The increasing importance of studies on soft matter and their impact on new technologies, including those associated with nanotechnology, has brought intermolecular and surface forces to the forefront of physics and materials science, for these are the prevailing forces in micro and nanosystems. With experimental methods such as the atomic force spectroscopy (AFS), it is now possible to measure these forces accurately, in addition to providing information on local material properties such as elasticity, hardness and adhesion. This review provides the theoretical and experimental background of afs, adhesion forces, intermolecular interactions and surface forces in air, vacuum and in solution.

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Theoretical Models for Surface Forces and Adhesion and Their Measurement Using Atomic Force Microscopy

It is well-known that micro- and nanoparticles can move by phoretic effects in response to externally imposed gradients of scalar quantities such as chemical concentration or electric potential. A class of active colloids can propel themselves through aqueous media by generating local gradients of concentration and electrical potential via surface reactions. Phoretic active colloids can be controlled using external stimuli and can mimic collective behaviors exhibited by many biological swimmers. Low–Reynolds number physicochemical hydrodynamics imposes unique challenges and constraints that must be understood for the practical potential of active colloids to be realized. Here, we review the rich physics underlying the operation of phoretic active colloids, describe their interactions and collective behaviors, and discuss promising directions for future research.

Phoretic Self-Propulsion

We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = −2γiHy exp(−D/DH) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length DH ≈ 0.3–2 nm for both hydrophobic and hydrophilic interactions, with the exact value of DH depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γi, of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfac...

Developing a general interaction potential for hydrophobic and hydrophilic interactions

We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system.

Developing a General Interaction Potential for Hydrophobic and Hydrophilic Interactions in Self-Assembled Systems

Ternary solutions containing one hydrotrope (such as ethanol) and two immiscible fluids, both being soluble in the hydrotrope at any proportion, show unexpected solubilization power and allow strange but yet unexplained membrane enzyme activity. We study the system ethanol-water-octanol as a simple model of such kinds of ternary solutions. The stability of “detergentless” micelles or microemulsions in such mixtures was proposed in the pioneering works of Barden and coworkers [Smith GD, Donelan CE, Barden RE (1977) J Colloid Interface Sci 60(3):488–496 and Keiser BA, Varie D, Barden RE, Holt SL (1979) J Phys Chem 83(10):1276–1281] in the 1970s and then, neglected, because no general explanation for the observations was available. Recent direct microstructural evidence by light, X-ray, and neutron scattering using contrast variation reopened the debate. We propose here a general principle for solubilization without conventional surfactants: the balance between hydration force and entropy. This balance explains the stability of microemulsions in homogeneous ternary mixtures based on cosolvents.

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How to explain microemulsions formed by solvent mixtures without conventional surfactants.

The hydration force between large molecules or large surfaces is built on weak perturbation of many solvent molecules. The structure of the surface sets boundary conditions on solvent while structural forces within the solvent set the range. For this collection of essays, we focused on forces between surfaces at nanometer separations. It is instructive to distinguish primary hydration, the binding of water and perturbation within a few layers, from secondary hydration related to redistribution of solutes. The subject is still basically empirical, lacking satisfactory theory and sufficient measurement.

T. Zemb

Papers

Hydration forces: Observations, explanations, expectations, questions