Catalytic bias in oxidation-reduction catalysis.

Catalytic bias in oxidation-reduction catalysis.
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DOI:
10.1039/d0cc07062a
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发表时间:
2021-01-18
期刊:
Chemical communications (Cambridge, England)
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催化偏置是指在非平衡条件下的化学反应中,催化剂在一个方向上对另一个方向产生不同速率加速度的倾向。在生物催化中,酶的固有偏倚通常有利于增强反应的固有热力学,以促进分解代谢和合成代谢途径协调的效率和保真度。在工业化学催化中,定向催化偏置是促进催化与诸如精细化学品或能量化合物的收获和储存相结合的系统工程所追求的特性。有趣的是,关于生物催化中催化偏倚的信息很少,这在很大程度上可能是由于难以开发出足够敏感的可跟踪分析方法来研究详细的动力学。对于氧化还原反应,比色法氧化还原指示剂存在于一系列还原电位中,为研究反应的两个方向提供了一种相当方便的机制。本文试图从概念上定义催化偏倚,并开发模型系统来定义酶催化氧化还原催化中控制催化偏倚的参数。
Cataytic bias refers to the propensity of a reaction catalyst to effect a different rate acceleration in one direction versus the other in a chemical reaction under non-equilibrium conditions. In biocatalysis, the inherent bias of an enzyme is often advantagous to augment the innate thermodynamics of a reaction to promote efficiency and fidelity in the coordination of catabolic and anabolic pathways. In industrial chemical catalysis a directional cataltyic bias is a sought after property in facilitating the engineering of systems that couple catalysis with harvest and storage of for example fine chemicals or energy compounds. Interestingly, there is little information about catalytic bias in biocatalysis likely in large part due to difficulties in developing tractible assays sensitive enough to study detailed kinetics. For oxidation-reduction reactions, colorimetric redox indicators exist in a range of reduction potentials to provide a mechanism to study both directions of reactions in a fairly facile manner. The current short review attempts to define catalytic bias conceptually and to develop model systems for defining the parameters that control catalytic bias in enzyme catalyzed oxidation-reduction catalysis.
DOI: 10.1073/pnas.86.13.4932
发表时间: 1989-07-01
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