Open AccessLead(II) Complex Formation with l -Cysteine in Aqueous Solution
Author(s) -
Farideh Jalilehvand,
Natalie S. Sisombath,
Adam C. Schell,
Glenn A. Facey
Publication year - 2015
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/ic5025668
Subject(s) - chemistry , aqueous solution , denticity , analytical chemistry (journal) , chemical shift , magic angle spinning , extended x ray absorption fine structure , chelation , nmr spectra database , nuclear chemistry , crystallography , nuclear magnetic resonance spectroscopy , absorption spectroscopy , inorganic chemistry , spectral line , stereochemistry , chromatography , crystal structure , physics , astronomy , quantum mechanics
The lead(II) complexes formed with the multidentate chelator L-cysteine (H2Cys) in an alkaline aqueous solution were studied using (207)Pb, (13)C, and (1)H NMR, Pb LIII-edge X-ray absorption, and UV-vis spectroscopic techniques, complemented by electrospray ion mass spectrometry (ESI-MS). The H2Cys/Pb(II) mole ratios were varied from 2.1 to 10.0 for two sets of solutions with CPb(II) = 0.01 and 0.1 M, respectively, prepared at pH values (9.1-10.4) for which precipitates of lead(II) cysteine dissolved. At low H2Cys/Pb(II) mole ratios (2.1-3.0), a mixture of the dithiolate [Pb(S,N-Cys)2](2-) and [Pb(S,N,O-Cys)(S-HCys)](-) complexes with average Pb-(N/O) and Pb-S distances of 2.42 ± 0.04 and 2.64 ± 0.04 Å, respectively, was found to dominate. At high concentration of free cysteinate (>0.7 M), a significant amount converts to the trithiolate [Pb(S,N-Cys)(S-HCys)2](2-), including a minor amount of a PbS3-coordinated [Pb(S-HCys)3](-) complex. The coordination mode was evaluated by fitting linear combinations of EXAFS oscillations to the experimental spectra and by examining the (207)Pb NMR signals in the chemical shift range δPb = 2006-2507 ppm, which became increasingly deshielded with increasing free cysteinate concentration. One-pulse magic-angle-spinning (MAS) (207)Pb NMR spectra of crystalline Pb(aet)2 (Haet = 2-aminoethanethiol or cysteamine) with PbS2N2 coordination were measured for comparison (δiso = 2105 ppm). The UV-vis spectra displayed absorption maxima at 298-300 nm (S(-) → Pb(II) charge transfer) for the dithiolate PbS2N(N/O) species; with increasing ligand excess, a shoulder appeared at ∼330 nm for the trithiolate PbS3N and PbS3 (minor) complexes. The results provide spectroscopic fingerprints for structural models for lead(II) coordination modes to proteins and enzymes.