2000
DOI: 10.1021/jp994318t
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NMR Determination of the Magnetic Susceptibility Anisotropy of Cytochromec‘ ofRhodobacterCapsulatusby1JHNDipolar Coupling Constants Measurement: Characterization of Its Monomeric State in Solution

Abstract: J NH splittings have been measured at 600 and 400 MHz on the paramagnetic (S ) 2 and S ) 5 / 2 ) and on the diamagnetic state (S ) 0) of cytochrome c′ of Rhodobacter capsulatus. Residual dipolar splittings and the magnetic susceptibility tensor have been then derived using two methods. The first method equaled for a paramagnetic species the dipolar splitting to the difference of the measured 1 J NH splittings between the paramagnetic and diamagnetic forms at one field. The second method consisted in deriving t… Show more

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Cited by 28 publications
(17 citation statements)
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“…The NMR data likewise led to divergent conclusions regarding a spin-state admixture. The susceptibility tensor was perpendicular to the porphyrin plane and axially symmetric, in agreement with results obtained from a determination based on 1 J HN dipolar coupling and in accord with expectation for a predominantly high-spin ferric iron configuration. The pyrrole methyl signals showed strong downfield shifts.…”
Section: 42 Nmr Spectroscopysupporting
confidence: 88%
See 1 more Smart Citation
“…The NMR data likewise led to divergent conclusions regarding a spin-state admixture. The susceptibility tensor was perpendicular to the porphyrin plane and axially symmetric, in agreement with results obtained from a determination based on 1 J HN dipolar coupling and in accord with expectation for a predominantly high-spin ferric iron configuration. The pyrrole methyl signals showed strong downfield shifts.…”
Section: 42 Nmr Spectroscopysupporting
confidence: 88%
“…The active site structures of some ferrocytochromes c ‘ have also been studied by NMR, and molecular structural studies have been reported for both oxidized and reduced states. ,,, …”
Section: 42 Nmr Spectroscopymentioning
confidence: 99%
“…Determination of residual dipolar splittings is an alternative to the use of dipolar chemical shifts for the study of the metal-center magnetism in paramagnetic proteins (Déméné et al, 2000;Tolman et al, 1995;Banci et al, 1998). The magnetic susceptibility tensor can be derived from the difference between the corresponding 1 J HN values for the paramagnetic and diamagnetic species, measured at the same field, according to Eq.…”
Section: Determination Of the Magnetic Susceptibility Anisotropymentioning
confidence: 99%
“…NMR spectra of paramagnetic hemoproteins are unique in that not only can they, under appropriate conditions, be interpreted almost as effectively as for a diamagnetic analogue to yield the molecular structure, but the resulting hyperfine shifts near the active site yield a wealth of information on the electronic structure and magnetic properties of the active site not available for a diamagnetic derivative. ,, The majority of the systems studied possess low-spin, ferric hemin for which there exist relatively robust quantitative interpretive bases for both the contact and dipolar shifts. While fewer high-spin ferric hemoproteins have been investigated in detail, the results provide a relatively simple, and for the contact shifts only empirical, correlation between molecular structure and electronic/magnetic properties. , The least understood iron oxidation/spin state is high-spin iron(II) heme, which is the only functional paramagnetic state of globins, , one of two functional states 27 of ferricytochromes c ‘, as well as one in many heme enzymes. , …”
Section: Introductionmentioning
confidence: 99%