Interfacial Forces in Aqueous Media, Second Edition

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ISBN: 9781574444827 | 1574444824
Cover: Hardcover
Copyright: 5/22/2006

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Thoroughly revised and reorganized, the second edition of Interfacial Forces in Aqueous Media examines the role of polar interfacial and noncovalent interactions among biological and nonbiological macromolecules as well as biopolymers, particles, surfaces, cells, and both polar and apolar polymers. The new edition includes four previously unpublished chapters on interfacial properties and structure of liquid water; new material throughout the text on the interplay between macroscopic-scale repulsions and microscopic-scale attractions in protein adsorption; and new chapters covering interfacial tension determination and examining the kinetics and energetics of protein adsorption onto metal oxide surfaces.

Introduction

(8)

Non-Covalent Interactions

(1)

van der Waals Forces

(1)

Polar, or Lewis Acid-Base (AB) Interactions

(1)

Electrostatic (EL) Interactions

(1)

Other Non-Covalent Forces

(1)

Brownian Movement (BR) Forces

(1)

General Bibliography

(5)

PART I Theory

Lifshitz--van der Waals (LW) Interactions

(10)

van der Waals Forces

(1)

Macroscopic Approximation

(2)

The Lifshitz Approach

(4)

Interfacial Lifshitz--van der Waals Interactions

(1)

Additivity of the Three Electrodynamic Contributions to the Surface Tension

(1)

Coda

(1)

Relation Between the Hamaker Constant and the Apolar Surface Tension Component

(6)

Proportionality Factor A/γLW

(1)

Significance of the Averaged L0 Value

(2)

Applicability of Eq. [III-1] to A12, A121, A132

(2)

Coda

(1)

Polar or Lewis Acid-Base Interactions

(26)

Interfacial Lewis Acid-Base Interactions

(3)

The Young-Dupre Equation

(1)

Attractive and Repulsive Polar Forces

(2)

Relative Values of the Electron-Acceptor and Electron-Donor Parameters of γ

(2)

Monopolar Surfaces and Substances

(3)

Different Modes of Interaction Between Two Polar Substances

(3)

The Surface Tension of Liquids and Solids

(1)

Interfacial Tensions Between Polar Liquids

(1)

Earlier Approaches to Correlate Contact Angles and Surface Tensions in Polar Systems

(1)

Comparison Between Repulsive Lifshitz--van der Waals and Repulsive Acid-Base Interactions

(4)

The Mechanisms Allowing ΔG LW/132 and ΔG AB/131 to Be Positive

(2)

Implications of ΔG AB/132 > 0

(1)

Implications of ΔG 132 > 0

(1)

Connection Between ``Hydrophobic'' and Hydrophilic Interactions

(1)

Coda

(3)

Electrical Double Layer Interactions

(20)

Electrokinetic Potential and Ionic Double Layer

(2)

Free Energy of Electrostatic Interactions

(1)

Electrokinetic Phenomena

(1)

ζ-Potential, Ionic Strength and Electrokinetic Mobility

(1)

Influence of the Double Layer

(4)

Thick Double Layer

(2)

Thin Double Layer

(2)

Relaxation

(2)

Validity Ranges of the Equations

(1)

Confrontation of the Equations with Experimental Data

(1)

Small κa

(1)

Large κa

(1)

Transition 0.1 < κa < 300

(1)

Calculation of ζ-Potentials from Mobility Data

(3)

The Brooks Effect

(1)

Coda

(3)

Brownian Movement Forces---Osmotic Interactions of Polymers

(8)

Brownian Movement Forces

(1)

Osmotic Interactions

(2)

Radius of Gyration

(1)

Polymer Concentration

(1)

Size and Shape of Polymer Molecules

(3)

Coda

(1)

Rate of Decay with Distance

(14)

Unretarded Lifshitz--van der Waals Forces

(1)

Retarded London--van der Waals Forces

(1)

Polar (AB) Interactions

(3)

Electrical Double Layer Interactions

(1)

Brownian Movement Interactions

(1)

Combined Interaction Forces Acting on Solids or on Suspended Particles in Polymer Solutions

(1)

The Derjaguin Approximation

(1)

Energy-Balance Diagrams

(3)

Coda

(4)

PART II Interfacial Properties and Structure of Liquid Water

Lifshitz--van der Waals and Lewis Acid-Base Properties of Liquid Water---Physical and Physico-Chemical Effects

(8)

Dominance of the Lewis Acid-Base Properties of Water

(1)

Effect of Temperature on the γ-Components of Water

(2)

The Surface Properties of Ice at 0°C

(1)

Cluster Formation in Liquid Water

(2)

Coda

(2)

Role of Water in Hydrophobic Attraction

101

(8)

The Hydrogen-Bonding (Lewis Acid-Base) Free Energy of Cohesion of Water and ``the Hydrophobic Effect''

101

(1)

Hydrophobic Hydration

102

(1)

Clathrate Formation

103

(1)

Action at a Distance

104

(1)

Modulation of the Hydrophobizing Capacity of Water

104

(3)

Decreasing |Δ AB/iwi|

104

(1)

Increasing |Δ AB/iwi|

105

(2)

Coda

107

(2)

Role of Water in Hydrophilic Repulsion

109

(8)

Water and Hydration Forces

109

(1)

Negative γiw Values and Hydrophilic Repulsion

110

(1)

Hydration Orientation and Action at a Distance

110

(2)

Hydrophilicity and Hydration Orientation

112

(1)

Hydration Orientation of Proteins

112

(2)

Modulation of the Hydrophilic Repulsion Through Temperature Changes

114

(1)

Raising Δ AB/iwi

114

(1)

Lowering Δ AB/iwi

114

(1)

Coda

115

(2)

The Water--Air Interface

117

(14)

Hyper-Hydrophobicity of Air at the Water--Air Interface

117

(2)

Quantitative Expression of the Total Hydrophobic Attraction Energy at the Water--Air Interface

119

(1)

Absence of Hydration of Air at the Water--Air Interface

120

(1)

Attraction of Partly Polar, or Amphiphilic Solutes to the Water--Air Interface, Which decreases the Apparent Surface Tension of Water

121

(2)

Repulsion of Hydrophilic, or Near-Hydrophilic Solutes by the Air-Side of the Water--Air Interface; the Increase of the Surface Tension of Aqueous Solutions by the Admixture of Sugars and Salts

123

(1)

The ζ--Potential of Air Bubbles in Water

124

(2)

Coda

126

(5)

PART III Experimental Measurement Methods

Contact Angle and Surface Tension Determination and Preparation of Solid Surfaces

131

(26)

The Sessile Drop as a Force Balance

131

(1)

Spreading Pressure

131

(3)

Contact Angle Measurement in Air--Hysteresis

134

(1)

Contact Angles on Heterogeneous Surfaces---Cassie's Equation

135

(2)

Contact Angle Measurement in Liquids

137

(4)

Contact Angle Measurement by Wicking

139

(2)

Surface Tension of Liquids

141

(1)

Apolar and Polar Surface Tension Component of Liquids

142

(1)

Estimation of the Polar Surface Tension Parameters γÅL and γL of Liquids

143

(5)

Gel Method

143

(1)

Polar Solids Method

144

(4)

Purity of Contact Angle Liquids

148

(1)

Surface Tension and Surface Free Energy

149

(1)

Influence of Temperature on the Properties of Water as a Contact Angle Liquid

149

(1)

Influence of the pH of Water as a Contact Angle Liquid on the Surface Properties of Electrically Charged Solid Surfaces

150

(1)

Influence of the pH of Water on the Properties of Water Itself, in Connection with Its Use as a Contact Angle Liquid

151

(1)

Preparation of Solid Surfaces

152

(1)

Particles and Cells

152

(1)

Dried Solutes

153

(1)

Hydrated Solutes

153

(2)

Coda

155

(2)

Interfacial Tension Determination---Influence of Macroscopic- and Microscopic-Scale Interactions

157

(8)

Interfacial Tensions and Free Energies of Interfacial Interaction

157

(1)

Interfacial Tension Between Immiscible Liquids

158

(1)

Determination of Interfacial Tensions Between Condensed-Phase Materials and Water

158

(2)

The Aqueous Solubility Approach for Determining γ 0/ow

160

(2)

Use of the cmc of Surfactant Molecules for Determining their γ 0/ow

162

(2)

Contact Angle-Based Methods for Determining γ 0/ow

164

(1)

Different Approaches for Interpreting Contact Angles and Determining the Surface Tension and Surface Tension Components of Solids

165

(14)

The Concept of Surface Tension of a Solid

165

(1)

Critical Surface Tensions of Solids

166

(1)

``Equation of State'' Approaches

166

(3)

The Concept of a Single Polar Surface Tension Component, ``Ygamma;P'', in Conjunction with a Geometric Mean Combining Rule

169

(1)

Comparison Between the γAB/12 and the ``γP/12'' Approaches

170

(3)

Sedimentation of Particle Suspensions

173

(1)

Advancing Solidification Fronts

174

(2)

Adhesion Methods

176

(1)

Other Approaches

177

(1)

γLW and Hamaker Constants

177

(1)

Phase Separation

178

(1)

Electrophoretic Mobility

178

(1)

Coda

178

(1)

Electrokinetic Methods

179

(24)

Microelectrophoresis of Particles and Cells

179

(1)

Moving Boundary Electrophoresis

180

(1)

Zone Electrophoresis

180

(2)

Zone Electrophoresis of Particles and Cells

182

(2)

Descending Density Gradient Electrophoresis

182

(1)

Ascending Electrophoresis

183

(1)

Packed Column Cell Electrophoresis

183

(1)

Enhanced Electrophoretic Separation of Subclasses of Cells Through Receptor-Tagging

184

(1)

Microgravity Electrophoresis

184

(2)

Molecular Sieve Zone Electrophoresis

186

(1)

Starch Gel Electrophoresis

186

(3)

Polyacrylamide Gel Electrophoresis

187

(1)

Sodium Dodecyl Sulfate Polyacrylamide Electrophoresis

187

(1)

Graded Porosity Gel Electrophoresis

188

(1)

Gel Electrophoresis of Nucleic Acids

188

(1)

Zone Electrophoresis of Adsorbed Proteins

189

(1)

Continuous Flow Electrophoresis

190

(4)

Curtain Electrophoresis

190

(2)

Free Flow Electrophoresis

192

(1)

Endless Belt Electrophoresis

192

(1)

Cylindrical Rotating Continuous Flow Electrophoresis

193

(1)

Stable Flow Electrophoresis

193

(1)

Electrophoretic Field Flow Fractionation

193

(1)

Horizontal Rotating Cylinder Electrophoresis

194

(1)

Capillary Electrophoresis

194

(1)

Isoelectric Focusing

195

(2)

Cell Isoelectric Focusing

197

(1)

Isotachophoresis

197

(1)

Bidimensional Methods

198

(1)

Electroosmosis

198

(1)

Streaming Potential and Sedimentation Potential

199

(1)

Electrophoresis in Non-Aqueous Media

200

(1)

Coda and Limitations

201

(2)

Direct Measurement Methods, Treating the Force Balance in Particular

203

(10)

Force Balance

203

(1)

Other Approaches

204

(2)

Interfacial Attraction Effects (Hydrophobic Interactions) in Water

206

(1)

Interfacial Repulsion Effects (Hydration Repulsion) in Water

207

(1)

Interactions Between Adsorbed Polymer Layers in Apolar Media

208

(1)

Interaction Between Adsorbed Biopolymers and Between Adsorbed Phospholipids in Aqueous Media

208

(1)

Measurement of the Decay-Length of Water

209

(1)

Electrostatic Effects

209

(1)

Oscillatory Effects

210

(1)

Atomic Force Microscopy

210

(1)

Coda

210

(3)

PART IV Associated Phenomena and Applications

Surface Tension Components and Parameters of Liquids and Solids

213

(14)

Completely Apolar Liquids

213

(1)

Monopolar Liquids, Immiscible with Water

214

(1)

Dipolar Liquids, Immiscible with Water

214

(1)

Naphthalene

215

(1)

Monopolar and Dipolar Water-Miscible Liquids

216

(1)

Synthetic Polymers

217

(1)

Biopolymers

217

(1)

Plasma Proteins

217

(3)

Other Proteins

220

(1)

Carbohydrates

221

(3)

Nucleic Acids

224

(1)

Contact Angle Liquids

224

(1)

Surface Tension Properties of Clays and Other Minerals

225

(1)

Coda

226

(1)

Attractive LW- and AB-Forces: Hydrophobic Interactions

227

(16)

Interaction Between Two Identical Organic Molecules, Immersed in Water

227

(2)

Enthalpy and Entropy of Hydrophobic Interactions

229

(2)

Apolar (LW) and Polar (AB) Contributions to Hydrophobic Interactions

231

(4)

Hydrophobic Attractions (ΔGiwi)

231

(2)

Hydrophobic Hydration (ΔGiw)

233

(1)

Conclusions

234

(1)

Propagation at a Distance of Attractive Hydrophobic Interactions

235

(1)

Cavitation Is an Effect, Not a Cause of Hydrophobic Interactions; When Wiw Is Smaller than Wiwi, Cavitation Is Favored Near the Interface

236

(1)

Attractive Interfacial Interactions in Non-Aqueous Media

237

(1)

Further to the Mechanism of Hydrophobic Interactions

237

(1)

Occurrence of Attractive Interfacial (''Hydrophobic'') Interactions Between Similar Sites

238

(1)

Interactions Between Two Different Organic Compounds Immersed in Water

238

(2)

Occurrence of Attractive Interfacial (''Hydrophobic'') Interactions Between Two Dissimilar Sites

240

(1)

Coda

240

(3)

Repulsive AB-Forces: Hydrophilic Interactions---Osmotic Pressures of PEO Solutions

243

(20)

Negative Interfacial Tensions and Polar Repulsion

243

(2)

Monopolar Surfaces

245

(1)

Quantitative Expression of Hydrophilicity and Hydrophobicity

246

(3)

Propagation at a Distance of Repulsive Hydrophilic Interactions

249

(1)

Linkage Between EL and AB Forces

250

(2)

Osmotic Pressure Effects

252

(1)

Osmotic Pressures of PEO-Water Solutions

253

(6)

Monopolar Repulsion Between Dissimilar Polar Entities

259

(1)

Monopolar Repulsion in Non-Aqueous Polar Media

259

(1)

Persistence of ΔGiwi Interactions at a Distance

260

(1)

Coda

261

(1)

Appendix: On the Interpolation of Values of γ12 versus PEO Concentration

262

(1)

The Primary and Secondary Interactions

263

(12)

van der Waals Interactions (Primary)

264

(1)

Electrostatic, or Coulombic Interactions (Primary)

265

(1)

Lewis Acid-Base Interactions (Primary)

265

(1)

Brownian Movement Interactions

266

(1)

Primary Forces and Secondary Phenomena

267

(1)

Osmotic Pressure

267

(1)

Disjoining Pressure

268

(1)

Structural Forces

268

(1)

Steric Interactions

269

(1)

Depletion Interactions

270

(2)

Entropy-Driven and Enthalpy-Driven Interactions

272

(1)

Cross-Binding Interactions

272

(1)

Specific Interactions

273

(1)

Coda

273

(2)

Phase Separation in Polymer Solutions; Coacervation and Complex Coacervation

275

(22)

Phase Separation of Polymers in Organic Media

275

(5)

Phase Separation of Polymers in Aqueous Media

280

(2)

Phase Separation of Water-Soluble Polymers in Polar Organic Media

282

(1)

Mechanism of Polymer Phase Separation in Apolar Systems

283

(1)

Mechanism of Polymer Phase Separation in Polar and Especially in Aqueous Systems

283

(1)

The Interfacial Tension Between Aqueous Phases

284

(1)

Use of Aqueous Two-Phase Systems for Cell and Biopolymer Separation

285

(1)

Polymer Phase Separation Summarized

285

(1)

Coacervation and Complex Coacervation

286

(1)

Role of Low Molecular Weight Solutes in Coacervation

287

(1)

Complex Coacervation

288

(3)

Flocculation

291

(2)

Phase Formation in Microemulsions

293

(3)

Coda

296

(1)

Solubility of Polymers and Other Solutes

297

(22)

Apolar Systems and Hildebrand's Solubility Parameter

297

(1)

Polar Systems

298

(2)

Solubility of Apolar Polymers

300

(1)

Miscibility of Polar Liquids

301

(3)

Miscibility and Solubility as Microscopic-Scale Phenomena

301

(2)

Miscibility and Immiscibility as Macroscopic-Scale Phenomena

303

(1)

Conclusion

304

(1)

Solubility of Polar Polymers

304

(3)

Solubility in Non-Aqueous Polar Liquids

307

(2)

Insolubilization of Biopolymers

309

(2)

The Flory-Huggins X-Parameter and the Solubility of Polar Compounds

311

(1)

Solubility and the cmc of Non-Ionic Surfactants

312

(4)

Relation Between ΔGTOT and the cmc

316

(1)

Solubility and the cmc of Anionic Surfactants

316

(1)

Solubility of Organic Liquids in Water

317

(1)

Solubility of Electrolytes

318

(1)

Coda

318

(1)

Cell and Particle Stability

319

(26)

Energy vs. Distance Plots in Aqueous Media

319

(6)

Particle Stability vs. Flocculation---The Schulze-Hardy Mechanism of Flocculation with Plurivalent Counterions

325

(2)

Polymer Molecules, Very Small Particles and Protuberances with Small Radii of Curvature

327

(1)

The Glycocalyx of Mammalian Cells

328

(1)

Blood Cell Stability

329

(1)

Rouleau Formation of Red Cells, or Pseudo-Attachment at the Secondary Minimum

330

(2)

Hemagglutination

332

(4)

The IgG Molecule as a Probe for Determining the Intercellular Distance, l, at the Secondary Minimum; Estimation of the Decay Length of Water

336

(3)

Cell and Particle Stability in the Absence and in the Presence of Polymers

339

(3)

Stability in the Absence of Polymers

339

(1)

Stability Induced by Attached Lyophilic Polymers; Depletion Phenomena

340

(2)

Coda

342

(3)

Adsorption and Adhesion in Aqueous Media, Including Ligand-Receptor Interactions

345

(40)

Interaction Between Two Different Materials Immersed in Water

345

(1)

Macroscopic and Microscopic-Scale Interactions

346

(1)

Adsorption

347

(13)

Influence of the Size of the Solute

347

(1)

Blotting

347

(2)

Protein Adsorption

349

(5)

Change in Configuration and Denaturation

354

(3)

Liquid Chromatography

357

(3)

Cell Adhesion

360

(8)

Influence of Protein Adsorption

360

(1)

Adhesion to High- and Low-Energy Surfaces

361

(1)

Prevention of Adhesion

361

(2)

The Influence of Cell-Shape on Adhesiveness

363

(1)

Cell Adhesion to Low-Energy Surfaces

363

(1)

Aspecific and Specific Interactions in Microbial Adhesion

363

(1)

Microbial Pathogenicity and Negative and Positive Cell Adhesion

364

(1)

Opsonization and Phagocytosis

365

(1)

Cell Fusion

366

(2)

Cell Freezing and Negative and Positive Adhesion to Advancing Ice Fronts

368

(3)

Aspecific and Specific Interactions

371

(11)

Smallness of Specific Sites

372

(1)

Interfacial (LW + AB) Specific Interactions

373

(1)

Role of Direct Hydrogen Bonding in Specific Interactions

374

(1)

H-Bonds Used in Ag-Ab Modeling

375

(1)

Role of H-Bonding in Specific Interactions in General

375

(1)

Specific Electrostatic Interactions

376

(1)

Bridging with Plurivalent Counterions---Calcium Bridging

376

(1)

Antigen-Antibody Binding Hysteresis

377

(1)

Role of Hydration

377

(2)

The ΔG1w2 → ΔG12 Transition

379

(1)

Specific Recombination DNA-DNA Interactions

379

(2)

Summary of the Mechanism of Specific Ligand-Receptor Interactions

381

(1)

Coda

382

(3)

Kinetics and Energetics of Protein Adsorption onto Metal Oxide Surfaces

385

(14)

Measurement of the Kinetic On-Rate Constant of Protein Adsorption onto Metal Oxide Surfaces---Experimental Constraints to Be Observed

385

(4)

Mass Transport

385

(1)

Steric Hindrance by Dissolved Protein Molecules

386

(2)

Decrease in the Adsorption of Protein onto Metal Oxide Surfaces When Dissolved in Some Common Buffer Solutions

388

(1)

Macroscopic-Scale Repulsion Between Albumin and Glass or Silica

388

(1)

Microscopic-Scale Attraction Between Proteins and Discrete Cationic Sites Imbedded in Hydrophilic Metal Oxide Surfaces

389

(1)

Extended DLVO (XDLVO) Analysis of Protein Adsorption as a Function of Distance and Geometric Shape

389

(1)

Incorporation of both Macroscopic-Scale Repulsion and Microscopic-Scale Attraction Energies in the Analysis of Measured Kinetic Association Rate Constants, Using von Smoluchowski's Formalism

390

(3)

von Smoluchowski's Equation

390

(1)

von Smoluchowski's f Factor

391

(1)

Determination of Xmac and Xmic

392

(1)

Determination and Significance of k mic/a

393

(4)

Influence of Hysteresis on the Determination of Ka and kd and Method for Obviating Its Effects

397

(1)

Coda

397

(2)

List of Symbols Used

399

(8)

References

407

(24)

Index

431

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Interfacial Forces in Aqueous Media, Second Edition

Summary

Table of Contents

Supplemental Materials