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

    Fogolari, F., Esposito, G., Cattarinussi, S., & Viglino, P. (1996). Quantitative analysis of total correlation spectra: Application to small biomolecules. Concepts in Magnetic Resonance, 8(4), 229-249.

    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

    Fogolari, F, Esposito, G, Cattarinussi, S & Viglino, P 1996, 'Quantitative analysis of total correlation spectra: Application to small biomolecules', Concepts in Magnetic Resonance, vol. 8, no. 4, pp. 229-249.
    Fogolari F, Esposito G, Cattarinussi S, Viglino P. Quantitative analysis of total correlation spectra: Application to small biomolecules. Concepts in Magnetic Resonance. 1996 Dec 1;8(4):229-249.
    Fogolari, F. ; Esposito, Gennaro ; Cattarinussi, S. ; Viglino, P. / Quantitative analysis of total correlation spectra : Application to small biomolecules. In: Concepts in Magnetic Resonance. 1996 ; Vol. 8, No. 4. pp. 229-249.
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