The binding of nitric oxide at the Cu(I) site of copper nitrite reductase and of inorganic models: DFT calculations of the energetics and EPR parameters of side-on and end-on structures

Ganga Periyasamy, Mahesh Sundararajan, Ian H. Hillier, Neil A. Burton, Joseph J W McDouall

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Density functional theory calculations have been used to probe the end-on and side-on bonding motifs of nitric oxide at the Cu(I) centre in the enzyme copper nitrite reductase and in three inorganic model systems. We find that irrespective of a range of functionals used, the end-on structure is preferred by up to 40 kJ mol-1, although this preference is smaller for the enzyme than for the inorganic model systems. We have calculated the g-tensor and atomic hyperfine coupling constants for these structures. When compared to available experimental data, for one model compound the calculated EPR parameters definitely favour an end-on structure, although this preference is somewhat less for the enzyme. Our prediction of NO end-on binding in the enzyme is at variance with structural data. © the Owner Societies.
    Original languageEnglish
    Pages (from-to)2498-2506
    Number of pages8
    JournalPhysical Chemistry Chemical Physics
    Volume9
    Issue number20
    DOIs
    Publication statusPublished - 2007

    Keywords

    • g-factor (DFT calcns. of energetics and EPR parameters of side-on and end-on structures in nitric oxide binding at Cu(I) site of copper nitrite reductase and inorg. models)
    • Enzyme functional sites (active
    • DFT calcns. of energetics and EPR parameters of side-on and end-on structures in nitric oxide binding at Cu(I) site of copper nitrite reductase and inorg. models)
    • Bond energy (coordinate
    • Hyperfine coupling (isotropic
    • nitric oxide copper site model nitrite reductase DFT

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