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- W2028781749 abstract "The complex formation between cadmium(II) and the ligands cysteine (H2Cys) and penicillamine (H2Pen = 3,3′-dimethylcysteine) in aqueous solutions, having CCd(II) ∼ 0.1 mol dm−3 and CH2L = 0.2−2 mol dm−3, was studied at pH = 7.5 and 11.0 by means of 113Cd NMR and Cd K- and L3-edge X-ray absorption spectroscopy. For all cadmium(II)−cysteine molar ratios, the mean Cd−S and Cd−(N/O) bond distances were found in the ranges 2.52−2.54 and 2.27−2.35 Å, respectively. The corresponding cadmium(II)−penicillamine complexes showed slightly shorter Cd−S bonds, 2.50−2.53 Å, but with the Cd−(N/O) bond distances in a similar wide range, 2.28−2.33 Å. For the molar ratio CH2L/CCd(II) = 2, the 113Cd chemical shifts, in the range 509−527 ppm at both pH values, indicated complexes with distorted tetrahedral CdS2N(N/O) coordination geometry. With a large excess of cysteine (molar ratios CH2Cys/CCd(II) ≥ 10), complexes with CdS4 coordination geometry dominate, consistent with the 113Cd NMR chemical shifts, δ ∼ 680 ppm at pH 7.5 and 636−658 ppm at pH 11.0, and their mean Cd−S distances were 2.53 ± 0.02 Å. At pH 7.5, the complexes are almost exclusively sulfur-coordinated as [Cd(S-cysteinate)4]n−, while at higher pH, the deprotonation of the amine groups promotes chelate formation. At pH 11.0, a minor amount of the [Cd(Cys)3]4− complex with CdS3N coordination is formed. For the corresponding penicillamine solutions with molar ratios CH2Pen/CCd(II) ≥ 10, the 113Cd NMR chemical shifts, δ ∼ 600 ppm at pH 7.5 and 578 ppm at pH 11.0, together with the average bond distances, Cd−S 2.53 ± 0.02 Å and Cd−(N/O) 2.30−2.33 Å, indicate that [Cd(penicillaminate)3]n− complexes with chelating CdS3(N/O) coordination dominate already at pH 7.5 and become mixed with CdS2N(N/O) complexes at pH 11.0. The present study reveals differences between cysteine and penicillamine as ligands to the cadmium(II) ion that can explain why cysteine-rich metallothionines are capable of capturing cadmium(II) ions, while penicillamine, clinically useful for treating the toxic effects of mercury(II) and lead(II) exposure, is not efficient against cadmium(II) poisoning." @default.
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- W2028781749 date "2009-05-26" @default.
- W2028781749 modified "2023-10-05" @default.
- W2028781749 title "Cadmium(II) Complex Formation with Cysteine and Penicillamine" @default.
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- W2028781749 doi "https://doi.org/10.1021/ic802278r" @default.
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