Hydrogen-deuterium exchange at non-labile sites: A new reaction facet with broad implications for structural and dynamic determinations

Dana R. Reed; Steven R. Kass

doi:10.1016/S1044-0305(01)00303-8

Hydrogen-deuterium exchange at non-labile sites: A new reaction facet with broad implications for structural and dynamic determinations

Dana R. Reed, Steven R. Kass

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

Hydrogen-deuterium exchange at non-labile sites is reported. The conjugate bases of isophthalic acid (m-C₆H₄(CO₂H)₂), 2-oxoglutaric acid (HO₂CCOCH₂CH₂CO₂H), and 2-methylisophthalic acid (2-CH₃-1,3-C₆H₄(CO₂H)₂) undergo scrambling with 1, 2, and 3 carbon-centered hydrogens under a variety of conditions. Likewise, protonated 2-(m-methoxyphenyl)ethylamine ((m-CH₃OC₆H₄)CH₂CH₂NH₂) undergoes up to 5 H/D exchanges upon gentle activation whereas the conjugate acid of 2-phenylethylamine (C₆H₅CH₂CH₂NH₂) requires the presence of ammonia-d₃ in order to be pushed to undergo up to 8 H/D exchanges. The very act of electrospraying ions can result in extensive movement of deuterium to carbon centers and, in some cases, could not be prevented. These findings offer great promise for future exploitation but also suggest that the interpretation of many H/D exchange experiments using mass spectrometry as the analytical tool could be in error.

Original language	English (US)
Pages (from-to)	1163-1168
Number of pages	6
Journal	Journal of the American Society for Mass Spectrometry
Volume	12
Issue number	11
DOIs	https://doi.org/10.1016/S1044-0305(01)00303-8
State	Published - 2001

Bibliographical note

Funding Information:
Support from the National Science Foundation, the donors of the Petroleum Research Foundation, as administered by the American Chemical Society, and the Minnesota Supercomputer Institute are gratefully acknowledged.

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title = "Hydrogen-deuterium exchange at non-labile sites: A new reaction facet with broad implications for structural and dynamic determinations",

abstract = "Hydrogen-deuterium exchange at non-labile sites is reported. The conjugate bases of isophthalic acid (m-C6H4(CO2H)2), 2-oxoglutaric acid (HO2CCOCH2CH2CO2H), and 2-methylisophthalic acid (2-CH3-1,3-C6H4(CO2H)2) undergo scrambling with 1, 2, and 3 carbon-centered hydrogens under a variety of conditions. Likewise, protonated 2-(m-methoxyphenyl)ethylamine ((m-CH3OC6H4)CH2CH2NH2) undergoes up to 5 H/D exchanges upon gentle activation whereas the conjugate acid of 2-phenylethylamine (C6H5CH2CH2NH2) requires the presence of ammonia-d3 in order to be pushed to undergo up to 8 H/D exchanges. The very act of electrospraying ions can result in extensive movement of deuterium to carbon centers and, in some cases, could not be prevented. These findings offer great promise for future exploitation but also suggest that the interpretation of many H/D exchange experiments using mass spectrometry as the analytical tool could be in error.",

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note = "Funding Information: Support from the National Science Foundation, the donors of the Petroleum Research Foundation, as administered by the American Chemical Society, and the Minnesota Supercomputer Institute are gratefully acknowledged. ",

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N2 - Hydrogen-deuterium exchange at non-labile sites is reported. The conjugate bases of isophthalic acid (m-C6H4(CO2H)2), 2-oxoglutaric acid (HO2CCOCH2CH2CO2H), and 2-methylisophthalic acid (2-CH3-1,3-C6H4(CO2H)2) undergo scrambling with 1, 2, and 3 carbon-centered hydrogens under a variety of conditions. Likewise, protonated 2-(m-methoxyphenyl)ethylamine ((m-CH3OC6H4)CH2CH2NH2) undergoes up to 5 H/D exchanges upon gentle activation whereas the conjugate acid of 2-phenylethylamine (C6H5CH2CH2NH2) requires the presence of ammonia-d3 in order to be pushed to undergo up to 8 H/D exchanges. The very act of electrospraying ions can result in extensive movement of deuterium to carbon centers and, in some cases, could not be prevented. These findings offer great promise for future exploitation but also suggest that the interpretation of many H/D exchange experiments using mass spectrometry as the analytical tool could be in error.

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Hydrogen-deuterium exchange at non-labile sites: A new reaction facet with broad implications for structural and dynamic determinations

Abstract

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