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Decarboxylation of Aromatic Carboxylic Acids by the Prenylated-FMN-dependent Enzyme Phenazine-1-carboxylic Acid Decarboxylase
ACS Catalysis ( IF 12.9 ) Pub Date : 2021-09-07 , DOI: 10.1021/acscatal.1c03040
Prathamesh M. Datar , E. Neil G. Marsh

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, with kcat = 2.6 s–1 and KM = 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.

中文翻译:

异戊二烯化-FMN 依赖性酶吩嗪-1-羧酸脱羧酶对芳香族羧酸的脱羧

吩嗪-1-羧酸脱羧酶 (PhdA) 是不断扩大的异戊二烯化 FMN 依赖性 (prFMN) 脱羧酶类的成员。这些酶因其在芳环和共轭双键上催化(脱)羧化反应的能力而引起了人们的兴趣。在这里,我们描述了一种用 prFMN 重建 PhdA 的方法,该方法产生一种活性和稳定形式的全酶,不需要用连二亚硫酸盐进行预还原。我们确定氧化吩嗪-1-羧酸盐 (PCA) 是脱羧的底物,k cat = 2.6 s –1K M = 53 μM。PhdA 还催化溶剂氘向产物吩嗪的缓慢交换,表观周转数为 0.8 分钟–1 . 发现该酶可催化多种多环芳族羧酸(包括蒽-1-羧酸)的脱羧。先前描述的依赖于 prFMN 的芳香族 (脱) 羧化酶已利用富含电子的酚类或杂环分子作为底物。PhdA 将 prFMN 依赖性(脱)羧酶的底物范围扩展到缺电子和未官能化的芳族系统,这表明它可能证明是一种有用的催化剂,可用于其他非反应性芳族分子的区域选择性(脱)羧化。
更新日期:2021-09-17
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