Unraveling the Way Acetaldehyde is Formed from Acetylene: A Study Based on DFT

乙炔 化学 质子化 乙醛 分子 反应机理 亲核细胞 光化学 催化作用 有机化学 乙醇 离子
作者
Uzma Habib,Mahum Riaz,Matthias Hofmann
出处
期刊:ACS omega [American Chemical Society]
卷期号:6 (10): 6924-6933 被引量:8
标识
DOI:10.1021/acsomega.0c06159
摘要

Acetylene hydratase (AH) of Pelobacter acetylenicus is a tungsten (W)-containing iron–sulfur enzyme that catalyzes the transformation of acetylene to acetaldehyde, the exact/true reaction mechanism of which is still in question. Scientists utilized different computational approaches to understand the reaction mechanism of acetylene hydration. Some identified it as a multistep (4–16) process that starts with the displacement of a water molecule present at the active site of AH with acetylene. However, some said that there is no need to displace water with acetylene at the active site of AH. As the reaction mechanism for the conversion of acetylene to acetaldehyde is still controversial and needs to be investigated further, DFT studies were performed on the model complexes derived from the native protein X-ray crystal structure of AH. Based on the computational results, here we are proposing the nucleophilic reaction mechanism where the water (Wat1424) molecule is coordinated to the W center and Asp13 is assumed to be in an anionic form. The Wat1424 molecule is activated by W and then donates one of its protons to the anionic Asp13, forming the W-bound hydroxide and protonated Asp13. The W-bound hydroxide then attacks the C1 atom of acetylene together with the transfer of a proton from Asp13 to its C2 atom, resulting in the formation of a vinyl alcohol intermediate complex. The energy barrier associated with this step is 14.4 kcal/mol. The final, rate-limiting, step corresponds to the tautomerization of the vinyl alcohol intermediate to acetaldehyde via intermolecular assistance of two water molecules, associated with an energy barrier of 18.9 kcal/mol. Also, the influence of the metal on the hydration of acetylene is studied when W is replaced with Mo.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
白白白完成签到 ,获得积分10
1秒前
MXene完成签到,获得积分10
1秒前
酒玖柒完成签到 ,获得积分10
3秒前
3秒前
称心嫣娆发布了新的文献求助10
4秒前
Owen应助zyf采纳,获得10
4秒前
5秒前
顾矜应助插秧露娜采纳,获得10
5秒前
6秒前
陈强强完成签到,获得积分10
7秒前
Tsuns完成签到 ,获得积分10
8秒前
大喵发布了新的文献求助10
9秒前
啦啦啦完成签到,获得积分10
10秒前
10秒前
11秒前
11秒前
13秒前
14秒前
Mano完成签到,获得积分10
15秒前
小熊饼干发布了新的文献求助10
15秒前
15秒前
奇拉维特完成签到 ,获得积分10
15秒前
zyf发布了新的文献求助10
16秒前
16秒前
17秒前
闪闪如南完成签到,获得积分10
18秒前
18秒前
插秧露娜发布了新的文献求助10
19秒前
Steven发布了新的文献求助10
21秒前
称心嫣娆完成签到,获得积分10
22秒前
漂亮白枫发布了新的文献求助10
23秒前
peanut发布了新的文献求助10
26秒前
一直向前发布了新的文献求助10
27秒前
liziqi完成签到,获得积分10
31秒前
烟花应助漂亮白枫采纳,获得10
34秒前
天才幸运鱼完成签到,获得积分10
34秒前
泡泡应助公冶笑白采纳,获得10
35秒前
华仔应助公冶笑白采纳,获得10
35秒前
恋雅颖月应助公冶笑白采纳,获得10
35秒前
莉莉娅发布了新的文献求助10
35秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
‘Unruly’ Children: Historical Fieldnotes and Learning Morality in a Taiwan Village (New Departures in Anthropology) 400
Indomethacinのヒトにおける経皮吸収 400
Phylogenetic study of the order Polydesmida (Myriapoda: Diplopoda) 370
基于可调谐半导体激光吸收光谱技术泄漏气体检测系统的研究 350
Robot-supported joining of reinforcement textiles with one-sided sewing heads 320
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3989797
求助须知:如何正确求助?哪些是违规求助? 3531910
关于积分的说明 11255394
捐赠科研通 3270563
什么是DOI,文献DOI怎么找? 1805008
邀请新用户注册赠送积分活动 882157
科研通“疑难数据库(出版商)”最低求助积分说明 809190