Chapter
2.1.3 Interfacial energies
2.1.4 Problems with pairwise additivity: cooperativity of permanent dipolar interactions
2.1.5 Many-body dispersion forces
2.2 Liquid structure at solid interfaces: many kinds of forces
2.2.1 'Young–Laplace’: continuum liquid approximation
2.2.2 Forces due to molecular granularity, oscillatory and exponential
2.2.3 The 'Poisson’ case: surface-induced liquid order
2.2.5 Double-layer electrostatic forces
2.2.6 Secondary hydration forces
2.2.9 Effects of dissolved gas
2.2.10 Hofmeister effects
2.3 Liquid structure at other interfaces and around solutes
2.3.1 Other solid–liquid surfaces
2.3.3 A remark on dissolved gas and effective potentials
2.3.4 Solvent structure around solutes: molecular size
2.3.5 'Size’ in van der Waals and ionic interactions
2.3.6 More accurate descriptions: intermediate distances
2.3.8 Water structure and ion size
3 Electrostatic forces in electrolytes in outline
3.1 The assumptions of classical theories
3.2 The electrostatic self energy of an ion and the Debye–Hückel theory
3.2.2 Digression on the Debye–Hückel interaction energy and activity coefficients
3.2.3 Osmotic coefficients
3.2.5 Other physicochemical parameters
3.2.6 Further quantification of ion specificity
3.2.7 Interfacial energies due to electrolytes
3.3 A first appearance of dispersion forces
3.3.1 Simplified sketch of technical details and digression
3.4 Electrostatic forces at and between charged interfaces
3.4.1 The electrostatic double layer
3.5 Mixed electrolytes and pixie dust
3.6 The Debye length in multivalent electrolytes
3.7 Salting in and salting out
3.8 Applications to colloidal suspensions
4.1 Forces in the DLVO theory of colloidal stability
4.1.1 Direct measurements, assumptions and inadequacies
4.1.2 Experiment and theory with the double layer
4.1.3 Ion specificity of double-layer forces
4.2 Forces of entropic origin
4.2.1 The ideas of Langmuir and Onsager
4.2.2 Clays and agriculture
4.2.3 Colloid science and genesis of ores and oil
4.3 Effects of molecular size on forces in liquids
4.3.1 Oscillatory or depletion forces and hydration
4.3.2 The notion of an interface
4.3.3 Solid surfaces, surface-induced liquid structure
4.3.4 Oscillations due to liquid structure or exponentially decaying forces?
4.3.5 Depletion forces stabilize colloidal suspensions and emulsions
4.3.6 Phospholipids and hydration
4.3.7 The role of hydration forces in membrane interactions
5 Quantum mechanical forces in condensed media
5.1 Lifshitz theory and its extensions: an overview
5.1.1 Molecular recognition
5.1.3 Derivations of Lifshitz theory
5.1.4 Inferences from Lifshitz theory: molecular recognition
5.1.6 'Oil–water’ systems: how molecules recognize each other
5.2 Measurements of forces
5.3 Effects of unlike media, size, shape and anisotropy
5.3.3 Size, geometry and anisometry
5.3.4 Conduction processes and peculiarities of cylindrical geometries
5.4 Dispersion self energy and atomic size
5.5 Connection to quantum field theory
5.6 Interactions between molecules and hydration
5.8 Self energy changes in adsorption: remarks on formal theory
5.9 Dispersion and Born free energies
5.10 Cooperative substrate effects with adsorption: catalysis
5.10.1 Remarks on catalysis
(1) Catalysis in zeolites
(2) Reverse catalysis: possible mechanism of dioxin poisoning
5.10.2 Other possible sources of specificity: defect substitution in drugs and DNA
(1) Defect substitution in drugs and DNA
(2) Why should enzymes be so big?
5.11 Casimir–Polder and excited-state–ground-state interactions
5.11.1 Effects of temperature and the finite velocity of light on atomic interactions
5.11.2 Resonance or ground-state–excited-state interaction
5.11.3 Speculations on insect pheromones and photon transfer
5.11.4 Casimir, mesons and nuclear interactions
6 The extension of the Lifshitz theory to include electrolytes and Hofmeister effects
6.1 Inclusion of electrolytes and Hofmeister effects in the theory
6.1.1 The effects of electrolytes and conduction processes
6.1.2 The effects of electrolytes on dispersion interactions
6.1.3 Extensions of Lifshitz theory and the Onsager limiting law
6.1.4 Where and how the theory breaks down
6.1.5 Explorers in difficulty: what went wrong?
6.2 Hofmeister effects and their universality
6.2.1 Are surface or bulk effects responsible for Hofmeister phenomena?
6.2.2 More examples of Hofmeister effects
6.2.3 Biochemical and biological examples of Hofmeister effects
6.3 Hofmeister effects with pH and buffers and implications
6.3.1 Foundations that underlie pH measurement
6.3.2 Implications of the pH issue for zeta and membrane potentials
6.4 Hofmeister effects with restriction enzymes and speculations on mechanisms
6.5 Clues to the Hofmeister problem
6.5.1 Resolution via bootstrapping: partial insights into the phenomena
6.5.2 Dispersion forces involving ions in the continuum solvent approximation: origins of ion specificity
6.5.3 Oil–water interfaces
6.6 Indirect effects of ionic dispersion forces: ion–solvent interactions, chaotropic and kosmotropic ions
6.6.1 Indirect dispersion forces: chaotropic vs. kosmotropic ions
6.6.2 Some consequences of anisotropy and anisometry
6.6.3 Anisotropy in the interfacial tension of water
6.6.4 Ion fluctuation or induction forces
7.1 Hofmeister effects in physical chemistry
7.1.2 Specific ion effects: the classical picture
7.1.3 Further exploration of classical ideas
7.1.4 Specific ion effects in electrolyte solutions
7.1.5 Activity coefficients
7.1.7 Conductivity and self diffusion
7.1.8 Refractive index, heat capacity and freezing point
7.1.9 Other problems, with pH and buffers
7.1.10 Classification of and non-universality of Hofmeister series
7.1.11 Specific ion effects in direct force measurements
7.1.12 Interfacial tensions and computer simulations
7.1.13 Dramatic Hofmeister effects in self assembly
7.1.14 Correlations and the approach of Collins
7.2 Manifestations of Hofmeister effects in biology and biochemistry
7.2.1 Optical rotation of chiral molecules
7.2.4 Rhodopsin and cytochrome c
(B) Horseradish peroxidase
7.2.8 Hofmeister effects in medicine
7.3 Inorganic and other systems
7.4 Towards a resolution by inclusion of dispersion forces
7.4.1 Ion polarizabilities and their frequency dependence
7.4.2 Consistent definitions of ion size
7.4.3 The deployment of ab initio quantum mechanics
7.4.4 Excess polarizabilities
7.4.5 Born energies revisited: induction forces
7.4.6 Dispersion and induction forces
7.4.7 Applications to activities and inclusion of water structure
7.4.8 Solvent structure: solvent–solvent correlations
7.4.9 Applications to adsorption and interfacial tensions
7.4.10 Comment on frequency contributions
7.4.11 Applications to forces in colloid science: a work in progress
7.4.12 An explicit example
7.4.13 Anisotropy and water ion clusters, hydroxide and other anisometric ions
7.4.14 The anisotropic tensor
7.4.15 Hints at specificity in complex matter and biology
7.4.16 Material properties – effects of dielectric anisotropy in colloidal interactions: repulsive van der Waals interactions
7.4.19 Conduction processes
7.5 Exploitation of specific ion effects
8 Effects of dissolved gas and other solutes on hydrophobic interactions
8.1 Bubble–bubble coalescence
8.1.1 Effect of electrolytes
8.2 Colloid stability and dissolved gas
8.2.1 The role of dissolved gas and other solutes in colloidal interactions
8.2.2 Emulsion stability and dissolved gas
8.2.3 Exploiting gas dependence
8.3 Other phenomena affected by dissolved gas
8.4 Water structure as revealed by laser cavitation: bubble–bubble experiments in electrolytes
8.5 Mechanisms of bubble–bubble and long-range -hydrophobic’ interactions
8.6 Bubble–bubble experiments in non-aqueous solvents
8.7 Hydrophobic interactions and the hydrophobic effect
8.8 Long-range hydrophobic forces and capillary forces: polywater
8.9 Molecular basis of long-range -hydrophobic’ interactions
8.10 Speculations on possible implications for Burgess Shale pre-Cambrian and other geological extinctions
9 Self assembly: overview
9.1 Surfactants and lipids
9.2 Emulsions and microemulsions
9.3 Order from complexity: theoretical challenges and bicontinuity
9.4 Evolution of theoretical ideas
9.6 Microstructures of self-assembled aggregates
9.7 Local interfacial curvature a determinant of microstructure
9.8 Mixed surfactants and illustration of local packing constraints
9.12 Detergency in other biosystems
9.13 High-density vs. low-density lipoproteins
9.15 Global packing restrictions and interactions
9.16 Global packing constraints and -dressed’ micelles
9.17 Packing of spherical ionic micelles
9.18 Non-ionics and cloud points: water structure
9.19 Renormalized variables for phase behaviour
Specific surfactants and lipids, molecular characteristics
Macroscopic manifestations of self assembly
10 Self assembly in theory and practice
10.1 Ideas and defects of theories of self assembly
10.2 Global packing restrictions and interactions
10.3 The question of vesicles: predictions and limitations of theory
10.3.1 The question of vesicles
10.3.2 Conditions for formation of single-walled vesicles: asymmetry of interior and exterior of vesicles: constraints due to chain packing
10.3.3 Vesicles and cubic phases
10.3.4 Constraints due to charge asymmetry
10.4 Supraself assembly: formation of spontaneous vesicles illustrated
10.4.1 Mixed surfactants and catanionic mixtures
10.4.2 Catanionic surfactants
10.4.3 Giant vesicles and the beginnings of supraself assembly
Hofmeister effects, interactions and ion binding
10.4.4 Vesicles with different physicochemical conditions inside and outside
10.4.5 Hofmeister effects on self organization and ion binding
10.4.6 Giant vesicles and critical phenomena with phospholipids
11 Bicontinuous phases and other structures: forces at work in biological systems
11.1.1 Introduction to cubic phases
11.1.2 Global packing and cubic phases
11.1.3 Mesh phases: two-dimensional analogues of cubic phases
Monolayers vs. other microstructures at interfaces
11.3 Hydrophobin and cubic phases in fungi
11.4 Cubosomes and chloroplasts
11.5 Cubic membranes and DNA
11.6 Immunosuppression induced by cationic surfactants: an example of physical chemistry in biology
11.7 Bacterial resistance
11.8 General anaesthesia: the possible role of lipid membrane phase transitions in conduction of nervous impulse in general anaesthesia
11.9 Metastasis and anaesthetics: other consequences of mesh phase transitions
11.10 Inter-aggregate transitions
11.11 Drug delivery and bicontinuity
11.12 Membrane fusion and unfolding
11.13 The tetradecane-DDAB microemulsion system: an exemplar for sponge and mesh phases
11.14 The anti-parallel, extended or splayed-chain conformation of amphiphilic lipids
11.15 Specific ion partitioning in two-phase systems: a contribution to ion pumps?
12 Emulsions and microemulsions
12.3 Three-component ionic microemulsions
12.4 Bicontinuity and spontaneous emulsions
12.5 Percolation exponents
12.6 Interfacial tensions at the oil–microemulsion interface
12.7 Single-chained surfactants and non-ionics
12.8 Specific ion effects and 'impurities’ change microstructure
12.9 Competitive anion binding
12.10 Cationic binding to cationic surfaces
12.11 Impurities and mixtures
12.12 Specificity of oils, cis and trans oils, alcohols and cholesterol
12.13 Supraself assembly and other -phases’
12.13.2 Supra-aggregation a general phenomenon
12.13.3 The copper AOT–isooctane–water microemulsion
12.14 Polymerization of microemulsions
12.15 Non-swelling lamellar phases
12.17 Some remarks on ion-binding models
12.18 When and why ion binding breaks down: Hofmeister effects
12.19 Inconsistency of the ion-binding theory with direct force measurements
12.19.1 The DLVO theory and ion binding
13 Forces at work: a miscellany of issues
13.2 Wishing reason upon the ocean!
13.3 Drawing threads together
13.4 Some consequences of conceptual locks
13.5 The tyranny of theory when theory meets reality: some examples
13.6.1 Microfossils and biomorphs
13.6.2 Frescoes and nanoparticles
Molecular Forces and Self Assembly
：In Colloid, Nano Sciences and Biology
( Cambridge Molecular Science )
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