Add time:08/31/2019         Source:sciencedirect.com

Iron(II) complexes, (Et4N)2[Fe(ZcysAlaAlacysOMe)2] (1) and (Et4N)2[Fe(ZcysAlaProcysOMe)2] (2), were synthesized by reaction of the corresponding SH-free peptides with (Et4N)2[Fe(StBu)4]. 1 and 2 give redox potentials at −0.49 and −0.58 V versus SCE in acetonitrile, respectively. The negatively shifted redox potential observed in 2 was explained by the lower contribution of NHS hydrogen bonds. In the 2H NMR spectra of 1 and 2 using N-deuterated cysteine peptide ligands, [Fe(Zcys(1)AlaProcys(2)OMe)2]2− (2) exhibits isotropically shifted N2H signals at 24.5 and 22.8 ppm in acetonitrile at 30 °C which were assigned to N2H of the cys(2) residue due to the formation of a Cys(2)-N2HS-Cys(1) hydrogen bond while [Fe(Zcys(1)Ala(1)Ala(2)cys(2)OMe)2]2− (1) gives signals at 33.3, 29.2 and −3.6 ppm due to the hydrogen bonds of Cys(2)-N2H SCys(1) and Ala(2)N2HSCys(1), respectively.

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