Gas-phase H/D exchange of solidated glycine oligomers with ND3: Exchange kinetics do not reflect parent ion structures

Heather A. Cox, Ryan R. Julian, Sang-Won Lee, J. L. Beauchamp

Research output: Contribution to journalArticle

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Abstract

H/D exchange is a method commonly used to probe molecular structure. The majority of studies in the gas phase have involved protonated molecular ions. The present study gives attention to molecular ions formed by coordination with a sodium ion. In particular, ND3 is reacted with sodiated glycine oligomers, Glyn, where n = 1-5, and the results are interpreted using density functional calculations. Experimentally, Gly1Na +, Gly4Na+, and Gly5Na+ all undergo three fast exchanges with ND3, while Gly 2Na+ and Gly3Na+ undergo one fast and two slow exchanges with ND3. The methyl esters Gly 3OMeNa+ and Gly5OMeNa+ do not exchange with ND3. In agreement with earlier experimental studies, theoretical calculations show that the lowest-energy conformers of the sodiated glycine oligomers are charge-solvated structures. Calculations further indicate that, in the process of H/D exchange with ND3, sodiated monoglycine and tetraglycine adopt zwitterionic structures, sodiated diglycine adopts a salt-bridge form, and sodiated triglycine takes on an ion-stabilized ion pair form. Sodiated monoglycine and diglycine exchange via an onium-ion mechanism. The proposed exchange mechanisms require a carboxylic acid hydrogen to complete the exchange, which is in agreement with the experimental results showing that no exchange occurs with methyl ester glycine oligomers. These studies clearly demonstrate that, in the process of H/D exchange, noncovalent complexation of the exchange reagent provides the energy required to access intermediates structurally distinct from the parent ions. H/D exchange is facile for these intermediates. Contrary to the assumption often expressed in earlier studies, H/D exchange kinetics may not directly reflect ion structures.

Original languageEnglish
Pages (from-to)6485-6490
Number of pages6
JournalJournal of the American Chemical Society
Volume126
Issue number20
DOIs
Publication statusPublished - 2004 May 26

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Oligomers
Glycine
Amino acids
Ion exchange
Gases
Ions
Kinetics
Glycylglycine
glycyl-glycyl-glycyl-glycine
glycyl-glycyl-glycine
Esters
Carboxylic Acids
Molecular Structure
Complexation
Carboxylic acids
Molecular structure
Density functional theory
Hydrogen
Theoretical Models
Salts

ASJC Scopus subject areas

  • Chemistry(all)

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Gas-phase H/D exchange of solidated glycine oligomers with ND3 : Exchange kinetics do not reflect parent ion structures. / Cox, Heather A.; Julian, Ryan R.; Lee, Sang-Won; Beauchamp, J. L.

In: Journal of the American Chemical Society, Vol. 126, No. 20, 26.05.2004, p. 6485-6490.

Research output: Contribution to journalArticle

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