Photoinduced Electron Transfer from a 1,4,5,6-Tetrahydro Nicotinamide Adenine Dinucleotide (Phosphate) Analogue to Oxidized Flavin in an Ene-Reductase Flavoenzyme.
Photoinduced Electron Transfer from a 1,4,5,6-Tetrahydro Nicotinamide Adenine Dinucleotide (Phosphate) Analogue to Oxidized Flavin in an Ene-Reductase Flavoenzyme.
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1，4，5，6-四氢烟酰胺腺嘌呤二核苷酸(磷酸)类似物在烯还原酶黄素中的光诱导电子转移。
DOI：
10.1021/acs.jpclett.3c00176
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发表时间：
2023-04-06
影响因子：
5.7
通讯作者：
Hay, Sam
中科院分区：
文献类型：
--
作者：
Speirs, Magnus;Hardman, Samantha J. O.;Iorgu, Andreea I.;Johannissen, Linus O.;Heyes, Derren J.;Scrutton, Nigel S.;Sazanovich, Igor, V;Hay, Sam
最近的报道描述了使用酶还原酶黄酮酶催化非自然光化学反应。这些研究主要集中在使用还原黄酶，但氧化黄素具有优越的光捕获特性。在氧化的烯还原酶季戊四醇四硝酸还原酶与非反应性烟酰胺辅酶类似物1,4,5,6-四氢NAD(P)H的二元配合物中，黄素单核苷酸（FMN）的可见光激发导致NAD(P)H4向FMN的单电子转移，生成NAD(P)H4阳离子自由基和阴离子FMN半醌。这种电子转移发生在~ 1ps，似乎在动力学上胜过活性位点芳香族残基的还原猝灭。时间分辨红外测量表明，弛豫过程似乎主要集中在FMN上，电荷分离状态是短暂的，弛豫可能是通过反向电子转移发生的，发生在~ 3 - 30ps。虽然这表明了非天然光活性的潜力，但有用的光催化可能需要更长的激发态，这可能通过酶工程和/或明智地选择底物来实现。
Recent reports have described the use of ene-reductase flavoenzymes to catalyze non-natural photochemical reactions. These studies have focused on using reduced flavoenzyme, yet oxidized flavins have superior light harvesting properties. In a binary complex of the oxidized ene-reductase pentaerythritol tetranitrate reductase with the nonreactive nicotinamide coenzyme analogs 1,4,5,6-tetrahydro NAD(P)H, visible photoexcitation of the flavin mononucleotide (FMN) leads to one-electron transfer from the NAD(P)H4 to FMN, generating a NAD(P)H4 cation radical and anionic FMN semiquinone. This electron transfer occurs in ∼1 ps and appears to kinetically outcompete reductive quenching from aromatic residues in the active site. Time-resolved infrared measurements show that relaxation processes appear to be largely localized on the FMN and the charge-separated state is short-lived, with relaxation, presumably via back electron transfer, occurring over ∼3–30 ps. While this demonstrates the potential for non-natural photoactivity, useful photocatalysis will likely require longer-lived excited states, which may be accessible by enzyme engineering and/or a judicious choice of substrate.
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影响因子：
16.6
作者：
Hay, Sam;Pudney, Christopher R.;Scrutton, Nigel S.
通讯作者：
Scrutton, Nigel S.
影响因子：
3.3
作者：
Lacombat, Fabien;Espagne, Agathe;Essen, Lars-Oliver
通讯作者：
Essen, Lars-Oliver
DOI：
10.1007/978-1-4939-0452-5_8
发表时间：
2014-01-01
期刊：
FLAVINS AND FLAVOPROTEINS: METHODS AND PROTOCOLS
影响因子：
--
作者：
Pudney, Christopher R.;Hay, Sam;Scrutton, Nigel S.
通讯作者：
Scrutton, Nigel S.
BLUF结构域功能不需要亚稳组织中间状态。
影响因子：
15
作者：
Lukacs A;Brust R;Haigney A;Laptenok SP;Addison K;Gil A;Towrie M;Greetham GM;Tonge PJ;Meech SR
通讯作者：
Meech SR
影响因子：
15
作者：
Gil, Agnieszka A.;Laptenok, Sergey P.;Tonge, Peter J.
通讯作者：
Tonge, Peter J.