Synthesis of Bifunctional Azobenzene Glycoconjugates for Cysteine-Based Photosensitive Cross-Linking with Bioactive Peptides.

Azobenzene linker molecules can be utilized to control peptide/protein function when they are ligated to appropriately spaced amino acid side chains of the peptide. This is because the photochemical E/Z isomerization of the azobenzene N=N double bond allows to switch peptide conformation between folded and unfolded. In this context, we have introduced carbohydrate-functionalized azobenzene derivatives in order to advance the biocompatible properties of azobenzene peptide linkers.

Synthesis and photochromic properties of configurationally varied azobenzene glycosides.

Spatial orientation of carbohydrates is a meaningful parameter in carbohydrate recognition processes. To vary orientation of sugars with temporal and spatial resolution, photosensitive glycoconjugates with favorable photochromic properties appear to be opportune. Here, a series of azobenzene glycosides were synthesized, employing glycoside synthesis and Mills reaction, to allow "switching" of carbohydrate orientation by reversible E/Z isomerization of the azobenzene N=N double bond.

Photodimerisation of glycothymidines in solution and in micelles.

Glycothymidines were designed and synthesized as a new class of functional glycomimetics in which a photochemical [2+2] cycloaddition of the thymine moiety induces structural changes of carbohydrate presentation. To test if photodimerisation of these glycothymidines is feasible within an array of molecules, the photochemical reaction was investigated using NMR and NMR diffusion experiments in solution as well as in the supramolecular context of detergent micelles that mimic cellular membranes.