Two-dimensional exchange NMR spectroscopy in fractionally deuterated molecules: Separation of exchange and cross-relaxation processes by proton dilution

Nenad Juranić, Zsolt Zolnai, Slobodan Macura

Research output: Contribution to journalArticle

2 Scopus citations

Abstract

The separation of cross-relaxation and chemical exchange is exploited by the difference in dependence on the degree of deuteration. The build-up rate of a normalized cross-peak from a proton-diluted spectrum is independent of the dilution for an exchange cross-peak, whereas it is proportional to the proton concentration for a cross-relaxation cross-peak. The method is demonstrated experimentally on the side chain NH2 protons of glutamine in aqueous solution with variable H2O/D2O ratio. The cross-relaxation between the non-equivalent NH2 protons is caused by their close proximity, whereas the chemical exchange is caused by the rotation of the whole NH2 group around the CN chemical bond. At 275 K and 500 MHz, in a fully protonated system, their cross-relaxation and chemical exchange rates are the same, 0.20 s-1. Hence, in a standard, either laboratory or rotating frame, exchange experiment the two processes cancel each other, leading to a false conclusion that neither chemical exchange nor cross-relaxation takes place. The separation of the two processes is of interest in the study of water-macromolecule interactions, in which the labile protons from a macromolecule exhibit simultaneous cross-relaxation and chemical exchange towards water protons. The short residence time of water molecules near the macromolecule precludes the use of alternative methods.

Original languageEnglish (US)
Pages (from-to)833-840
Number of pages8
JournalMolecular Physics
Volume95
Issue number5
DOIs
StatePublished - Dec 10 1998

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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