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Title: Lead(II) complex formation with l-cysteine in aqueous solution

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic5025668· OSTI ID:1345620
 [1];  [1];  [1];  [2]
  1. Univ. of Calgary, Calgary, AB (Canada)
  2. Univ. of Ottawa, Ottawa, ON (Canada)

The lead(II) complexes formed with the multidentate chelator l-cysteine (H2Cys) in an alkaline aqueous solution were studied using 207Pb, 13C, and 1H NMR, Pb LIII-edge X-ray absorption, and UV–vis spectroscopic techniques, complemented by electrospray ion mass spectrometry (ESI-MS). The H2Cys/PbII mole ratios were varied from 2.1 to 10.0 for two sets of solutions with CPbII = 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/PbII 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 207Pb 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) 207Pb 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 → PbII 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. Finally, the results provide spectroscopic fingerprints for structural models for lead(II) coordination modes to proteins and enzymes.

Research Organization:
Univ. of Calgary, Calgary, AB (Canada)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1345620
Journal Information:
Inorganic Chemistry, Vol. 54, Issue 5; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 48 works
Citation information provided by
Web of Science

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Cited By (8)

Pre-concentration and determination of cadmium and lead ions in real water, soil and food samples using a simple and sensitive green solvent-based ultrasonic assisted dispersive liquid–liquid microextraction and graphite furnace atomic absorption spectrometry journal January 2018
Synthesis, characterization and biological activity of copper(II) complexes with ligands derived from β-amino acids journal August 2018
Comprehensive understanding of multiple binding of D-penicillamine with Cu2+-hexa aqua complex: a DFT approach journal July 2019
New Insights into the Configurations of Lead(II)-Benzohydroxamic Acid Coordination Compounds in Aqueous Solution: A Combined Experimental and Computational Study journal August 2018
A non-interpenetrating lead-organic framework with large channels based on 1D tube-shaped SBUs journal January 2017
l-Cysteine-Assisted Synthesis of Urchin-Like γ-MnS and Its Lithium Storage Properties journal October 2016
Novel Insights into the Configurations of Lead(II)-Benzohydroxamic Acid Coordination Compounds in Aqueous: A Combined Experimental and Computational Study journal June 2018
Comparative biochemical profile of protein-rich products obtained from industrial rapeseed meal journal January 2017

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