The in situ gas‐phase formation of a C‐glycoside ion obtained during electrospray ionization tandem mass spectrometry. A unique intramolecular mechanism involving an ion‐molecule reaction

Banoub, Joseph; Demian, Wael L. L.; Piazzetta, Paolo; Sarkis, George Anis; Kanawati, Basem; Lafont, Dominique; Laurent, Nicolas; Vaillant, Celine; Randell, Edward; Giorgi, Gianluca; Fridgen, Travis D.

doi:10.1002/rcm.7269

Cited by 4 publications

(3 citation statements)

References 47 publications

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“…Although the mechanisms in sugars is still unknown, it (Brüll et al, 1998;Wuhrer et al, 2011). A somewhat similar case is the loss of a polyether spacer of 3 in positive ionization mode using several types of instruments and for which a charge remote mechanism was proposed (Banoub et al, 2015). Several examples can be found where strong inorganic acids migrate: Internal loss of formaldehyde was found in the reverse transcriptase inhibitor adefovir 4 upon migration of the phosphonic acid in the positive ionization mode (Chen et al, 2004).…”

Section: Discussionmentioning

confidence: 99%

Gas-Phase Rearrangement of the O-Glucuronide of Vildagliptin Forms Product-Ion Fragments Suggesting Wrongly an N-Glucuronide

et al. 2018

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The O-glucuronide of vildagliptin, a dipeptidyl peptidase 4 inhibitor, is a major metabolite in monkeys and a minor metabolite in humans, rats, and dogs. Its product ion spectrum shows fragments that can be explained only by an N-glucuronide. Biotransformation using rat liver yielded milligram amounts of the O-glucuronide, and its structure was assigned unambiguously by nuclear magnetic resonance. The tandem mass spectra (MS/MS) of this compound was investigated in detail using MS n and accurate mass spectrometers and was identical to the animal metabolite. Thus, the MS/MS fragments suggesting an N-glucuronide had to be formed by gas-phase rearrangement. This gas-phase rearrangement can be observed on quadrupole timeof-flight and ion-trap mass instruments. The literature on gasphase rearrangements is reviewed.

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Section: Discussionmentioning

confidence: 99%

Gas-Phase Rearrangement of the O-Glucuronide of Vildagliptin Forms Product-Ion Fragments Suggesting Wrongly an N-Glucuronide

et al. 2018

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“…Note: Intramolecular hydrogen transfers in some fragments can occur by backbiting, [39], and Mclafferty rearrangement from the alcohol side, as indicated by red arrows. [40,41] 3.…”

Section: Maldi-tof-ms (+Ion Mode) and Cid-ms/ms (Haba Matrix)mentioning

confidence: 99%

Demystifying and Unravelling the Factual Molecular Structure of the Biopolymer Sporopollenin

Mikhael¹,

Jurčić²,

Schneider³

et al. 2019

Preprint

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Sporopollenin is a natural, highly cross-linked biopolymer composed of carbon, hydrogen, and oxygen, which forms the outer wall of pollen grains. Sporopollenin is resilient to chemical degradation. Because of this stability, its exact chemical structure and the biochemical pathways involved in its biosynthesis remains a mystery and unresolved. We have identified and characterized the molecular structure of the clean, intact sporopollenin using soft ionization mass spectrometric and nuclear magnetic resonance techniques. These analyses showed that sporopollenin contained a poly(hydroxyacid) dendrimer-like network, which accounted for the sporopollenin empirical formula. In addition, the identified hydroxy acid monomers contained a beta diketone moiety, which most probably accounts for the known antioxidant activity of sporopollenin. Moreover, our elucidation studies allowed us to identify a unique circular polyhydroxylated tetraketide polymer. This polymer acted as the rigid backbone on which the poly(hydroxyacid) network can be built, forming the scaffold of the spherical sporopollenin exine.

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“…Note: Intramolecular hydrogen transfers in some fragments can occur by backbiting, [39], and Mclafferty rearrangement from the alcohol side, as indicated by red arrows. [40,41] 3.…”

Section: Maldi-tof-ms (+Ion Mode) and Cid-ms/ms (Haba Matrix)mentioning

confidence: 99%

Demystifying and Unravelling the Factual Molecular Structure of the Biopolymer Sporopollenin

Mikhael¹,

Jurčić²,

Schneider³

et al. 2019

Preprint

Self Cite

View full text Add to dashboard Cite

Sporopollenin is a natural highly cross-linked biopolymer composed of carbon, hydrogen, and oxygen which forms the outer wall of pollen grains. Sporopollenin is resilient to chemical degradation. Because of this stability, its exact chemical structure and the biochemical pathways involved in its biosynthesis remains a mystery and unresolved. It is obvious that a well-conceived coherent study of the sporopollenin structure details will help immensely scientists in better understanding the chemistry of their current applications of sporopollenin exines such as drug delivery, peptide synthesis, micro-reactors, and wastewater purification. As well, it may also lead to the discovery of newer biomedical applications in the next coming years. We have identified and characterized the molecular structure of the clean, intact sporopollenin using mass spectrometric and nuclear magnetic resonance techniques. These analyses showed that sporopollenin is composed of a circular polyhydroxylated tetraketide polymer rigid backbone and a poly(hydroxyacid) branched network. The poly(hydroxyacid) network chains are attached by covalantly ether bonds to the polyhydroxylated tetraketides rigid backbone, forming the scaffold of the spherical sporopollenin.

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The in situ gas‐phase formation of a C‐glycoside ion obtained during electrospray ionization tandem mass spectrometry. A unique intramolecular mechanism involving an ion‐molecule reaction

Cited by 4 publications

References 47 publications

Gas-Phase Rearrangement of the O-Glucuronide of Vildagliptin Forms Product-Ion Fragments Suggesting Wrongly an N-Glucuronide

Gas-Phase Rearrangement of the O-Glucuronide of Vildagliptin Forms Product-Ion Fragments Suggesting Wrongly an N-Glucuronide

Demystifying and Unravelling the Factual Molecular Structure of the Biopolymer Sporopollenin

Demystifying and Unravelling the Factual Molecular Structure of the Biopolymer Sporopollenin

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