Macromolecular Chemistry and New Polymeric Materials, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Macromolecular Chemistry and New Polymeric Materials, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Carbohydr Polym. 2018 Aug 1;193:196-204. doi: 10.1016/j.carbpol.2018.03.098. Epub 2018 Mar 30.
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, respectively. The majority of the bonds at the alpha position of acrylate units in oligocellulosyl-ethyl acrylate was fragmented as characterized by H 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.
以纤维二糖磷酸化酶为生物催化剂，在缓冲溶液中合成了基于乙烯基的低聚糖。各种带有（甲基）丙烯酰基/（甲基）丙烯酰胺官能团的乙烯基葡萄糖苷作为酶催化反向磷酸解反应中的葡萄糖基受体，α-葡萄糖 1-磷酸作为葡萄糖基供体。通过薄层层析法跟踪酶反应，分离得到的产物产率约为 65%。合成的基于乙烯基的低聚糖的重复葡萄糖基单元的平均数量和数均分子量分别高达 8.9 和 1553g/mol。通过 H NMR 光谱和 MALDI-ToF 光谱表征，发现低聚纤维素基乙基丙烯酰胺中丙烯酰基单元α位的大部分键断裂。然而，在低聚纤维素基乙基甲基丙烯酸酯和低聚纤维素基丁基丙烯酰胺中观察到少量的键断裂，但在基于（甲基）丙烯酰胺的低聚糖中未检测到键断裂。通过广角 X 射线衍射实验研究了制备的基于乙烯基的低聚糖的晶体晶格。
