Decarboxylation of Aromatic Carboxylic Acids by the Prenylated-FMN-dependent Enzyme Phenazine-1-carboxylic Acid Decarboxylase
Decarboxylation of Aromatic Carboxylic Acids by the Prenylated-FMN-dependent Enzyme Phenazine-1-carboxylic Acid Decarboxylase
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异戊二烯化 FMN 依赖性酶吩嗪-1-羧酸脱羧酶对芳香族羧酸进行脱羧
DOI：
10.1021/acscatal.1c03040
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发表时间：
2021
期刊：
影响因子：
12.9
通讯作者：
Marsh, E. Neil
中科院分区：
文献类型：
--
作者：
Datar, Prathamesh M.;Marsh, E. Neil
吩嗪-1-羧酸脱羧酶（PhdA）是异戊烯化-FMN依赖性（prFMN）脱羧酶的扩展类别的成员。这些酶因其催化芳环和共轭双键上的羧化（脱羧）反应的能力而引起人们的兴趣。在这里，我们描述了一种方法来重建PhdA与prFMN，产生一种活性和稳定形式的全酶，不需要预还原连二亚硫酸盐的活性。我们确定氧化的吩嗪-1-羧酸（PCA）是脱羧的底物，kcat = 2.6 s-1，KM = 53 μM。PhdA还催化溶剂氘到产物吩嗪中的慢得多的交换，表观周转数为0.8 min-1。该酶被发现催化广泛的聚芳族羧酸，包括蒽-1-羧酸的脱羧。先前描述的prFMN依赖性芳族（脱）羧化酶已经利用富电子酚或杂环分子作为底物。PhdA将prFMN依赖性（脱）羧化酶的底物范围扩展到电子贫乏和未官能化的芳族系统，表明它可能证明是一种有用的催化剂，用于区域选择性（脱）羧化，否则不反应的芳族分子。
Phenazine-1-carboxylic acid decarboxylase (PhdA) is a member of the expanding class of prenylated-FMN-dependent (prFMN) decarboxylase enzymes. These enzymes have attracted interest for their ability to catalyze (de)carboxylation reactions on aromatic rings and conjugated double bonds. Here we describe a method to reconstitute PhdA with prFMN that produces an active and stable form of the holo-enzyme that does not require prereduction with dithionite for activity. We establish that oxidized phenazine-1-carboxylate (PCA) is the substrate for decarboxylation, withkcat= 2.6 s–1andKM= 53 μM. PhdA also catalyzes the much slower exchange of solvent deuterium into the product, phenazine, with an apparent turnover number of 0.8 min–1. The enzyme was found to catalyze the decarboxylation of a broad range of polyaromatic carboxylic acids, including anthracene-1-carboxylic acid. Previously described prFMN-dependent aromatic (de)carboxylases have utilized electron-rich phenolic or heterocyclic molecules as substrates. PhdA extends the substrate range of prFMN-dependent (de)carboxylases to electron-poor and unfunctionalized aromatic systems, suggesting that it may prove a useful catalyst for the regioselective (de)carboxylation of otherwise unreactive aromatic molecules.
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影响因子：
4.8
作者：
Marshall, Stephen A.;Fisher, Karl;Leys, David
通讯作者：
Leys, David
影响因子：
12.9
作者：
Jordan, Frank;Patel, Hetalben
通讯作者：
Patel, Hetalben
影响因子：
3.7
作者：
Jacewicz A;Izumi A;Brunner K;Schnell R;Schneider G
通讯作者：
Schneider G
DOI：
--
发表时间：
1977
期刊：
影响因子：
--
作者：
H. Ansell;M. Hirschler;R. Taylor
通讯作者：
R. Taylor
多环芳烃与3,5-二氯-2,4,6-三甲基-和2,4,6-三甲基苯甲腈氧化物的1,3-偶极环加成反应
DOI：
--
发表时间：
1996
期刊：
影响因子：
--
作者：
A. Corsaro;V. Librando;U. Chiacchio;V. Pistarà
通讯作者：
V. Pistarà