Solid-State NMR of N-Acylureas Derived from the Reaction of Hyaluronic Acid with Isotopically-Labeled Carbodiimides

Tara Pouyani, Jing Wen Kuo, Gerard S. Harbison, Glenn D. Prestwich

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Abstract

Hyaluronic acid (HA) is a naturally-occurring linear polysaccharide consisting of alternating D-glucuronic acid and fV-acetyl-D-glucosamine residues. Reaction of the carboxyl group of the glucuronate residues with 1-ethyl-3-(3-(dimethylamino) propyl)carbodiimide (EDC) in the presence of primary amines yielded only the N-acylurea adducts rather than the expected amide coupling products. To determine the nature of this linkage unambiguously and to deduce the primary structure of the N-acylurea products, 13C- and 15N-labeled 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide were synthesized. The isotopically-labeled carbodiimides were coupled to the carboxyl group of HA (molecular size ca. 2000000 Da) in water at pH = 4.75. The modified polysaccharides were then isolated, purified, and examined by cross polarization and magic angle spinning (CP-MAS) solid-state 13C and 15N NMR. The chemical shifts and states of protonation of the nitrogens confirmed the presence of two isomeric N-acylureas in unequal amounts and ruled out the presence of any unrearranged O-acylurea product.

Original languageEnglish (US)
Pages (from-to)5972-5976
Number of pages5
JournalJournal of the American Chemical Society
Volume114
Issue number15
DOIs
Publication statusPublished - Jul 1 1992

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ASJC Scopus subject areas

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

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