The Effect of Dicarboxylic Acid Catalyst Structure on Hydrolysis of Cellulose Model Compound D-Cellobiose in Water

IF 0.9 Q4 CHEMISTRY, PHYSICAL

Current Organocatalysis Pub Date : 2021-11-29 DOI:10.2174/2213337208666211129090444

Harshica Fernando, A. Amarasekara

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引用次数: 1

Abstract

Polycarboxylic acids are of interest as simple mimics for cellulase enzyme catalyzed depolymerization of cellulose. In this study, DFT calculations were used to investigate the effect of structure on dicarboxylic acid organo-catalyzed hydrolysis of cellulose model compound D-cellobiose to D-glucose. Binding energy of the complex formed between D-cellobiose and acid (Ebind), as well as glycosidic oxygen to dicarboxylic acid closest acidic H distance were studied as key parameters affecting the turn over frequency of hydrolysis in water. α-D-cellobiose - dicarboxylic acid catalyst down face approach showed high Ebind values for five of the six acids studied; indicating the favorability of down face approach. Maleic, cis-1,2-cyclohexane dicarboxylic, and phthalic acids with the highest catalytic activities showed glycosidic oxygen to dicarboxylic acid acidic H distances 3.5-3.6 Å in the preferred configuration. The high catalytic activities of these acids may be due to the rigid structure, where acid groups are held in a fixed geometry.

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二羧酸催化剂结构对纤维素模型化合物d -纤维素二糖在水中水解的影响

聚羧酸是纤维素酶催化纤维素解聚的简单模拟物。在本研究中，采用DFT计算研究了结构对二羧酸有机催化纤维素模型化合物d -纤维素二糖水解为d -葡萄糖的影响。研究了d -纤维素二糖与酸(Ebind)形成的配合物结合能，以及糖苷氧与二羧酸最接近的酸性H距离作为影响水解翻转频率的关键参数。α- d -纤维二糖-二羧酸催化剂下表面法对所研究的6种酸中的5种具有较高的Ebind值;表明正面向下的方法是有利的。催化活性最高的马来酸、顺式-1,2-环己烷二羧酸和邻苯二甲酸在优选构型中表现为糖苷氧到二羧酸的酸性H距离为3.5 ~ 3.6 Å。这些酸的高催化活性可能是由于刚性结构，其中酸基团保持在固定的几何形状。

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来源期刊

Current Organocatalysis CHEMISTRY, PHYSICAL-

CiteScore

2.00

自引率

0.00%

发文量

期刊介绍： Current Organocatalysis is an international peer-reviewed journal that publishes significant research in all areas of organocatalysis. The journal covers organo homogeneous/heterogeneous catalysis, innovative mechanistic studies and kinetics of organocatalytic processes focusing on practical, theoretical and computational aspects. It also includes potential applications of organocatalysts in the fields of drug discovery, synthesis of novel molecules, synthetic method development, green chemistry and chemoenzymatic reactions. This journal also accepts papers on methods, reagents, and mechanism of a synthetic process and technology pertaining to chemistry. Moreover, this journal features full-length/mini review articles within organocatalysis and synthetic chemistry. It is the premier source of organocatalysis and synthetic methods related information for chemists, biologists and engineers pursuing research in industry and academia.