Kinetics of Thiol/Disulfide Exchange Correlate Weakly with the Restoring Force in the Disulfide Moiety

被引:82
作者
Kucharski, Timothy J. [1 ]
Huang, Zhen [1 ]
Yang, Qing-Zheng [1 ]
Tian, Yancong [1 ]
Rubin, Nicholas C. [1 ]
Concepcion, Carlos D. [1 ]
Boulatov, Roman [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
基金
美国国家科学基金会;
关键词
kinetics; macrocycles; nucleophilic substitution; strained molecules; sulfur; INTERCHANGE; SUBSTITUTION; SPECTROSCOPY; SOLVATION; CHEMISTRY; MECHANISM; BOND;
D O I
10.1002/anie.200901511
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
S-S-Stretch! A series of increasingly strained macrocyclic disulfides investigated experimentally and by high-level DFT calculations reveals that the kinetics of thiol/disulfide exchange are independent of the restoring force in the disulfide moiety. This finding is consistent with the SN2 mechanism of thiol/disulfide exchange and lends insight into the acceleration of disulfide reduction upon stretching of certain proteins. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:7040 / 7043
页数:4
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