Detection of intercatechol cross-links in insect cuticle by solid-state carbon-13 and nitrogen-15 NMR

Matthew E. Merritt, Allyson M. Christensen, Karl J. Kramer, Theodore L. Hopkins, Jacob Schaefer

Research output: Contribution to journalArticle

31 Scopus citations

Abstract

Solid-state NMR has been used to detect an intercatechol covalent bond in sclerotized cuticle of the tobacco hornworm (Manduca sexta). Rotational-echo, double-resonance (REDOR) 13C and 15N NMR, in combination with 1H-13C dipolar modulation and 15N-15N dipolar restoration at the magic angle, were used to examine hornworm pupal exuviae labeled with β-[15N]alanine and either [β-13C]dopamine or [α-13C,15N]dopamine. The REDOR spectra showed the incorporation of N-β-alanyldopamine into insect cuticle by the formation of a variety of covalent bonds. One of these bonds links the terminal nitrogen of one N-β-alanyldopamine molecule to the β carbon of another to form an intercatechol covalent bond. This result is interpreted in terms of a novel structure for stabilized cuticle that postulates protein-catechol-catechol-protein cross-links. REDOR spectra also showed oxygen substitution at both α and β carbons of N-β-alanyldopamine, consistent with the possibility of intercatechol oxygen bridges in dimeric or oligomeric forms of catecholamines in the cuticle.

Original languageEnglish (US)
Pages (from-to)11278-11282
Number of pages5
JournalJournal of the American Chemical Society
Volume118
Issue number45
DOIs
StatePublished - Nov 13 1996

ASJC Scopus subject areas

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

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    Merritt, M. E., Christensen, A. M., Kramer, K. J., Hopkins, T. L., & Schaefer, J. (1996). Detection of intercatechol cross-links in insect cuticle by solid-state carbon-13 and nitrogen-15 NMR. Journal of the American Chemical Society, 118(45), 11278-11282. https://doi.org/10.1021/ja961621o