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涉及酵母转酮醇酶催化的酮转移反应中的二自由基的证据。

Evidence of Diradicals Involved in the Yeast Transketolase Catalyzed Keto-Transferring Reactions.

机构信息

Genomics Research Center, Academia Sinica, Taipei, 115, Taiwan.

Institute of Biochemistry and Molecular Biology, National Yang-Ming University, Taipei, 112, Taiwan.

出版信息

Chembiochem. 2018 Nov 16;19(22):2395-2402. doi: 10.1002/cbic.201800378. Epub 2018 Oct 18.

DOI:10.1002/cbic.201800378
PMID:30155962
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6282555/
Abstract

Transketolase (TK) catalyzes a reversible transfer of a two-carbon (C ) unit between phosphoketose donors and phosphoaldose acceptors, for which the group-transfer reaction that follows a one- or two-electron mechanism and the force that breaks the C2"-C3" bond of the ketose donors remain unresolved. Herein, we report ultrahigh-resolution crystal structures of a TK (TKps) from Pichia stipitis in previously undiscovered intermediate states and support a diradical mechanism for a reversible group-transfer reaction. In conjunction with MS, NMR spectroscopy, EPR and computational analyses, it is concluded that the enzyme-catalyzed non-Kekulé diradical cofactor brings about the C2"-C3" bond cleavage/formation for the C -unit transfer reaction, for which suppression of activation energy and activation and destabilization of enzymatic intermediates are facilitated.

摘要

转酮醇酶 (TK) 催化两个碳原子 (C) 单元在磷酸酮糖供体和磷酸醛糖受体之间的可逆转移，对于遵循单电子或双电子机制的基团转移反应以及打破酮糖供体的 C2"-C3" 键的力，仍然没有得到解决。在此，我们报告了来自酿酒酵母的 TK（TKps）在以前未发现的中间状态的超高分辨率晶体结构，并支持可逆基团转移反应的自由基机制。结合 MS、NMR 光谱、EPR 和计算分析，得出结论，酶催化的非共振自由基辅因子为 C -单元转移反应带来了 C2"-C3" 键的断裂/形成，从而促进了活化能的抑制以及酶中间产物的活化和失稳。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/8156dad20d16/CBIC-19-2395-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/33ab1a5d15b0/CBIC-19-2395-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/7ddb0a1d27de/CBIC-19-2395-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/2704467b9625/CBIC-19-2395-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/2c808272c25e/CBIC-19-2395-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/8156dad20d16/CBIC-19-2395-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/33ab1a5d15b0/CBIC-19-2395-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/7ddb0a1d27de/CBIC-19-2395-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/2704467b9625/CBIC-19-2395-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/2c808272c25e/CBIC-19-2395-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e2a2/6282555/8156dad20d16/CBIC-19-2395-g003.jpg

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Thiamine Deficiency and Neurodegeneration: the Interplay Among Oxidative Stress, Endoplasmic Reticulum Stress, and Autophagy.
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Structural and biochemical interrogation on transketolase from Pichia stipitis for new functionality.对树干毕赤酵母转酮醇酶进行结构和生化研究以探索新功能。
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