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Nuclear magnetic resonance and potentiometric studies of the complexation of methylmercury(II) by dithiols

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Arnold, AP and Canty, AJ and Reid, RS and Rabenstein, DL (1985) Nuclear magnetic resonance and potentiometric studies of the complexation of methylmercury(II) by dithiols. Canadian Journal of Chemistry, 63 (9). pp. 2430-2436. ISSN 0008-4042

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Abstract

Complexation of methylmercury, CH3Hg(II), by 2,3-dimercaptosuccinic acid (DMSA), 2,3-dimercaptopropanesulfonate (DMPS, Unithiol), dithioerythritol (DTE), and 2,3-dimercaptopropanol (British Anti-Lewisite, BAL) has been studied by 1H nuclear magnetic resonance spectroscopy and by potentiometric titration. In the nmr study, the equilibrium constants for displacement of mercaptoacetate from its CH3Hg(II) complex by the dithiols were determined over a wide pH range, from mercaptoacetate chemical shift data. Similar competition reactions between the dithiols and mercaptoethanol were used in the potentiometric study. Using previously determined CH3Hg(II) formation constants for the competing ligands, equilibrium constants for the formation of mono-and bis-CH3Hg(II) complexes with the dithiols have been determined. The formation constants for the mono-CH3Hg(II) complexes with the vicinal dithiols BAL and DMPS are significantly higher than expected by consideration of the basicity of the sulfhydryl donors, in comparison with those for DMSA, non-vicinal DTE, and monothiols. We interpret this to indicate chelation of CH3Hg(II) by BAL and DMPS but not by DMSA. The conditional formation constants at physiological pH are discussed with reference to the effectiveness of BAL, DMPS, and DMSA as antidotes for methylmercury poisoning. In particular, the constants obtained indicate that, for dithiol antidotes at concentrations greater than that of methylmercury(II), methylmercury(II) complexes formed at physiological pH are of 1:1 stoichiometry. For BAL, a substantial proportion of the complex will be in the neutral form, in contrast to DMPS and DMSA which form anionic species only.

Item Type: Article
Journal or Publication Title: Canadian Journal of Chemistry
Page Range: pp. 2430-2436
ISSN: 0008-4042
Identification Number - DOI: 10.1139/v85-402
Additional Information: Copyright 1985. National Research Council. Please refer to the journal link for access to the definitive, published version. Under the Canadian Copyright Act, individuals may download or print single copies of articles for personal research or study. Any person may reproduce short excerpts from articles in the journals for any purpose that respects the moral rights of authors, provided that the source is fully acknowledged. As a courtesy, the consent of authors of such material should be obtained directly from the author.
Date Deposited: 18 Feb 2008 02:54
Last Modified: 18 Nov 2014 03:30
URI: http://eprints.utas.edu.au/id/eprint/3216
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