title: Long-lived ¹H nuclear spin singlet in dimethyl maleate revealed by addition of thiols.
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 (1)H spins in [D4]MeOH are seen in this system.
authors.affiliation: Department of Chemistry, New York University, 100 Washington Sq. East, New York, NY 10003 (USA) http://www.nyu.edu/projects/jerschow/ http://www.nyu.edu/pages/canary/home.html.
authors.forename: Yuning
authors.initials: Y
authors.lastname: Zhang
authors.forename: Pei Che
authors.initials: PC
authors.lastname: Soon
authors.forename: Alexej
authors.initials: A
authors.lastname: Jerschow
authors.forename: James W
authors.initials: JW
authors.lastname: Canary
keywords: NMR spectroscopy; cysteine; long-lived spin states; parahydrogen; thiol conjugate addition