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Pregled bibliografske jedinice broj: 1121846

Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers


Schorr, Pascal; Kovačević, Borislav; Volmer, Dietrich A.
Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers // Journal of the American Society for Mass Spectrometry, 32 (2021), 4; 1116-1125 doi:10.1021/jasms.1c00054 (međunarodna recenzija, članak, znanstveni)


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Naslov
Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers

Autori
Schorr, Pascal ; Kovačević, Borislav ; Volmer, Dietrich A.

Izvornik
Journal of the American Society for Mass Spectrometry (1044-0305) 32 (2021), 4; 1116-1125

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
vitamin D3 ; epimers ; LC−MS/MS ; response factor ; electrospray ionization ; computational calculations

Sažetak
The metabolism of vitamin D3 includes a parallel C-3 epimerization pathway—in addition to the standard metabolic processes for vitamin D3— reversing the stereochemical configuration of the −OH group at carbon-3 (β→α). While the biological function of the 3α epimer has not been elucidated yet, the additional species cannot be neglected in the analytical determination of vitamin D3, as it has the potential to introduce analytical errors if not properly accounted for. Recently, some inconsistent mass spectral behavior was seen for the 25-hydroxyvitamin D3 (25(OH)D3) epimers during quantification using electrospray LC–MS/MS. The present work extends that of Flynn et al. ( Ann. Clin. Biochem. 2014, 51, 352−559) and van den Ouweland et al. ( J. Chromatogr. B 2014, 967, 195−202), who reported larger electrospray ionization response factors for the 3α epimer of 25(OH)D3 in human serum samples as compared to the regular 3β variant. The present work was concerned with the mechanistic reasons for these differences. We used a combination of electrospray ionization, atmospheric pressure chemical ionization, and density functional theory calculations to uncover structural dissimilarities between the epimers. A plausible mechanism is described based on intramolecular hydrogen bonding in the gas phase, which creates a small difference of proton affinities between the epimers. More importantly, this mechanism allows the explanation of the different ionization efficiencies of the epimers based on kinetic control of the ionization process, where ionization initially takes place at the hydroxyl group with subsequent proton transfer to a basic carbon atom. The barrier for this transfer differs between the epimers and is in direct competition with H2O elimination from the protonated hydroxyl group. The “hidden” site of high gas phase basicity was revealed through computational calculations and appears to be inaccessible via direct protonation.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Ustanove:
Institut "Ruđer Bošković", Zagreb

Profili:

Avatar Url Borislav Kovačević (autor)

Citiraj ovu publikaciju

Schorr, Pascal; Kovačević, Borislav; Volmer, Dietrich A.
Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers // Journal of the American Society for Mass Spectrometry, 32 (2021), 4; 1116-1125 doi:10.1021/jasms.1c00054 (međunarodna recenzija, članak, znanstveni)
Schorr, P., Kovačević, B. & Volmer, D. (2021) Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers. Journal of the American Society for Mass Spectrometry, 32 (4), 1116-1125 doi:10.1021/jasms.1c00054.
@article{article, year = {2021}, pages = {1116-1125}, DOI = {10.1021/jasms.1c00054}, keywords = {vitamin D3, epimers, LC−MS/MS, response factor, electrospray ionization, computational calculations}, journal = {Journal of the American Society for Mass Spectrometry}, doi = {10.1021/jasms.1c00054}, volume = {32}, number = {4}, issn = {1044-0305}, title = {Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers}, keyword = {vitamin D3, epimers, LC−MS/MS, response factor, electrospray ionization, computational calculations} }
@article{article, year = {2021}, pages = {1116-1125}, DOI = {10.1021/jasms.1c00054}, keywords = {vitamin D3, epimers, LC−MS/MS, response factor, electrospray ionization, computational calculations}, journal = {Journal of the American Society for Mass Spectrometry}, doi = {10.1021/jasms.1c00054}, volume = {32}, number = {4}, issn = {1044-0305}, title = {Overestimation of 3α- over 3β-25-Hydroxyvitamin D3 Levels in Serum: A Mechanistic Rationale for the Different Mass Spectral Properties of the Vitamin D Epimers}, keyword = {vitamin D3, epimers, LC−MS/MS, response factor, electrospray ionization, computational calculations} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


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