Quantitative analysis of total correlation spectra: Application to small biomolecules

F. Fogolari, Gennaro Esposito, S. Cattarinussi, P. Viglino

Research output: Contribution to journalArticle

Abstract

The peak intensities of total correlation spectra are intimately related to J-coupling constants, which in turn are related to local geometry. Knowledge of J values is therefore useful in determining molecular structure. In the past, the complexity of the time development of total correlation cross-peaks has hindered their use in extracting structural information. This paper reviews the relevant quantum-mechanical equations. The series expansion of the density matrix for the most general spin-1/2 system undergoing isotropic mixing offers a convenient approximation that can be exploited to evaluate the extent of net transfer as a function of J values. A method for evaluating J-coupling constants from total correlation spectra of small biomolecules is presented as an application and as an illustration of the theory. Peak amplitude quantitation of short-mixing-time spectra provides tentative estimates of scalar couplings (accurate up to the third order of the series expansion as a function of mixing time). These estimates can be further refined by fitting the experimental data with theoretical transfers obtained by a full density matrix calculation. An experimental illustration of the method is given for a nucleic acid and a coenzyme system, although the conclusions should hold for every similar spin system.

Original languageEnglish (US)
Pages (from-to)229-249
Number of pages21
JournalConcepts in Magnetic Resonance
Volume8
Issue number4
StatePublished - Dec 1 1996

Fingerprint

Biomolecules
quantitative analysis
series expansion
Chemical analysis
coenzymes
Coenzymes
nucleic acids
estimates
cross correlation
Nucleic Acids
Molecular structure
molecular structure
scalars
Geometry
geometry
approximation

ASJC Scopus subject areas

  • Chemistry(all)
  • Spectroscopy
  • Physical and Theoretical Chemistry

Cite this

Quantitative analysis of total correlation spectra : Application to small biomolecules. / Fogolari, F.; Esposito, Gennaro; Cattarinussi, S.; Viglino, P.

In: Concepts in Magnetic Resonance, Vol. 8, No. 4, 01.12.1996, p. 229-249.

Research output: Contribution to journalArticle

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