Details
Original language | English |
---|---|
Pages (from-to) | 1315-1329 |
Number of pages | 15 |
Journal | Journal of the American Society for Mass Spectrometry |
Volume | 34 |
Issue number | 7 |
Early online date | 13 Jun 2023 |
Publication status | E-pub ahead of print - 13 Jun 2023 |
Externally published | Yes |
Abstract
While developing a DMS-based separation method for beer’s bittering compounds, we observed that the argentinated forms of humulone tautomers (i.e., [Hum + Ag]+) were partially resolvable in a N2 environment seeded with 1.5 mol % of isopropyl alcohol (IPA). Attempting to improve the separation by introducing resolving gas unexpectedly caused the peaks for the cis-keto and trans-keto tautomers of [Hum + Ag]+ to coalesce. To understand why resolution loss occurred, we first confirmed that each of the tautomeric forms (i.e., dienol, cis-keto, and trans-keto) responsible for the three peaks in the [Hum + Ag]+ ionogram were assigned to the correct species by employing collision-induced dissociation, UV photodissociation spectroscopy, and hydrogen-deuterium exchange (HDX). The observation of HDX indicated that proton transfer was stimulated by dynamic clustering processes between IPA and [Hum + Ag]+ during DMS transit. Because IPA accretion preferentially occurs at Ag+, which can form pseudocovalent bonds with a suitable electron donor, solvent clustering also facilitated the formation of exceptionally stable microsolvated ions. The exceptional stability of these microsolvated configurations disproportionately impacted the compensation voltage (CV) required to elute each tautomer when the temperature within the DMS cell was varied. The disparity in CV response caused the peaks for the cis- and trans-keto species to merge when a temperature gradient was induced by the resolving gas. Moreover, simulations showed that microsolvation with IPA mediates dienol to trans-keto tautomerization during DMS transit, which, to the best of our knowledge, is the first observation of keto/enol tautomerization occurring within an ion-mobility device.
Keywords
- differential mobility spectrometry, FAIMS, humulone, microsolvation, tautomerization
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Structural Biology
- Chemistry(all)
- Spectroscopy
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In: Journal of the American Society for Mass Spectrometry, Vol. 34, No. 7, 13.06.2023, p. 1315-1329.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Chemical Transformations Can Occur during DMS Separations
T2 - Lessons Learned from Beer’s Bittering Compounds
AU - Ieritano, Christian
AU - Haack, Alexander
AU - Hopkins, W. Scott
N1 - Funding Information: The authors would like to acknowledge Dr. J. C. Yves Le Blanc and Dr. Bradley B. Schneider of SCIEX for helpful discussions and software support as well as the high-performance computing support from Compute Canada. W.S.H. acknowledges financial support provided by the Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of Discovery, Engage, and Alliance grants, the Ontario Centres of Excellence in the form of a VIP-II grant, the InnoHK Initiative, and the Hong Kong Special Administrative Region government. C.I. acknowledges financial support from the Government of Canada for the Vanier Canada Graduate Scholarship. A.H. acknowledges his contribution being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) 449651261.
PY - 2023/6/13
Y1 - 2023/6/13
N2 - While developing a DMS-based separation method for beer’s bittering compounds, we observed that the argentinated forms of humulone tautomers (i.e., [Hum + Ag]+) were partially resolvable in a N2 environment seeded with 1.5 mol % of isopropyl alcohol (IPA). Attempting to improve the separation by introducing resolving gas unexpectedly caused the peaks for the cis-keto and trans-keto tautomers of [Hum + Ag]+ to coalesce. To understand why resolution loss occurred, we first confirmed that each of the tautomeric forms (i.e., dienol, cis-keto, and trans-keto) responsible for the three peaks in the [Hum + Ag]+ ionogram were assigned to the correct species by employing collision-induced dissociation, UV photodissociation spectroscopy, and hydrogen-deuterium exchange (HDX). The observation of HDX indicated that proton transfer was stimulated by dynamic clustering processes between IPA and [Hum + Ag]+ during DMS transit. Because IPA accretion preferentially occurs at Ag+, which can form pseudocovalent bonds with a suitable electron donor, solvent clustering also facilitated the formation of exceptionally stable microsolvated ions. The exceptional stability of these microsolvated configurations disproportionately impacted the compensation voltage (CV) required to elute each tautomer when the temperature within the DMS cell was varied. The disparity in CV response caused the peaks for the cis- and trans-keto species to merge when a temperature gradient was induced by the resolving gas. Moreover, simulations showed that microsolvation with IPA mediates dienol to trans-keto tautomerization during DMS transit, which, to the best of our knowledge, is the first observation of keto/enol tautomerization occurring within an ion-mobility device.
AB - While developing a DMS-based separation method for beer’s bittering compounds, we observed that the argentinated forms of humulone tautomers (i.e., [Hum + Ag]+) were partially resolvable in a N2 environment seeded with 1.5 mol % of isopropyl alcohol (IPA). Attempting to improve the separation by introducing resolving gas unexpectedly caused the peaks for the cis-keto and trans-keto tautomers of [Hum + Ag]+ to coalesce. To understand why resolution loss occurred, we first confirmed that each of the tautomeric forms (i.e., dienol, cis-keto, and trans-keto) responsible for the three peaks in the [Hum + Ag]+ ionogram were assigned to the correct species by employing collision-induced dissociation, UV photodissociation spectroscopy, and hydrogen-deuterium exchange (HDX). The observation of HDX indicated that proton transfer was stimulated by dynamic clustering processes between IPA and [Hum + Ag]+ during DMS transit. Because IPA accretion preferentially occurs at Ag+, which can form pseudocovalent bonds with a suitable electron donor, solvent clustering also facilitated the formation of exceptionally stable microsolvated ions. The exceptional stability of these microsolvated configurations disproportionately impacted the compensation voltage (CV) required to elute each tautomer when the temperature within the DMS cell was varied. The disparity in CV response caused the peaks for the cis- and trans-keto species to merge when a temperature gradient was induced by the resolving gas. Moreover, simulations showed that microsolvation with IPA mediates dienol to trans-keto tautomerization during DMS transit, which, to the best of our knowledge, is the first observation of keto/enol tautomerization occurring within an ion-mobility device.
KW - differential mobility spectrometry
KW - FAIMS
KW - humulone
KW - microsolvation
KW - tautomerization
UR - http://www.scopus.com/inward/record.url?scp=85163554754&partnerID=8YFLogxK
U2 - 10.1021/jasms.3c00040
DO - 10.1021/jasms.3c00040
M3 - Article
C2 - 37310853
AN - SCOPUS:85163554754
VL - 34
SP - 1315
EP - 1329
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
SN - 1044-0305
IS - 7
ER -