76

4 Passive Transport 79

4.1 How do Ion Channels Look Like? 79

4.2 The Nernst Equation and the Resting Potential 84

4.3 A First Approach to the Action Potential 89

4.4 Single-channel Open Probability 94

4.4.1 The Variance 98

4.5 The Goldman–Hodgkin–Katz Equation 100

4.6 Open Probability and Gating Charge of Ion Channels 108

4.6.1 The Gap Junction 112

4.7 RateTheory of Membrane Transport 115

4.8 Action Potential Revisited 117

4.8.1 The Shape of the Action Potential 124

4.8.2 The Gating Current of the Potassium Channel 125

References 127

5 Active Transport 129

5.1 The Ion Pumps 129

5.2 Electromotive Force and Inversion Potential of Ion Pumps 136

5.3 Energy Levels of the Enzymatic Cycle of Ion Pumps 138

5.4 Kinetics of Ion Pumps Under Steady-State Conditions 144

5.5 Electrogenicity of the Ion Pumps 147

5.6 Kinetics of Ion Pumps Under Pre-Steady-State Conditions 150

5.6.1 Ca2+-ATPase of the Sarcoplasmic Reticulum 161

5.6.2 Na+, K+-ATPase 166

5.7 Transporters 168

5.7.1 Cotransporters 168

5.7.2 Countertransporters 170

References 172

6 BiomimeticMembranes 175

6.1 The Various Types of BiomimeticMembranes 175

6.2 Electrochemical Techniques for the Investigation of Biomimetic Membranes 177

6.2.1 Electrochemical Impedance Spectroscopy 177

6.2.2 Potential-Step Chronoamperometry (Current–Time Curves) 185

6.2.3 Potential-Step Chronocoulometry 193

6.2.4 Cyclic Voltammetry 198

6.2.5 AC Voltammetry 216

6.3 Lipid Bilayers Interposed Between Two Aqueous Phases 218

6.4 Biomimetic Membranes Noncovalently Supported by Metals 224

6.4.1 Lipid Monolayers Self-Assembled on Mercury 224

6.4.2 Solid-Supported Bilayer Lipid Membranes (sBLMs) 227

6.4.3 S-Layer Stabilized Bilayer Lipid Membranes (ssBLMs) 232

6.5 Biomimetic Membranes Covalently Supported by Metals 233

6.5.1 Alkanethiol/Lipid Hybrid Bilayers 233

6.5.2 Tethered Bilayer Lipid Membranes (tBLMs) 236

6.5.3 Polymer-Cushioned Bilayer Lipid Membranes (pBLMs) 242

6.5.4 Protein-Tethered Bilayer Lipid Membranes (ptBLMs) 242

6.6 Conclusions 244

References 248

7 Auxiliary Techniques 255

7.1 Physical Properties of ElectromagneticWaves 255

7.2 Surface Plasmon Resonance 262

7.3 Infrared Spectroscopy 272

7.4 Neutron Reflectivity 279

7.5 Fluorescence Microscopy 286

7.6 Scanning Probe Microscopy 296

7.6.1 Atomic Force Microscopy 297

7.6.2 Scanning Tunneling Microscopy 302

7.7 Langmuir–Blodgett and Langmuir–Schaefer Transfers 305

7.8 Quartz-CrystalMicrobalance 310

References 314

Index 317