在以太交叉链形成基质SAM酶中进行基质控制的催化
Journal of the American Chemical Society
|September 28, 2023
概括
激进的S-adenosylmethionine (rSAM) 酶在达洛巴丁等抗生素中建立了独特的交叉链接. 这项研究表明这些酶具有多功能性,基质基因控制和C-C交叉链的形成.
科学领域:
- 生物化学
- 自然产品生物合成
- 酵素学
背景情况:
- 达罗巴丁是一种复杂的七抗生素.
- 它具有以太和C-C交叉链接.
- 负责的酶DarE是一种激进的S-腺甲 (rSAM) 酶,但它如何形成两种交叉链路尚不清楚.
研究的目的:
- 研究达洛巴类RiPPs (通过核糖体合成和翻译后修改的) 的生物合成途径.
- 了解 rSAM 酶形成交叉链的酶机制.
- 发现新的达罗,并阐明控制它们结构多样性的因素.
主要方法:
- 生物合成基因集群分析
- 对成熟酶的基因分析.
- 达罗成熟酶中关键残留物的位点定向突变.
- 酶活性的生化表征
主要成果:
- 鉴定和描述两种仅含以太交叉链的新型达罗.
- 证明达罗成熟酶具有内在的多功能性.
- 证据表明基质特异性图案决定了以太交叉链接,C-C交叉链接和Ser氧化.
- 基于基质识别,rSAM酶可以催化不同的化学转化.
结论:
- 达洛成熟酶是多功能酶,能够催化多种类型的翻译后修饰.
- 基质序列直接影响rSAM酶活性的化学结果.
- 这项工作为发现新的RiPP和了解rSAM酶多功能性的调节提供了框架.
更多相关视频
11:17Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction
Published on: January 19, 2016
21.8K
06:49Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
11.9K
相关概念视频
Base-Catalyzed Ring-Opening of Epoxides
8.6K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.6K
Free-Radical Chain Reaction and Polymerization of Alkenes
7.9K
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
7.9K
Radical Reactivity: Electrophilic Radicals
1.9K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
1.9K
E2 Reaction: Kinetics and Mechanism
10.4K
SN2 substitutions and E2 eliminations of alkyl halides proceed via a concerted pathway. While the nucleophile attacks the alpha carbon in SN2 reactions, it functions as a strong base and abstracts a beta hydrogen in the E2 mechanism. The rate-limiting transition state in E2 elimination reactions is characterized by partially broken carbon–hydrogen and carbon–halogen bonds and a partially formed pi bond between the alpha and beta carbons. The beta hydrogen and halide are eliminated...
10.4K
Radical Reactivity: Overview
2.1K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.1K
Acid-Catalyzed Ring-Opening of Epoxides
7.4K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.4K
