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• W2040881092 abstract "The effect of metal binding on the structure of ferrichrome in [2H6]Me2SO solutions at 45 °C, was studied by comparing the 13C spin-lattice relaxation of deferriferrichrome and alumichrome at 25.1 MHz. As has been found for other flexible cyclic oligopeptides, the metal-free siderophore exhibits consistent NT1 values for α-carbons with a marked trend towards smaller relaxation rates for sidechain carbons. The rotational correlation time, τr, calculated on the basis of the average NT1 for the cyclohexapeptide backbone, <NT1> = 93 ms, and under the assumption of isotropic motion is ≈ 0.56 ns. After binding Al3+ the overall carbon skeleton exhibits rather uniform N∗T1 values, with a mean value <N∗T1> = 125 ms which yields an effective τr ≈ 0.40 ns. Compared with the results for deferriferrichrome, these data indicate a more rigid compact structure with a faster rotational motion for the coordination compound. The 13C T1 values were also measured at 90.5 MHz. It was found that agreement between the low and high field data can be obtained by assuming the C-H bond to be somewhat longer than 1.09 Å. A consistent value for the alumichrome isotropic rotational correlation time, τr = 0.58 ns, was thus derived under the assumption that the effective <rCH> = 1.15 Å. Nuclear Overhauser enhancements as well as the T1 data indicate that at 25.1 MHz the 1H-13C dipolar interaction is the dominant relaxation mechanism for the various peptide carbonyls. The observations agree well with expectations fromσir−6CHIcalculations based on the crystallographic coordinates for the isomorphic analogue ferrichrome A." @default.
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• W2040881092 date "1977-05-01" @default.
• W2040881092 modified "2023-09-27" @default.
• W2040881092 title "A carbon-13 spin lattice relaxation study of alumichrome at 25.1 MHz and 90.5 MHz" @default.
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• W2040881092 doi "https://doi.org/10.1016/0005-2795(77)90208-2" @default.
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