Lanthanide Induced Shift and Relaxation Rate Studies of Aqueous L-Proline Solutions

Mangal Singh, Joe J. Reynolds, A. Dean Sherry

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Abstract

The structure of aqueous L-proline at pH 3 has been studied with use of the lanthanide-induced-shift technique. Paramagnetic nuclear shifts and enhancement of nuclear-relaxation rates have been measured for all 13C and 1H nuclei of L-proline in the presence of ten different lanthanide cations. The relaxation-rate data indicate that isostructural complexes are formed between proline and all ten lanthanide cations. An attempted separation of the observed lanthanide-induced shifts into pseudocontact and contact components with use of the Reilley method (C. N. Reilley, B. W. Good, and R. D. Allendoerfer, Anal. Chem., 48, 1446 (1976)) gave inconsistent results for the α and carboxyl carbons indicating that either the shifts at these nuclei have a nonaxial dipolar contribution or the hyperfine coupling constant is lanthanide ion dependent. The pseudocontact shifts at Cβ, Cγ, and CΔ and at all protons conform well to the axial symmetry model with the lanthanide ion principal symmetry axis intersecting a single oxygen atom 2.9 ±0.1 Å from the lanthanide cation.

Original languageEnglish (US)
Pages (from-to)4172-4177
Number of pages6
JournalJournal of the American Chemical Society
Volume105
Issue number13
DOIs
StatePublished - Jun 1983

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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