Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

Maleki, Hossein; Karanji, Ahmad Kiani; Majuta, Sandra N.; Maurer, Megan M.; Valentine, Stephen J.

doi:10.1007/s13361-017-1798-5

“…Under mild conditions, the number of exchanges can be predicted if the structure of the molecule (SMILES or SMARTS) is known. Thus, by applying modern tools of chemical informatics, the number of exchanges observed experimentally for unknown molecules can be used as a structural descriptor or filter parameter when performing a database search. , …”

mentioning

confidence: 99%

“…Thus, by applying modern tools of chemical informatics, the number of exchanges observed experimentally for unknown molecules can be used as a structural descriptor or filter parameter when performing a database search. 11,12 The first hydrogen/deuterium (H/D) and 16 O/ 18 O isotopic exchange reactions were observed by Lewis in 1933. 13,14 Simply dissolving the sample in D 2 O instead of H 2 O leads to the instant exchange of protons from all functional groups such as −OH, −COOH, −NH, and −SH.…”

mentioning

confidence: 99%

Hydrogen/Deuterium Exchange Aiding Compound Identification for LC-MS and MALDI Imaging Lipidomics

Kostyukevich

¹

,

Vladimirov

²

,

Stekolshchikova

³

et al. 2019

View full text Add to dashboard Cite

We present a novel approach for the increasing reliability of compound identification for LC-MS and MALDI imaging lipidomics. Our approach is based on the characterization of compounds not only by the elution time, accurate mass, and fragmentation spectra but also by the number of labile hydrogens that can be measured using the hydrogen/deuterium (H/D) exchange approach. The number of labile hydrogens (those from −OH and −NH groups) serves as an additional structural descriptor used when performing a database search. For LC-MS experiment, the H/D exchange was performed in the heating capillary of the modified electrospray ionization (ESI) source, while for MALDI imaging, the exchange was performed in the ion funnel at 10 Torr pressure. It was observed that such an approach allowed one to achieve a considerable degree of deuteration, enough to unambiguously distinguish between different classes of lipids. The proposed analytical approach may be successfully used for the identification not only of lipids but also of peptides and metabolites. A special software for the automatic filtration of molecules based on the number of functional groups was also developed.

show abstract

“…: 943.68) (only observed during fragmentation of a‐I ) after desorption of the produced CO 2 (Figure 3 a and Figure 4). Other peaks were ascribed to a cation exchange reaction in the gas phase that commonly occur during ESI‐MS experiments [25] . Reaction of a‐I at relatively low collision energy indicated that the reaction barrier towards the oxygen vacant species was low.…”

Section: Resultsmentioning

confidence: 99%

Observing Single‐Atom Catalytic Sites During Reactions with Electrospray Ionization Mass Spectrometry

Hülsey

¹

,

Sun

²

,

Sautet

³

et al. 2020

View full text Add to dashboard Cite

Single‐atom catalysts (SACs) have become a prominent theme in heterogeneous catalysis, not least because of the potential fundamental insight into active sites. The desired level of understanding, however, is prohibited due to the inhomogeneity of most supported SACs and the lack of suitable tools for structure–activity correlation studies with atomic resolution. Herein, we describe the potency of electrospray ionization mass spectrometry (ESI‐MS) to study molecularly defined SACs supported on polyoxometalates in catalytic reactions. We identified the exact composition of active sites and their evolution in the catalytic cycle during CO and alcohol oxidation reactions performed in the liquid phase. Critical information on metal‐dependent reaction mechanisms, the key intermediates, the dynamics of active sites and even the stepwise activation barriers were obtained, which would be challenging to gather via prevailingly adopted techniques in SAC research. DFT calculations revealed intricate details of the reaction mechanisms, and strong synergies between ESI‐MS defined SAC sites and electronic structure theory calculations become apparent.

show abstract

“…Other peaks were ascribed to ac ation exchange reaction in the gas phase that commonly occur during ESI-MS experiments. [25] Reaction of a-I at relatively low collision energy indicated that the reaction barrier towards the oxygen vacant species was low.W hent he solution was treated with CO for 1h,the previously observed species (a-I)disappeared and two species: + H + + K + } 2À (a-III/a-IV,calc. : 1432.06, expt.…”

Section: àmentioning

confidence: 99%

Observing Single‐Atom Catalytic Sites During Reactions with Electrospray Ionization Mass Spectrometry

Hülsey

¹

,

Sun

²

,

Sautet

³

et al. 2020

View full text Add to dashboard Cite

Single‐atom catalysts (SACs) have become a prominent theme in heterogeneous catalysis, not least because of the potential fundamental insight into active sites. The desired level of understanding, however, is prohibited due to the inhomogeneity of most supported SACs and the lack of suitable tools for structure–activity correlation studies with atomic resolution. Herein, we describe the potency of electrospray ionization mass spectrometry (ESI‐MS) to study molecularly defined SACs supported on polyoxometalates in catalytic reactions. We identified the exact composition of active sites and their evolution in the catalytic cycle during CO and alcohol oxidation reactions performed in the liquid phase. Critical information on metal‐dependent reaction mechanisms, the key intermediates, the dynamics of active sites and even the stepwise activation barriers were obtained, which would be challenging to gather via prevailingly adopted techniques in SAC research. DFT calculations revealed intricate details of the reaction mechanisms, and strong synergies between ESI‐MS defined SAC sites and electronic structure theory calculations become apparent.

show abstract

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

Cited by 17 publications

References 74 publications

Hydrogen/Deuterium Exchange Aiding Compound Identification for LC-MS and MALDI Imaging Lipidomics

Hydrogen/Deuterium Exchange Aiding Compound Identification for LC-MS and MALDI Imaging Lipidomics

Observing Single‐Atom Catalytic Sites During Reactions with Electrospray Ionization Mass Spectrometry

Observing Single‐Atom Catalytic Sites During Reactions with Electrospray Ionization Mass Spectrometry

Contact Info

Product

Resources

About