Long-lived 1H nuclear spin singlet in dimethyl maleate revealed by addition of thiols

Yuning Zhang, Pei Che Soon, Alexej Jerschow, James Canary

Research output: Contribution to journalArticle

Abstract

Nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) have become important techniques in many research areas. One major limitation is the relatively low sensitivity of these methods, which recently has been addressed by hyperpolarization. However, once hyperpolarization is imparted on a molecule, the magnetization typically decays within relatively short times. Singlet states are well isolated from the environment, such that they acquire long lifetimes. We describe herein a model reaction for read-out of a hyperpolarized long-lived state in dimethyl maleate using thiol conjugate addition. This type of reaction could lend itself to monitoring oxidative stress or hypoxia by sensitive detection of thiols. Similar reactions could be used in biosensors or assays that exploit molecular switching. Singlet lifetimes of about 4.7 min for 1H spins in [D4]MeOH are seen in this system. Hyperpolarized singlet states are well isolated from the environment, such that they acquire long lifetimes. Here, we used the thiol conjugate addition to unveil the hyperpolarized long-lived singlet state in deuterated dimethyl maleate (see picture). Singlet lifetimes of 4.7 min for 1H spins in [D4]MeOH are seen in this system.

Original languageEnglish (US)
Pages (from-to)3396-3399
Number of pages4
JournalAngewandte Chemie - International Edition
Volume53
Issue number13
DOIs
StatePublished - Mar 24 2014

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Oxidative stress
Magnetic resonance
Sulfhydryl Compounds
Biosensors
Nuclear magnetic resonance spectroscopy
Assays
Magnetization
Imaging techniques
Molecules
Monitoring
dimethyl maleate

Keywords

  • cysteine
  • long-lived spin states
  • NMR spectroscopy
  • parahydrogen
  • thiol conjugate addition

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Long-lived 1H nuclear spin singlet in dimethyl maleate revealed by addition of thiols. / Zhang, Yuning; Soon, Pei Che; Jerschow, Alexej; Canary, James.

In: Angewandte Chemie - International Edition, Vol. 53, No. 13, 24.03.2014, p. 3396-3399.

Research output: Contribution to journalArticle

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