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Title: Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO)

Abstract

The toxicity of heavy metals such as lead (Pb), cadmium (Cd) and tin (Sn) has long been known but accidental exposures of large populations to these elements remain unfortunately a topical issue. Chelating agents against Pb, Cd, or Sn poisoning are still limited to classical ligands such as ethylenediamine tetraacetic acid (EDTA). In this paper, we evaluate the ability of 3,4,3-LI(1,2-HOPO) (L 4-), an octadentate ligand currently under evaluation for actinide decorporation, to bind Pb, Cd and Sn metal ions in aqueous solutions. This ligand forms 1 : 1 complexes with Pb(II), Cd(II) and Sn(IV) as well as bimetallic 2 : 1 species with Pb(II) and Cd(II), all of which were characterized by high resolution mass spectrometry and spectrophotometric titrations. The 3,4,3-LI(1,2-HOPO) ligand exhibits an extreme affinity for Sn(IV) ions (log β 110 > 40), with the complex remaining stable from highly acidic conditions to alkaline media (from 3 M HCl to pH 8). Single crystals of the neutral complex [Sn IV3,4,3-LI(1,2-HOPO)·3H 2O] were obtained and its structure determined, revealing a chiral conformation. Finally, although not initially designed for hexacoordinated metals such as Pb(II) and Cd(II), the octadentate ligand shows promise for the in vitro or in vivo sequestration ofmore » toxic heavy metals, as evidenced by decorporation experiments performed in mice contaminated with 210Pb(II) and treated with either EDTA or 3,4,3-LI(1,2-HOPO).« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Nuclear Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1458507
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
New Journal of Chemistry
Additional Journal Information:
Journal Volume: 42; Journal Issue: 10; Journal ID: ISSN 1144-0546
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Deblonde, Gauthier J. -P., Lohrey, Trevor D., An, Dahlia D., and Abergel, Rebecca J. Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO). United States: N. p., 2018. Web. doi:10.1039/c7nj04559j.
Deblonde, Gauthier J. -P., Lohrey, Trevor D., An, Dahlia D., & Abergel, Rebecca J. Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO). United States. doi:10.1039/c7nj04559j.
Deblonde, Gauthier J. -P., Lohrey, Trevor D., An, Dahlia D., and Abergel, Rebecca J. Fri . "Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO)". United States. doi:10.1039/c7nj04559j. https://www.osti.gov/servlets/purl/1458507.
@article{osti_1458507,
title = {Toxic heavy metal – Pb, Cd, Sn – complexation by the octadentate hydroxypyridinonate ligand archetype 3,4,3-LI(1,2-HOPO)},
author = {Deblonde, Gauthier J. -P. and Lohrey, Trevor D. and An, Dahlia D. and Abergel, Rebecca J.},
abstractNote = {The toxicity of heavy metals such as lead (Pb), cadmium (Cd) and tin (Sn) has long been known but accidental exposures of large populations to these elements remain unfortunately a topical issue. Chelating agents against Pb, Cd, or Sn poisoning are still limited to classical ligands such as ethylenediamine tetraacetic acid (EDTA). In this paper, we evaluate the ability of 3,4,3-LI(1,2-HOPO) (L4-), an octadentate ligand currently under evaluation for actinide decorporation, to bind Pb, Cd and Sn metal ions in aqueous solutions. This ligand forms 1 : 1 complexes with Pb(II), Cd(II) and Sn(IV) as well as bimetallic 2 : 1 species with Pb(II) and Cd(II), all of which were characterized by high resolution mass spectrometry and spectrophotometric titrations. The 3,4,3-LI(1,2-HOPO) ligand exhibits an extreme affinity for Sn(IV) ions (log β110 > 40), with the complex remaining stable from highly acidic conditions to alkaline media (from 3 M HCl to pH 8). Single crystals of the neutral complex [SnIV3,4,3-LI(1,2-HOPO)·3H2O] were obtained and its structure determined, revealing a chiral conformation. Finally, although not initially designed for hexacoordinated metals such as Pb(II) and Cd(II), the octadentate ligand shows promise for the in vitro or in vivo sequestration of toxic heavy metals, as evidenced by decorporation experiments performed in mice contaminated with 210Pb(II) and treated with either EDTA or 3,4,3-LI(1,2-HOPO).},
doi = {10.1039/c7nj04559j},
journal = {New Journal of Chemistry},
issn = {1144-0546},
number = 10,
volume = 42,
place = {United States},
year = {2018},
month = {2}
}

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    Works referencing / citing this record:

    Forensic Estimates of Lead Release from Lead Service Lines during the Water Crisis in Flint, Michigan
    journal, July 2017

    • Olson, Terese M.; Wax, Madeleine; Yonts, James
    • Environmental Science & Technology Letters, Vol. 4, Issue 9
    • DOI: 10.1021/acs.estlett.7b00226

    Cadmium Toxicity and Treatment
    journal, January 2013


    New Insights into Structure and Luminescence of Eu III and Sm III Complexes of the 3,4,3-LI(1,2-HOPO) Ligand
    journal, February 2015

    • Daumann, Lena J.; Tatum, David S.; Snyder, Benjamin E. R.
    • Journal of the American Chemical Society, Vol. 137, Issue 8
    • DOI: 10.1021/ja5116524

    Optimized Relaxivity and Stability of [Gd(H(2,2)-1,2-HOPO)(H 2 O)] - for Use as an MRI Contrast Agent 1
    journal, June 2007

    • Jocher, Christoph J.; Botta, Mauro; Avedano, Stefano
    • Inorganic Chemistry, Vol. 46, Issue 12
    • DOI: 10.1021/ic700399p

    Chelating Agents for Uranium(Vi): 2. Efficacy and Toxicity of Tetradentate Catecholate and Hydroxypyridinonate Ligands in mice
    journal, January 2000


    Chelation and stabilization of berkelium in oxidation state +IV
    journal, April 2017

    • Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.
    • Nature Chemistry, Vol. 9, Issue 9
    • DOI: 10.1038/nchem.2759

    Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones
    journal, January 2019

    • Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; Abergel, Rebecca J.
    • Dalton Transactions, Vol. 48, Issue 23
    • DOI: 10.1039/c9dt01031a

    Using the Antenna Effect as a Spectroscopic Tool: Photophysics and Solution Thermodynamics of the Model Luminescent Hydroxypyridonate Complex [Eu III (3,4,3-LI(1,2-HOPO))]
    journal, December 2009

    • Abergel, Rebecca J.; D’Aléo, Anthony; Ng Pak Leung, Clara
    • Inorganic Chemistry, Vol. 48, Issue 23
    • DOI: 10.1021/ic9013703

    Chelation of cadmium.
    journal, March 1984


    Hydroxypyridinonate Complex Stability of Group (IV) Metals and Tetravalent f-Block Elements: The Key to the Next Generation of Chelating Agents for Radiopharmaceuticals
    journal, March 2015


    Alternative Chelator for 89 Zr Radiopharmaceuticals: Radiolabeling and Evaluation of 3,4,3-(LI-1,2-HOPO)
    journal, December 2013

    • Deri, Melissa A.; Ponnala, Shashikanth; Zeglis, Brian M.
    • Journal of Medicinal Chemistry, Vol. 57, Issue 11
    • DOI: 10.1021/jm500389b

    p -SCN-Bn-HOPO: A Superior Bifunctional Chelator for 89 Zr ImmunoPET
    journal, November 2015


    Four phases of the Flint Water Crisis: Evidence from blood lead levels in children
    journal, August 2017


    Redox behavior of Ce(IV)/Ce(III) in the presence of nitrilotriacetic acid: A surrogate study for An(IV)/An(III) redox behavior
    journal, January 2010

    • Suzuki, Yoshinori; Nankawa, T.; Francis, Arokiasamy J.
    • Radiochimica Acta, Vol. 98, Issue 7
    • DOI: 10.1524/ract.2010.1735

    Solution thermodynamic evaluation of hydroxypyridinonate chelators 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO) for UO 2 (VI) and Th(IV) decorporation
    journal, June 2013

    • Sturzbecher-Hoehne, M.; Deblonde, G. J. -P.; Abergel, R. J.
    • Radiochimica Acta, Vol. 101, Issue 6
    • DOI: 10.1524/ract.2013.2047

    From early prophylaxis to delayed treatment: Establishing the plutonium decorporation activity window of hydroxypyridinonate chelating agents
    journal, April 2017

    • An, Dahlia D.; Kullgren, Birgitta; Jarvis, Erin E.
    • Chemico-Biological Interactions, Vol. 267
    • DOI: 10.1016/j.cbi.2016.03.034

    3,4,3-LI(1,2-HOPO): In vitro formation of highly stable lanthanide complexes translates into efficacious in vivo europium decorporation
    journal, January 2011

    • Sturzbecher-Hoehne, Manuel; Ng Pak Leung, Clara; D'Aléo, Anthony
    • Dalton Transactions, Vol. 40, Issue 33
    • DOI: 10.1039/c1dt10840a

    Gross Composition and Plasma and Extracellular Water Volumes of Tissues of a Reference Mouse
    journal, January 1992


    Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones
    journal, January 2019

    • Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; Abergel, Rebecca J.
    • Dalton Transactions, Vol. 48, Issue 23
    • DOI: 10.1039/c9dt01031a