Ultrafast Dynamics and Catalytic Mechanism of Fatty Acid Photodecarboxylase.
Ultrafast Dynamics and Catalytic Mechanism of Fatty Acid Photodecarboxylase.
复制标题
脂肪酸光脱羧酶的超快动力学及催化机理
DOI：
10.1002/anie.202209180
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发表时间：
2022-12-12
影响因子：
16.6
通讯作者：
Zhong, Dongping
中科院分区：
文献类型：
--
作者：
Wu, Ruiqi;Li, Xiankun;Wang, Lijuan;Zhong, Dongping
关键词：
脂肪酸光脱羧酶是新近发现的一种黄素类光酶，它能将羧酸通过脱羧反应转化为烃和二氧化碳。酶促反应知之甚少。在这里，我们仔细地其特征在于其动态演化与飞秒光谱，我们观察到初始电子转移从基板到黄素辅因子在347 ps的拉伸动态行为，随后捕获的关键羰基氧基自由基占主导地位，其次是脱羧过程在5.8 ns，形成一个烷基和二氧化碳。我们进一步确定了羰基氧和烷基中间体的两个自由基的吸收带。由我们获得的时间尺度确定的整体酶量子效率为0.81，与稳态值一致。这些结果对阐明酶的作用机理和催化光循环具有重要意义，为设计基于黄素的人工光酶提供了分子基础。脂肪酸光脱羧酶通过脱羧作用将羧酸转化为烃和二氧化碳。通过深紫外检测捕获了催化反应中的两个关键中间体羰氧基和烷基自由基，并利用实际反应时间尺度确定了它们的动力学，揭示了酶促反应的分子机理，绘制了这种高效光酶的催化光循环图谱。
Fatty acid photodecarboxylase is a newly discovered flavin photoenzyme to convert a carboxylic acid into a hydrocarbon and a carbon dioxide through decarboxylation. The enzymatic reactions are poorly understood. Here, we carefully characterized its dynamic evolution with femtosecond spectroscopy; we observed initial electron transfer from the substrate into the flavin cofactor in 347 ps with a stretched dynamic behavior and subsequently captured the critical carbonyloxy radical dominantly followed by a decarboxylation process in 5.8 ns to form an alkyl radical and a carbon dioxide. We further identified the absorption bands of two radicals of carbonyloxy and alkyl intermediates. The overall enzymatic quantum efficiency determined by our obtained timescales is 0.81, consistent with the steady-state value. The results are essential to the elucidation of the enzyme mechanism and catalytic photocycle, providing a molecular basis for potential design of flavin-based artificial photoenzymes. Fatty acid photodecarboxylase converts a carboxylic acid into a hydrocarbon and a carbon dioxide through decarboxylation. Two critical intermediates of carbonyloxy and alkyl radicals in the catalytic reactions were captured by deep UV detection and their dynamics were determined with actual reaction timescales, revealing the molecular mechanism of the enzymatic reaction and mapping out the catalytic photocycle of this efficient photoenzyme.
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影响因子：
15
作者：
Chang, Chih-Wei;He, Ting-Fang;Guo, Lijun;Stevens, Jeffrey A.;Li, Tanping;Wang, Lijuan;Zhong, Dongping
通讯作者：
Zhong, Dongping
DOI：
10.1073/pnas.1311073110
发表时间：
2013-08-06
影响因子：
11.1
作者：
Liu, Zheyun;Tan, Chuang;Zhong, Dongping
通讯作者：
Zhong, Dongping
影响因子：
15
作者：
Kao, Ya-Ting;Tan, Chuang;Zhong, Dongping
通讯作者：
Zhong, Dongping
DOI：
10.1002/anie.200390100
发表时间：
2003-01-20
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Abel, Bernd;Assmann, Jens;Schroeder, Jorg
通讯作者：
Schroeder, Jorg
影响因子：
2.9
作者：
Adams, Ellen M.;Allen, Heather C.
通讯作者：
Allen, Heather C.