Microgel-Catalyzed Hydrolysis of Nonactivated Disaccharides
Microgel-Catalyzed Hydrolysis of Nonactivated Disaccharides
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DOI：
10.1021/acscatal.0c03401
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发表时间：
2020-12-18
期刊：
影响因子：
12.9
通讯作者：
Orizu, Ifedi
中科院分区：
文献类型：
--
作者：
Striegler, Susanne;Sharma, Babloo;Orizu, Ifedi
控制和选择性水解未衍生化的二糖和寡糖仍然是一个挑战，酶和非酶的方法。为了利用最近的进展，在开发的功能酶模拟水解的糖苷键，我们开发了交联微凝胶嵌入双核铜（II）络合物，在这里显示水解1.4超过1.6糖苷键在温和的碱性条件下，在高温下。微凝胶催化剂显示出对1 -> 4 β-糖苷键水解的不寻常的偏好，在72小时内从纤维二糖产生高达25 μ g L-1的葡萄糖，并且在校正背景效应后，在麦芽糖水解期间产生约一半的葡萄糖。嵌入式催化剂和非活化的二糖之间的相互作用的计算分析的非活化的糖苷键的水解过程中，在假定的过渡态结构的组装合理化这一观察结果的实验结果是支持的。
The controlled and selective hydrolysis of underivatized disaccharides and oligosaccharides remains a challenge that is met by enzymatic and nonenzymatic approaches. In an effort to capitalize on recent progress in the development of functional enzyme mimics for the hydrolysis of glycosidic bonds, we developed cross-linked microgels with embedded binuclear copper(II) complexes that are shown here to hydrolyze 1.4 over 1.6 glycosidic bonds under mildly alkaline conditions at elevated temperatures. The microgel catalysts show an unusual preference for the hydrolysis of 1 -> 4 beta- over 1 -> 4 alpha-glycosidic bonds yielding up to 25 mu g L-1 of glucose from cellobiose over 72 h and about half of that during the hydrolysis of maltose after correction for background effects. The experimental results are supported by computational analyses of the interactions between the embedded catalyst and the nonactivated disaccharide in putative transition state structures of the assembly during hydrolysis of the nonactivated glycosidic bond to rationalize this observation.