Lead(II) binding to the chelating agent d-penicillamine in aqueous solution

Sisombath, Natalie S.; Jalilehvand, Farideh; Schell, Adam C.; Wu, Qiao

doi:10.1021/ic5018714

Title: Lead(II) binding to the chelating agent d-penicillamine in aqueous solution

Journal Article · Tue Nov 11 00:00:00 EST 2014 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic5018714· OSTI ID:1345619

Sisombath, Natalie S. ^[1]; Jalilehvand, Farideh ^[1]; Schell, Adam C. ^[1]; Wu, Qiao ^[1]

Univ. of Calgary, Calgary, AB (Canada)

Here, a spectroscopic investigation of the complexes formed between the Pb(II) ion and d-penicillamine (H₂Pen), a chelating agent used in the treatment of lead poisoning, was carried out on two sets of alkaline aqueous solutions with C_Pb(II) ≈ 10 and 100 mM, varying the H₂Pen/Pb(II) molar ratio (2.0, 3.0, 4.0, 10.0). Ultraviolet–visible (UV-vis) spectra of the 10 mM Pb(II) solutions consistently showed an absorption peak at 298 nm for S^– → Pb(II) ligand-to-metal charge-transfer. The downfield ¹³C NMR chemical shift for the penicillamine COO^– group confirmed Pb(II) coordination. The ²⁰⁷Pb NMR chemical shifts were confined to a narrow range between 1806 ppm and 1873 ppm for all Pb(II)-penicillamine solutions, indicating only small variations in the speciation, even in large penicillamine excess. Those chemical shifts are considerably deshielded, relative to the solid-state ²⁰⁷Pb NMR isotropic chemical shift of 909 ppm obtained for crystalline penicillaminatolead(II) with Pb(S,N,O-Pen) coordination. The Pb L_III-edge extended X-ray absorption fine structure (EXAFS) spectra obtained for these solutions were well-modeled with two Pb–S and two Pb-(N/O) bonds with mean distances 2.64 ± 0.04 Å and 2.45 ± 0.04 Å, respectively. The combined spectroscopic results, reporting δ(²⁰⁷Pb) ≈ 1870 ppm and λ_max ≈ 298 nm for a Pb^IIS₂NO site, are consistent with a dominating 1:2 lead(II):penicillamine complex with [Pb(S,N,O-Pen)(S-H_nPen)]^2–n (n = 0–1) coordination in alkaline solutions, and provide useful structural information on how penicillamine can function as an antidote against lead toxicity in vivo.

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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:: 1345619

Journal Information:: Inorganic Chemistry, Vol. 53, Issue 23; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 37 works

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