Development and applications of the interfacial tension between water and organic or biological surfaces

The interfacial tension (gamma(SW)) between a condensed-phase material (S) and water (W) is one of the most important terms occurring (directly or indirectly) in the major surface thermodynamic combining rules, such as the different variants of the Dupré equation, as well as the Young and the Young-Dupré equations. Since the late 1950s, gamma(SL) (where L stands for liquid in general) could be correctly expressed, as long as one only took van der Waals attractions and electrical double layer repulsions into account, i.e., as long as both S and L were apolar. However for interfacial interactions taking place in water among apolar as well as polar solutes, particles or surfaces, gamma(SW) was not properly worked out until the late 1980s, due in particular to uncertainties about the treatment of the polar properties of liquid water and other condensed-phase materials. In this review the historical development of the understanding of these polar properties is outlined and the polar equation for gamma(SW), as well as the equations derived there from for the free energies of interaction between apolar or polar entities, immersed in water (deltaG(SWS)) are discussed. Also discussed is the role of the various terms of deltaG(SWS), in hydrophobic attraction (the "hydrophobic effect"), hydrophilic repulsion ("hydration forces") and in the quantitative expression of hydrophobicity and hydrophilicity. The DLVO theory of attractive and repulsive free energies between particles immersed in liquids, as a function of distance between suspended particles, was extended to allow its use in the expression of the polar interactions occurring in water. Finally, the free energy term, deltaG(SWS) and the related gamma(SW), have been directly linked to the aqueous solubility of organic and biological solutes, which allows the determination of interfacial tensions between such solutes and water from their solubilities.