Molecular self association in liquids is a physical process that can dominate cohesion (interfacial tension) and miscibility. In water, self association is a powerful organizational force leading to a three-dimensional hydrogen-bonded network (water structure). Localized perturbations in the chemical potential of water as by, for example, contact with a solid surface, induces compensating changes in water structure that can be sensed tens of nanometers from the point of origin using the surface force apparatus (SFA) and ancillary techniques. These instruments reveal attractive or repulsive forces between opposing surfaces immersed in water, over and above that anticipated by continuum theory (DLVO), that are attributed to a variable density (partial molar volume) of a more-or-less ordered water structure, depending on the water wettability (surface energy) of the water-contacting surfaces. Water structure at surfaces is thus found to be a manifestation of hydrophobicity and, while mechanistic/theoretical interpretation of experimental results remain the subject of some debate in the literature, convergence of experimental observations permit, for the first time, quantitative definition of the relative terms 'hydrophobic' and 'hydrophilic'. In particular, long-range attractive forces are detected only between surfaces exhibiting a water contact angle θ > 65° (herein defined as hydrophobic surfaces with pure water adhesion tension τ° = γ° cos θ < 30 dyn/cm where γ° is water interfacial tension = 72.8 dyn/cm). Repulsive forces are detected between surfaces exhibiting θ < 65° (hydrophilic surfaces, τ° > 30 dyn/cm). These findings suggest at least two distinct kinds of water structure and reactivity: a relatively less-dense water region against hydrophobic surfaces with an open hydrogen-bonded network and a relatively more-dense water region against hydrophilic surfaces with a collapsed hydrogen-bonded network. Importantly, membrane and SFA studies reveal a discrimination between biologically-important ions that preferentially solubilizes divalent ions in more-dense water regions relative to less-dense water regions in which monovalent ions are enriched. Thus, the compelling conclusion to be drawn from the collective scientific evidence gleaned from over a century of experimental and theoretical investigation is that solvent properties of water within the interphase separating a solid surface from bulk water solution vary with contacting surface chemistry. This interphase can extend tens of nanometers from a water-contacting surface due to a propagation of differences in self association between vicinal water and bulk-phase water. Physicochemical properties of interfacial water profoundly influence the biological response to materials in a surprisingly straightforward manner when key measures of biological activity sensitive to interfacial phenomena are scaled against water adhesion tension τ° of contacting surfaces. As examples, hydrophobic surfaces (τ° < 30 dyn/cm) support adsorption of various surfactants and proteins from water because expulsion of solute from solution into the interphase between bulk solid and solution phases is energetically favorable. Adsorption to hydrophobic surfaces is driven by the reduction of interfacial energetics concomitant with replacement of water molecules at the surface by adsorbed solute (surface dehydration). Hydrophilic surfaces (τ° > 30 dyn/cm) do not support adsorption because this mechanism is energetically unfavorable. Protein-adsorbing hydrophobic surfaces are inefficient contact activators of the blood coagulation cascade whereas protein-repellent hydrophilic surfaces are efficient activators of blood coagulation. Mammalian cell attachment is a process distinct from protein adsorption that occurs efficiently to hydrophilic surfaces but inefficiently to hydrophobic surfaces. Thus, the hydrophobic/hydrophilic contrast in the biological response to materials, often disputed in biomaterials science, is very clear when viewed from the perspective of water structure and reactivity at surfaces. The key measure of water structure and activity important to biomaterial scientists is τ° rather than parameters such as Zisman's critical surface tension γc or 'surface free energy' γs that are shown not to correlate sensibly with either τ° or results from the surface force apparatus.
All Science Journal Classification (ASJC) codes
- Surfaces and Interfaces
- Physical and Theoretical Chemistry
- Colloid and Surface Chemistry