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Stabilization of hydrolytically labile iron(II)–cysteine peptide thiolate complexes in aqueous triton X-100 micelle solution: Spectroscopic properties mimicking of reduced rubredoxin

✍ Scribed by Wei-Yin Sun; Norikazu Ueyama; Akira Nakamura


Publisher
Wiley (John Wiley & Sons)
Year
1998
Tongue
English
Weight
121 KB
Volume
46
Category
Article
ISSN
0006-3525

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✦ Synopsis


The absorption, CD, and 1 H-and 19 F-nmr spectroscopic features of Fe(II) complexes with a series of cysteine-containing oligopeptides were investigated in aqueous (H 2 O or D 2 O) 10% Triton X-100 micelle solution. The complexes with distal aromatic rings, [Fe(Zcys-Pro-Leu-cys-Gly-X) 2 ] 20 (Z Å benzyloxycarbonyl; X Å NH-C 6 H 4 -p-F, NH-CH 2 -CH 2 -C 6 H 4p-F, and Phe-OMe), were found to be quite stable in such aqueous micelle solution. The coordination of cysteine-peptide ligands to the Fe(II) ion is revealed by isotropically shifted 1 H-nmr signals due to the Cys C b H 2 protons occurring at 120 Ç 250 ppm in a D 2 O Triton X-100 micelle solution (10%) at 60ЊC that are very similar to those reported for native reduced rubredoxin. The high stability of these cysteine peptide-Fe(II) complexes in aqueous micellar system was explained by the combined contributions from NH{S hydrogen bonds and the effect of the proximity of aromatic groups. The existence of such NH{S hydrogen bonds and interactions between aromatic ring and sulfur atom was confirmed by 19 F-nmr spectral and 19 F spin-lattice relaxation times (T 1 ) measurements.