Accurate Single-Molecule Kinetic Isotope Effects

被引：15

作者：

Guo, Yilin ^{[5
]}

Yang, Chen ^{[5
]}

Li, Huiping ^{[2
]}

Zhang, Lei ^{[3
]}

Zhou, Shuyao ^{[5
]}

Zhu, Xin ^{[6
]}

Fu, Huanyan ^{[6
]}

Li, Zhizhou ^{[5
]}

Liu, Zhirong ^{[5
]}

Jia, Chuancheng ^{[6
]}

Liu, Zitong ^{[1
]}

Zhu, Wenguang ^{[2
]}

Mo, Fanyang ^{[3
]}

Zhang, Deqing ^{[4
]}

Guo, Xuefeng ^{[5
,6
]}

机构：

[1] Lanzhou Univ, State Key Lab Appl Organ Chem, Coll Chem & Chem Engn, Lanzhou 730000, Gansu, Peoples R China

[2] Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Dept Phys, ICQD, Hefei 230026, Anhui, Peoples R China

[3] Peking Univ, Sch Mat Sci & Engn, Beijing 100871, Peoples R China

[4] Chinese Acad Sci, Beijing Natl Lab Mol Sci, CAS Key Lab Organ Solids, Inst Chem, Beijing 100190, Peoples R China

[5] Peking Univ, Beijing Natl Lab Mol Sci, Natl Biomed Imaging Ctr, Coll Chem & Mol Engn, Beijing 100871, Peoples R China

[6] Nankai Univ, Coll Elect Informat & Opt Engn, Frontiers Sci Ctr New Organ Matter, Ctr Single Mol Sci,Inst Modern Opt, Tianjin 300350, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2022年 / 144卷 / 07期

基金：

国家重点研发计划; 中国国家自然科学基金;

关键词：

TRANSITION-STATE STRUCTURE; CLAISEN REARRANGEMENT; HYDROGEN; JUNCTIONS; WATER;

D O I：

10.1021/jacs.1c12490

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An accurate single-molecule kinetic isotope effect (sm-KIE) was applied to circumvent the inherent limitation of conventional ensemble KIE by using graphene-molecule-graphene single-molecule junctions. In situ monitoring of the single-molecule reaction trajectories in real time with high temporal resolution has the capability to characterize the deeper information brought by KIE. The C-O bond cleavage and the C-C bond formation of the transition state (TS) were observed in the Claisen rearrangement through the secondary kinetic isotope effect, demonstrating the high detection sensitivity and accuracy of this method. More interestingly, this sm-KIE can be used to determine TS structures under different electric fields, revealing the multidimensional regulation of the TS. The detection and manipulation of the TS provide a broad perspective to understand and optimize chemical reactions and biomimetic progress.

引用

页码：3146 / 3153

页数：8

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