Assignment of gas-phase dipeptide amide hydrogen exchange rate constants by site-specific substitution: GlyGly

被引:20
作者
He, F
Marshall, AG [1 ]
Freitas, MA
机构
[1] Florida State Univ, Natl High Magnet Field Lab, Tallahassee, FL 32310 USA
[2] Ohio State Univ, Columbus, OH 43210 USA
关键词
D O I
10.1021/jp003492a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Amide hydrogen deuterium exchange is widely used to probe conformations of gas-phase biomacromolecular ions. Meaningful interpretation of such experiments depends on relating the experimentally determined H/D exchange rate constants to specific exchangeable hydrogen sites on the molecule. Here, we present the first definitive assignment of H/D exchange rate constants for the N-terminal ammonium, amide hydrogen, and carboxyl hydrogens in diglycine, based on comparison of site-specific gas-phase H/D exchange rate constants for diglycine (GlyGly) and its selectively methylated homologues (GlySar, GlyGly-OMe, and GlySar-OMe). The present method may be extended to identification of site-specific H/D exchange rate constants for other dipeptides, to provide insight into H/D exchange reaction mechanisms.
引用
收藏
页码:2244 / 2249
页数:6
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