Long‐range and short‐range mechanisms of hydrophobic attraction and hydrophilic repulsion in specific and aspecific interactions

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Abstract
Among the three different non‐covalent forces acting in aqueous media, i.e. Lifshitz–van der Waals (LW), Lewis acid–base (AB) and electrical double layer (EL) forces, the AB forces or electron–acceptor/electron–donor interactions are quantitatively by far the predominant ones. A subset of the AB forces acting in water causes the hydrophobic effect, which is the attraction caused by the hydrogen‐bonding (AB) free energy of cohesion between the water molecules which surround all apolar as well as polar molecules and particles when they are immersed in water. As the polar energy of cohesion among water molecules is an innate property of water, the hydrophobic attraction (due to the hydrophobic effect) is unavoidably always present in aqueous media and has a value of ΔGhydrophobic = −102 mJ/m2, at 20 °C, being equal to the AB free energy of cohesion between the water molecules at that temperature. The strong underlying hydrophobic attraction due to this effect can, however, be surmounted by very hydrophilic molecules and particles that attract water molecules more strongly than the free energy of attraction of these molecules or particles for one another, plus the hydrogen‐bonding free energy of cohesion between the water molecules, thus resulting in a net non‐electrical double layer repulsion. Each of the three non‐covalent forces, LW, AB or EL, any of which can be independently attractive or repulsive, decays, dependent on the circumstances, as a function of distance according to different rules. These rules, following an extended DLVO (XDLVO) approach, are given, as well as the measurement methods for the LW, AB and EL surface thermodynamic properties, determined at ‘contact’. The implications of the resulting hydrophobic attractive and hydrophilic repulsive free energies, as a function of distance, are discussed with respect to specific and aspecific interactions in biological systems. The discussion furnishes a description of the manner by which shorter‐range specific attractions can surmount the usually much stronger long‐range aspecific repulsion, and ends with examples of in vitro and in vivo effects of hydrophilization of biopolymers, particles or surfaces by linkage with polyethylene oxide (PEO; also called polyethylene glycol, PEG). Copyright © 2003 John Wiley & Sons, Ltd.