Light-Controlled Lyotropic Liquid Crystallinity of Polyaspartates
<p><b>In nature, proteins like rhodopsin act as transducer for photo-chemical reactions causing biological responses (e.g. enabling vision)</b><b>. The underlying concept – a photo-induced conformational change of the protein as amplifier of the photo-responsive moiety – can also be adopted by synthetical polymers or foldamers</b><b> </b><b>that have the propensity to form ordered secondary structures (e.g. polypeptides)</b><b>. An alternative approach to amplify photo-chemical responses is their incorporation into liquid crystals</b><b>. With only a few exceptions</b><b>, photo-insensitive liquid crystals are doped with dyes</b><b> </b><b>that favour disorder upon irradiation</b><b>. In theory, photo-responsive polypeptides</b><b>, capable of forming lyotropic liquid crystals</b><b>, could exploit both amplification approaches but, in practice, their photo-responsivity is hampered by the reduced mobility of polypeptides in concentrated solutions</b><b>. Here we show that the E/Z photo-isomerisation of an azobenzene containing polyaspartate initiates a helix-coil backbone transition, which reversibly alters the polypeptide solution from anisotropic to isotropic. In contrast to other photo-responsible polymers</b><b>14</b><b>, in which thermal relaxation to the more stable photo-isomer is quite fast, both photo-isomers are thermally stable and interconvertible by visible light in a single solvent. Local irradiation and magnetic fields lead to spatial resolution and unidirectional architectures of the liquid crystal, respectively. Our results demonstrate that photo-isomerisation on a molecular level is amplified in three stages via intra- and intermolecular interactions to yield a unidirectional, chiral liquid crystal. We believe, the morphological changes of the liquid crystal induced by light will facilitate a multitude of applications, like photo-alignment</b><b> </b><b>or the photo-control of solution viscosity</b><b> </b><b>and anisotropic </b><br></p> <p><b>diffusion</b><b>. When incorporated into layer-by-layer architectures the polymer could find application in biomedicine</b><b> </b><b>and the spatial and temporal resolution could be exploited in nano-technology</b><b>. </b></p>