Photoregulation of ion permeation through a polyelectrolyte multilayer membrane by manipulating the chromophore orientation.

Toward the realization of nanoscale device control, we report a novel method for photoregulation of ion flux through a polyelectrolyte multilayer membrane by chromophore orientation that is adjusted either by illumination at normal incidence or by slantwise irradiation at an angle of 10 degrees with respect to the surface. Our results indicate that the chromophore reorientation caused by the slantwise irradiation controls the effective pore size and, consequently, the transport behavior on the nanoscale. The slantwise illumination, which includes six EZE photoisomerization cycles generated by alternately irradiating with ultraviolet (lambda = 360 nm) and visible (lambda = 450 nm) light, reversibly switches the orientation of E-azobenzene in the membrane between 53 +/- 2 degrees (high tilt) and 17 +/- 5 degrees (low tilt) with respect to the surface. The novel feature of this light-gated valve system is its extremely long-lived open-switch state; this behavior stands in contrast to that of other systems based on labile photoisomers, which tend to instantly return to the thermodynamically stable state.