While recent research on interfacial water has focused mainly on the few interfacial layers adjacent to the solid boundary, century-old studies have extensively shown that macroscopic domains of liquids near interfaces acquire features different from the bulk. Interest in these long-range effects has been rekindled by recent observations showing that colloidal and molecular solutes are excluded from extensive regions next to many hydrophilic surfaces [Zheng and Pollack Phys. Rev. E 2003, 68, 031408]. Studies of these aqueous "exclusion zones" reveal a more ordered phase than bulk water, with local charge separation between the exclusion zones and the regions beyond [Zheng et al. Colloid Interface Sci. 2006, 127, 19; Zheng and Pollack Water and the Cell: Solute exclusion and potential distribution near hydrophilic surfaces; Springer: Netherlands, 2006; pp 165-174], here confirmed using pH measurements. The main question, however, is where the energy for building these charged, low-entropy zones might come from. It is shown that radiant energy profoundly expands these zones in a reversible, wavelength-dependent manner. It appears that incident radiant energy may be stored in the water as entropy loss and charge separation.

Large, solute-free interfacial zones have recently been described in aqueous solutions. Found next to hydrophilic surfaces, these "exclusion zones" are commonly several hundred micrometers wide and represent regions of water that appear to be more ordered than bulk water. We report here that other polar solvents including methanol, ethanol, isopropanol, acetic acid, D 2 O and dimethyl sulfoxide (DMSO) show similar near-surface exclusion zones, albeit of smaller magnitude. Microelectrode measurements show that these zones are negatively charged and grow in response to incident infrared radiation, similar to exclusion zones in aqueous solutions. Hence, near-surface exclusion zones appear to be features characteristic not only of water but of other polar liquids as well.

Colloidal crystals were formed from microsphere suspensions via a simple and novel approach using gel beads. The microspheres self-assembled not only around each bead but also between beads in an ordered pattern. The crystals shrunk under incident light, with the effect of blue (wavelength 450 to 500 nm) being the most profound. The results shed new light on the fundamental issue of self-assembly and colloid science.

Solute–free zones, termed “exclusion zones” are routinely seen next to hydrophilic surfaces in aqueous solution. Here we report similar zones next to various metals. The largest, approximately 200 µm in width, was found adjacent to zinc. Other reactive metals, including aluminum, tin, lead, and tungsten exhibited distinct but smaller exclusion zones, while precious metals such as platinum and gold did not produce any. Electrical potential measurements showed positive potentials within the exclusion zones, while pH measurements revealed an abundance of OH− groups in the aqueous regions beyond the exclusion zones. A correspondence was found between exclusion-zone size and the respective metal’s position within the galvanic series. The presence of these interfacial exclusion zones is unexpected, and may shed new light on electrochemical processes taking place at metal interfaces.

Experiments were carried out to determine whether the newly identified "exclusion zone" found adjacent to hydrophilic surfaces might play a role in osmosis. Two chambers were juxtaposed face to face, separated by a membrane made of cellulose acetate or Nafion. One chamber contained water, the other 100 mM sodium sulfate solution. Osmotically driven transmembrane fluid flow from low to high salt was observed using both membranes, in agreement with previous reports. Characteristic pH differences and potential differences between chambers were also noted. Visual examination with microsphere markers revealed extensive exclusion zones adjacent to both types of membrane. As these zones routinely generate protons in the water regions beyond, unequal proton concentrations in the respective chambers may be responsible for creating both the pH and potential gradients, which may be ultimately responsible for the osmotic drive.