Amine additives for improved in-ESI H/D exchange

Osipenko, Sergey; Nikolaev, Eugene; Kostyukevich, Yury

doi:10.1039/d2an00081d

Cited by 3 publications

(3 citation statements)

References 26 publications

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“…The general scheme of our experiment is presented in Figure 1B. The vapors of the D 2 O were infused into the ESI source leading to the exchange of all labile hydrogens (–OH and –NH groups) for deuterium 33 . Deuterium also attaches to the molecule during ionization.…”

Section: Resultsmentioning

confidence: 99%

In‐Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions

Kostyukevich,

Osipenko,

Borisova

et al. 2024

J Mass Spectrom

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Identification of molecules in complex natural matrices relies on matching the fragmentation spectra of ions under investigation and the spectra acquired for the corresponding analytical standards. Currently, there are many databases of experimentally measured tandem mass spectrometry spectra (such as NIST, MzCloud, and Metlin), and considerable progress has been made in the development of software for predicting tandem mass spectrometry fragments in silico using combinatorial, machine learning, and quantum chemistry approaches (such as MetFrag, CFM‐ID, and QCxMS). However, the electrospray ionization molecules can be ionized at different sites (protonated or deprotonated), and the fragmentation spectra of such ions are different. Here, we are using the combination of the in‐ESI source hydrogen/deuterium exchange reaction and MSn fragmentation for the investigation of the fragmentation pathways for different protomers of organic molecules. It is shown that the distribution of the deuterium in the fragment ions reflects the presence of different protomers. For several molecules, the distribution of deuterium was traced up to the MS5 level of fragmentation revealing many unusual and unexpected effects. For example, we investigated the loss of HF from the ciprofloxacin and norfloxacin ions and observed that for ions protonated at –COOH group, the eliminating hydrogen always comes from –NH group. When ions are protonated at another site, the elimination of hydrogen with a probability of 30% occurs from the –NH group, and with a probability of 70%, it originates from other sites on the molecule. Such effects were not described previously. Quantum chemical simulation was used for the verification of the protonated structures and simulation of the corresponding fragmentation spectra.

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Section: Resultsmentioning

confidence: 99%

In‐Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions

Kostyukevich,

Osipenko,

Borisova

et al. 2024

J Mass Spectrom

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“…Besides the opportunity to highlight the routes of molecules in metabolic cycles, stable isotopes provide valuable techniques to elucidate chemical structures and discriminate between isobaric compounds [28]. Although such techniques are often deployed ex vivo, for example as in-solution [29][30][31] or in-source H/D [32][33][34][35] and 16 O/ 18 O exchange [36][37][38][39][40], it was shown that in vivo labelling may improve molecular formula assignment [41] and the identification of unknown flavonoids [42]. In vivo labeling is also applied to evaluate metabolic turnover rates in mammals [43][44][45] or rodents [46].…”

Section: Introductionmentioning

confidence: 99%

Investigating the Metabolism of Plants Germinated in Heavy Water, D2O, and H218O-Enriched Media Using High-Resolution Mass Spectrometry

Osipenko,

Bashilov,

Vishnevskaya

et al. 2023

IJMS

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Mass spectrometry has been an essential technique for the investigation of the metabolic pathways of living organisms since its appearance at the beginning of the 20th century. Due to its capability to resolve isotopically labeled species, it can be applied together with stable isotope tracers to reveal the transformation of particular biologically relevant molecules. However, low-resolution techniques, which were used for decades, had limited capabilities for untargeted metabolomics, especially when a large number of compounds are labelled simultaneously. Such untargeted studies may provide new information about metabolism and can be performed with high-resolution mass spectrometry. Here, we demonstrate the capabilities of high-resolution mass spectrometry to obtain insights on the metabolism of a model plant, Lepidium sativum, germinated in D2O and H218O-enriched media. In particular, we demonstrated that in vivo labeling with heavy water helps to identify if a compound is being synthesized at a particular stage of germination or if it originates from seed content, and tandem mass spectrometry allows us to highlight the substructures with incorporated isotope labels. Additionally, we found in vivo labeling useful to distinguish between isomeric compounds with identical fragmentation patterns due to the differences in their formation rates that can be compared by the extent of heavy atom incorporation.

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“…Recently, our research group worked on the application of an isotope exchange approach (both H/D and 16 O/ 18 O) for targeted [18][19][20][21][22] and untargeted [23][24][25][26][27][28][29][30][31][32][33] screening of compounds in complex natural and biological matrixes. We have developed an analytical platform for the enumeration of the number of isotope exchanges for all compounds in an LC-MS/MS run.…”

Section: Introductionmentioning

confidence: 99%

Untargeted Lipidomics after D2O Administration Reveals the Turnover Rate of Individual Lipids in Various Organs of Living Organisms

Kostyukevich,

Stekolshikova,

Levashova

et al. 2023

IJMS

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The administration of low doses of D2O to living organisms was used for decades for the investigation of metabolic pathways and for the measurement of the turnover rate for specific compounds. Usually, the investigation of the deuterium uptake in lipids is performed by measuring the deuteration level of the palmitic acid residue using GC-MS instruments, and to our knowledge, the application of the modern untargeted LC-MS/MS lipidomics approaches was only reported a few times. Here, we investigated the deuterium uptake for >500 lipids for 13 organs and body liquids of mice (brain, lung, heart, liver, kidney, spleen, plasma, urine, etc.) after 4 days of 100% D2O administration. The maximum deuteration level was observed in the liver, plasma, and lung, while in the brain and heart, the deuteration level was lower. Using MS/MS, we demonstrated the incorporation of deuterium in palmitic and stearic fragments in lipids (PC, PE, TAG, PG, etc.) but not in the corresponding free forms. Our results were analyzed based on the metabolic pathways of lipids.

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Amine additives for improved in-ESI H/D exchange

Abstract: In-ESI H/D exchange is a convenient technique for analyzing small-molecular complex mixtures. However, such experiments do not yield sufficient levels of exchange or require an elevated temperature of the ion...

Cited by 3 publications

References 26 publications

In‐Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions

In‐Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions

Investigating the Metabolism of Plants Germinated in Heavy Water, D2O, and H218O-Enriched Media Using High-Resolution Mass Spectrometry

Untargeted Lipidomics after D2O Administration Reveals the Turnover Rate of Individual Lipids in Various Organs of Living Organisms

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