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Long-Lived 1H Nuclear Spin Singlet in Dimethyl Maleate Revealed by Addition of Thiols


  • This work was supported by NSF grants CHE-0848234 (J.C.) and CHE-0957586 (A.J.). The experiments were performed in the Shared Instrument Facility of the Department of Chemistry, New York University, supported by the US National Science Foundation under Grant No. CHE0116222.


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.