Observation of Zwitterion Formation in the Gas-Phase H/D-Exchange with CH3OD: Solution-Phase Structures in the Gas Phase

Infrared spectroscopy of gas-phase singly deuterated [Trp + K](+) (formed by H/D exchange with CH(3)OD) shows that some (approximately 20%) kinetically stable zwitterionic (ZW) conformer is formed, based on the diagnostic antisymmetric CO stretch of the deprotonated carboxylate moiety, upsilon(as)(CO(2)(-)), at 1680 cm(-1). A majority of the deuterated [Trp + K](+) is found to be in the charge solvation (CS) conformation, with deuterium exchange occurring on both the acid and amino groups, which is consistent with H/D scrambling. Interestingly, H/D exchange with the more basic ND(3) reagent did not result in the stabilization of a kinetically stable zwitterion, although it is not clear yet what causes this observation. The result for CH(3)OD shows that H/D exchange can in fact alter the structure of the analyte and, hence, care needs to be taken when interpreting gas-phase H/D exchange studies. Moreover, this result shows the possibility of forming solution-phase structures that are thermodynamically disfavored in the gas phase, thus opening a new area of study.