The complete microspeciation of ovothiol A, the smallest octafarious antioxidant biomolecule

Arash Mirzahosseini, Gábor Orgován, Sándor Hosztafi, B. Noszál

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Ovothiol A, a small biomolecule with highly potent antioxidant capacity, and three newly synthesized derivatives were studied by 1H NMR, 15N NMR, UV-pH titrations, and a customized evaluation method. The omni-interactive imidazole, amino, carboxylate, and thiolate moieties of ovothiol A are quantified in terms of 32 microscopic protonation constants, the relative concentrations of 16 microspecies, 6 pairwise interactivity parameters, and 8 protonation shifts. The highest and lowest imidazole basicities differ by a record-breaking five orders of magnitude, and the predominant thiolate protonation constant is by far the smallest known thiolate logK value. The latter provides an indication as to why ovothiol A occurs naturally under deep-water circumstances only. Since thiolate basicities are in correlation with thiol-disulfide redox potentials, the eight different, fine-tunable thiolate basicities offer versatile and highly specific antioxidant capacities within one single molecular skeleton. This work is the first complete microspeciation of a tetrabasic, nonsymmetrical natural compound. [Figure not available: see fulltext.]

Original languageEnglish
Pages (from-to)2377-2387
Number of pages11
JournalAnalytical and Bioanalytical Chemistry
Volume406
Issue number9-10
DOIs
Publication statusPublished - 2014

Fingerprint

Protonation
Biomolecules
Alkalinity
Antioxidants
Nuclear magnetic resonance
Titration
Sulfhydryl Compounds
Skeleton
Disulfides
Oxidation-Reduction
Derivatives
Water
ovothiol A
imidazole

Keywords

  • Acid-base chemistry
  • Antioxidant capacity
  • Microspeciation
  • Ovothiol
  • Oxidative stress
  • Thiolate basicity

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Medicine(all)

Cite this

The complete microspeciation of ovothiol A, the smallest octafarious antioxidant biomolecule. / Mirzahosseini, Arash; Orgován, Gábor; Hosztafi, Sándor; Noszál, B.

In: Analytical and Bioanalytical Chemistry, Vol. 406, No. 9-10, 2014, p. 2377-2387.

Research output: Contribution to journalArticle

Mirzahosseini, Arash ; Orgován, Gábor ; Hosztafi, Sándor ; Noszál, B. / The complete microspeciation of ovothiol A, the smallest octafarious antioxidant biomolecule. In: Analytical and Bioanalytical Chemistry. 2014 ; Vol. 406, No. 9-10. pp. 2377-2387.
@article{9e237a7da9984ed3a3fe2a702d4ab2f1,
title = "The complete microspeciation of ovothiol A, the smallest octafarious antioxidant biomolecule",
abstract = "Ovothiol A, a small biomolecule with highly potent antioxidant capacity, and three newly synthesized derivatives were studied by 1H NMR, 15N NMR, UV-pH titrations, and a customized evaluation method. The omni-interactive imidazole, amino, carboxylate, and thiolate moieties of ovothiol A are quantified in terms of 32 microscopic protonation constants, the relative concentrations of 16 microspecies, 6 pairwise interactivity parameters, and 8 protonation shifts. The highest and lowest imidazole basicities differ by a record-breaking five orders of magnitude, and the predominant thiolate protonation constant is by far the smallest known thiolate logK value. The latter provides an indication as to why ovothiol A occurs naturally under deep-water circumstances only. Since thiolate basicities are in correlation with thiol-disulfide redox potentials, the eight different, fine-tunable thiolate basicities offer versatile and highly specific antioxidant capacities within one single molecular skeleton. This work is the first complete microspeciation of a tetrabasic, nonsymmetrical natural compound. [Figure not available: see fulltext.]",
keywords = "Acid-base chemistry, Antioxidant capacity, Microspeciation, Ovothiol, Oxidative stress, Thiolate basicity",
author = "Arash Mirzahosseini and G{\'a}bor Orgov{\'a}n and S{\'a}ndor Hosztafi and B. Nosz{\'a}l",
year = "2014",
doi = "10.1007/s00216-014-7631-0",
language = "English",
volume = "406",
pages = "2377--2387",
journal = "Fresenius Zeitschrift fur Analytische Chemie",
issn = "1618-2642",
publisher = "Springer Verlag",
number = "9-10",

}

TY - JOUR

T1 - The complete microspeciation of ovothiol A, the smallest octafarious antioxidant biomolecule

AU - Mirzahosseini, Arash

AU - Orgován, Gábor

AU - Hosztafi, Sándor

AU - Noszál, B.

PY - 2014

Y1 - 2014

N2 - Ovothiol A, a small biomolecule with highly potent antioxidant capacity, and three newly synthesized derivatives were studied by 1H NMR, 15N NMR, UV-pH titrations, and a customized evaluation method. The omni-interactive imidazole, amino, carboxylate, and thiolate moieties of ovothiol A are quantified in terms of 32 microscopic protonation constants, the relative concentrations of 16 microspecies, 6 pairwise interactivity parameters, and 8 protonation shifts. The highest and lowest imidazole basicities differ by a record-breaking five orders of magnitude, and the predominant thiolate protonation constant is by far the smallest known thiolate logK value. The latter provides an indication as to why ovothiol A occurs naturally under deep-water circumstances only. Since thiolate basicities are in correlation with thiol-disulfide redox potentials, the eight different, fine-tunable thiolate basicities offer versatile and highly specific antioxidant capacities within one single molecular skeleton. This work is the first complete microspeciation of a tetrabasic, nonsymmetrical natural compound. [Figure not available: see fulltext.]

AB - Ovothiol A, a small biomolecule with highly potent antioxidant capacity, and three newly synthesized derivatives were studied by 1H NMR, 15N NMR, UV-pH titrations, and a customized evaluation method. The omni-interactive imidazole, amino, carboxylate, and thiolate moieties of ovothiol A are quantified in terms of 32 microscopic protonation constants, the relative concentrations of 16 microspecies, 6 pairwise interactivity parameters, and 8 protonation shifts. The highest and lowest imidazole basicities differ by a record-breaking five orders of magnitude, and the predominant thiolate protonation constant is by far the smallest known thiolate logK value. The latter provides an indication as to why ovothiol A occurs naturally under deep-water circumstances only. Since thiolate basicities are in correlation with thiol-disulfide redox potentials, the eight different, fine-tunable thiolate basicities offer versatile and highly specific antioxidant capacities within one single molecular skeleton. This work is the first complete microspeciation of a tetrabasic, nonsymmetrical natural compound. [Figure not available: see fulltext.]

KW - Acid-base chemistry

KW - Antioxidant capacity

KW - Microspeciation

KW - Ovothiol

KW - Oxidative stress

KW - Thiolate basicity

UR - http://www.scopus.com/inward/record.url?scp=84898021753&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84898021753&partnerID=8YFLogxK

U2 - 10.1007/s00216-014-7631-0

DO - 10.1007/s00216-014-7631-0

M3 - Article

C2 - 24510213

AN - SCOPUS:84898021753

VL - 406

SP - 2377

EP - 2387

JO - Fresenius Zeitschrift fur Analytische Chemie

JF - Fresenius Zeitschrift fur Analytische Chemie

SN - 1618-2642

IS - 9-10

ER -