Photomodulation of polypeptide conformation by sunlight in spiropyran-containing poly(L-glutamic acid)

Abstract

Photochromic vinyl polymers, such as polyacrylates containing spiropyran groups, were found to undergo photoinduced variations of their viscosity. Since the viscosity of a polymer system is in part a reflection of polymer conformation, the photoviscosity effects were generically attributed to photoinduced conformational changes of the macromolecules. From the point of view of conformational properties, photochromic polypeptides are much more attractive systems, since they can exist in definite ordered structures such as {alpha}-helix or {beta}-structures, and their conformational variations can be directly investigated by means of CD measurements. In addition, their structure is much more relevant to the proteic nature of biological photoreceptors. In this context the authors report the first preparation of a photoresponsive polypeptide containing spiropyran units in the side chains and clear CD evidence that the polypeptide can undergo large random coil {r equilibrium} {alpha}-helix conformational changes upon exposure to sunlight and dark conditions, alternately. Moreover, irradiation in solvent mixtures having appropriate compositions allows the extent of the photoresponse to be controlled.