Exciting Novel Polyaspartates: Design, Synthesis, and Photo-Responsive Behavior in Solution and Lyotropic Liquid Crystalline Phase Upon Irradiation with Visible Light

Many polypeptides form stable, helical secondary structures enabling the formation of lyotropic liquid crystalline (LLC) phases. Contrary to the well-studied polyglutamate, their counterparts based on polyaspartates exhibit a much lower helix inversion barrier. Therefore, the helix sense is not solely dictated by the chirality of the amino acid used, but additionally by the nature and conformation of the polymer sidechain. In this work, polymers responsive to irradiation with visible light are designed achieving conformational transitions from helix-to-coil and helix-to-helix. The synthesis and the application as LLC mesogens of several (co-)polyaspartates bearing ortho-fluorinated azobenzene (FAB) as a photochromic group are presented. Many of the obtained polymers undergo changes in their secondary structure upon E-Z-isomerization of the FAB-containing sidechain. Of special interest are copolymers that exhibit photo-responsive helix inversion without loss of their helical secondary structure. These copolymers form stable LLC phases in helicogenic solvents, where the effect of photo-switching on the macroscopic behavior is studied by NMR spectroscopy. Especially, the irradiation of the different LLC phases of the helix inversion polymers displays a change in the LLC order experienced by the solvent. These peculiar properties are promising for future applications as photo-responsive alignment media for structure elucidation in NMR. The synthesis of novel (co-)aspartates bearing ortho-fluorinated azobenzenes as photochromic group in the sidechain is presented. The influence of photo-induced E-Z-isomerization on the secondary structure is studied revealing helix-to-helix and helix-to-coil transitions. Polyaspartates forming LLC phases in organic solvents allow studying the effect of photoswitching on macroscopic behavior with distinct anisotropic environments becoming accessible by irradiation with visible light. image