Reversible photochemical tuning of net charge separation from contact electrification.

This paper describes the photochemical tuning of net charge that develops from contact electrification. The net charge separation and/or rate of charging of photochromic spiropyran (SP)-containing polymer films can be controlled by irradiation with UV light. The isomerization of the SP form to the more hydrophilic merocyanine (MC) by irradiation with UV light always leads to films that charge more positively than before irradiation. The incorporation of a halogenated comonomer into ring-opening metathesis polymerization (ROMP) yields films that charged negatively before irradiation so that a change in sign of the net charge separation of the film could be observed upon irradiation. An important advantage to our photochromic system is that light can be used to tune the charging behavior of the material, with spatial or temporal control of irradiation, leading to films that resist charging. Furthermore, the observed trends can be reversed by the exposure of the SP-containing polymer films to heat or visible light.

Photoresponsive gels prepared by ring-opening metathesis polymerization.

This communication describes photoresponsive gels, prepared using ring-opening metathesis polymerization (ROMP), that dissolve upon irradiation with ultraviolet light. Exposure of mixtures of norbornene-type ROMP monomers and new photoreactive cross-linkers comprising two norbornene units bound through a chain containing o-nitrobenzyl esters (NBEs) to well-known ruthenium carbene catalysts gave cross-linked polymer networks that swelled in organic solvents or water depending on the structure of the monomer. These gels became homogeneous upon irradiation with UV light, consistent with breaking of the cross-links through photolysis of the NBE groups. The irradiation time required for homogenization of the gels depended on the cross-link density and the structure of the photoresponsive cross-linker.

Photochemical disruption of polyelectrolyte multilayers.

Photoreactive polyelectrolyte multilayers (PEMs) that dissolve upon UV irradiation are described. Light-induced switching of the formal charge of a photoreactive polycation resulted in repulsive interlayer electrostatic forces, and caused the dissolution of PEM films. Combining both photoreactive and inert polycations in the same film yielded additional control over the light-induced change in film thickness.