Kinetics and thermodynamics of oxidation mediated reaction in L-cysteine and its methyl and ethyl esters in dimethyl sulfoxide-d6 by NMR spectroscopy

Ryan J. Dougherty, Jaideep Singh, Viswanathan V Krishnan

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.

Original languageEnglish (US)
Pages (from-to)196-200
Number of pages5
JournalJournal of Molecular Structure
Volume1131
DOIs
StatePublished - Mar 5 2017

Fingerprint

Dimethyl Sulfoxide
Nuclear magnetic resonance spectroscopy
Thermodynamics
Cysteine
Oxidation
Kinetics
Sulfhydryl Compounds
Disulfides
Esters
Nuclear magnetic resonance
mecysteine
ethyl cysteine

Keywords

  • C
  • H
  • Kinetics
  • L-cysteine. L-Cysteine methyl ester (L-CysME) and L-Cysteine ethyl ester (L-CysEE)
  • NMR
  • Oxidation
  • Short title
  • Solvent effect

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{73f74e40b78345d2942cf8efd0be4540,
title = "Kinetics and thermodynamics of oxidation mediated reaction in L-cysteine and its methyl and ethyl esters in dimethyl sulfoxide-d6 by NMR spectroscopy",
abstract = "L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.",
keywords = "C, H, Kinetics, L-cysteine. L-Cysteine methyl ester (L-CysME) and L-Cysteine ethyl ester (L-CysEE), NMR, Oxidation, Short title, Solvent effect",
author = "Dougherty, {Ryan J.} and Jaideep Singh and Krishnan, {Viswanathan V}",
year = "2017",
month = "3",
day = "5",
doi = "10.1016/j.molstruc.2016.11.038",
language = "English (US)",
volume = "1131",
pages = "196--200",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",

}

TY - JOUR

T1 - Kinetics and thermodynamics of oxidation mediated reaction in L-cysteine and its methyl and ethyl esters in dimethyl sulfoxide-d6 by NMR spectroscopy

AU - Dougherty, Ryan J.

AU - Singh, Jaideep

AU - Krishnan, Viswanathan V

PY - 2017/3/5

Y1 - 2017/3/5

N2 - L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.

AB - L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.

KW - C

KW - H

KW - Kinetics

KW - L-cysteine. L-Cysteine methyl ester (L-CysME) and L-Cysteine ethyl ester (L-CysEE)

KW - NMR

KW - Oxidation

KW - Short title

KW - Solvent effect

UR - http://www.scopus.com/inward/record.url?scp=84996995514&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84996995514&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2016.11.038

DO - 10.1016/j.molstruc.2016.11.038

M3 - Article

AN - SCOPUS:84996995514

VL - 1131

SP - 196

EP - 200

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

ER -