Azido derivatives of cellobiose: oxidation at C1 with cellobiose dehydrogenase from Sclerotium rolfsii

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• 作者：Dafina Mulla ; Daniel Kracher ; Rol ; Ludwig ; Gabor Nagy ; Melanie Gr ; its ; Wolfgang Holzer ; Yasser Saber ; Nermeen Gabra ; Helmut Viernstein ; Frank M. Unger
• 关键词：Azidocellobiose ; Cellobiose dehydrogenase ; Chemo-enzymatic synthesis ; Molecular docking ; Substrate specificity ; Sclerotium rolfsii
• 刊名：Carbohydrate Research
• 出版年：15 December, 2013
• 年：2013
• 卷：382
• 期：Complete
• 页码：86-94
• 全文大小：1468 K

文摘

We report the chemo-enzymatic synthesis of three cellobiono-1,5-lactone azido derivatives, designed as building blocks for biomedical polymer scaffolds. The synthesis is based on regioselective protection of cellobiose or 1,6-O-anhydro-尾-d-cellobiose before azidation and subsequent deprotection. The oxidation to the corresponding cellobiono-1,5-lactones was investigated with 6鈥?azido-6鈥?deoxycellobiose (6鈥睳₃Clb, 5), 6-azido-6-deoxycellobiose (6N₃Clb, 11) and 2-azido-2-deoxycellobiose (2N₃Clb, 15) under the catalysis of cellobiose dehydrogenase (CDH) from the plant-pathogenic fungus m>Sclerotium rolfsiim>. Substrate binding characteristics and kinetics of CDH for the three cellobiose azido derivatives were studied employing computational docking, steady-state and presteady-state techniques. The process of enzymatic oxidation of the cellobiose azido intermediates was optimized by using the available kinetic information. Whereas the conversion of 15 by CDH is very slow, the conversion of 5 and 11 by a regenerated, bi-enzymatic process (CDH/redox mediator/laccase/O₂) is fast, quantitative and produces azido derivatives of cellobiono-1,5-lactone in an environmentally friendly, oxygen-driven process.