Environmentally friendly pathways towards the synthesis of vinyl-based oligocelluloses

The synthesis of vinyl-based oligocelluloses using cellodextrin phosphorylase as biocatalyst in buffer solution is presented. Various types of vinyl glucosides bearing (meth)acrylates/(meth)acrylamides functionalities served as the glucosyl acceptor in the enzyme catalyzed reverse phosphorolysis reaction and α-glucose 1-phosphate as the glucosyl donor. The enzymatic reaction was followed by thin layer chromatography and the isolated product yields were about 65%. The synthesized vinyl-based oligocelluloses had an average number of repeating glucosyl units and a number average molecular weight up to 8.9 and 1553 g mol−1, respectively. The majority of the bonds at the alpha position of acrylate units in oligocellulosyl-ethyl acrylate was fragmented as characterized by 1H NMR spectroscopy and MALDI-ToF spectrometry. Nevertheless, a minor amount of fragmentation was observed in oligocellulosyl-ethyl methacrylate and oligocellulosyl-butyl acrylate but no fragmentation was detected in the (meth)acrylamide-based oligocelluloses. Crystal lattice of the prepared vinyl-based oligocelluloses was investigated via wide-angle X-ray diffraction experiments.