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Ultratrace Metal Speciation Analysis by Coupling of Sector-Field ICP-MS to High-Resolution Size Exclusion and Reversed-Phase Liquid Chromatography
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    Ultratrace Metal Speciation Analysis by Coupling of Sector-Field ICP-MS to High-Resolution Size Exclusion and Reversed-Phase Liquid Chromatography
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    • Hendrik Küpper*
      Hendrik Küpper
      Department of Plant Biophysics and Biochemistry, Institute of Plant Molecular Biology, Biology Center of the Czech Academy of Sciences, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
      Department of Experimental Plant Biology, University of South Bohemia, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
      *E-mail: [email protected]
    • Syed Nadeem Hussain Bokhari
      Syed Nadeem Hussain Bokhari
      Department of Plant Biophysics and Biochemistry, Institute of Plant Molecular Biology, Biology Center of the Czech Academy of Sciences, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
    • Noelia Jaime-Pérez
      Noelia Jaime-Pérez
      Department of Plant Biophysics and Biochemistry, Institute of Plant Molecular Biology, Biology Center of the Czech Academy of Sciences, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
    • Lyudmila Lyubenova
      Lyudmila Lyubenova
      Department of Plant Biophysics and Biochemistry, Institute of Plant Molecular Biology, Biology Center of the Czech Academy of Sciences, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
    • Nermeen Ashraf
      Nermeen Ashraf
      Department of Plant Biophysics and Biochemistry, Institute of Plant Molecular Biology, Biology Center of the Czech Academy of Sciences, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
      Department of Experimental Plant Biology, University of South Bohemia, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
    • Elisa Andresen
      Elisa Andresen
      Department of Plant Biophysics and Biochemistry, Institute of Plant Molecular Biology, Biology Center of the Czech Academy of Sciences, Branišovská 31/1160, 370 05 České Budějovice, Czech Republic
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    Analytical Chemistry

    Cite this: Anal. Chem. 2019, 91, 17, 10961–10969
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    https://doi.org/10.1021/acs.analchem.9b00222
    Published August 2, 2019
    Copyright © 2019 American Chemical Society

    Abstract

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    Techniques for metal speciation analysis with subnanomolar (ppt) detection limits in complex matrices, with simultaneous quantification of matrix elements, have become a necessity for investigating targets of trace metal binding to macromolecules and pigments at environmentally relevant concentrations. In this work we optimized the analysis of such metal binding in a custom-built HPLC-ICP-MS system. Key elements of the optimization were the choice of components for the metal-free HPLC-DAD system and sector-field ICP-MS detection (ICF-sfMS) with desolvating injection and optimization of sample handling. Protein analysis was done using ammonium bicarbonate buffer and size exclusion chromatography (SEC-ICP-sfMS), with possible addition of anion exchange chromatography. Detection of metal exchange in pigments (chlorophylls and bacteriochlorophylls) was based on reversed-phase chromatography with a methanol-acetone gradient and coupling to the ICP-sfMS via a dedicated organic matrix interface (RPC-ICP-sfMS). The resulting HPLC-DAD-ICP-sfMS system has detection limits in the picomolar range in protein buffer, limited by the maximal achievable purity of buffers/solvents and not by system sensitivity. Tests for method optimization showed that sonication, meant to increase protein solubilization, leads to artifacts of metal loss from metalloproteins. Examples for Cd binding to soybean proteins and chlorophyll, Cr binding to Arabidopsis thaliana proteins, La binding to Desmodesmus quadricauda proteins, and Cu binding to Rhodospirillum rubrum proteins and pigments are shown. These application examples demonstrate that the system is sensitive enough to detect binding of metals to proteins and pigments at background concentration levels of typical nutrient solutions made from analytical grade chemicals, equivalent to ultratrace metal concentrations in nonpolluted environments.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem.9b00222.

    • Table S1, examples ICP-MS methods optimized for measurements shown in this work; Figure S1, analysis of copper abundance in a LH1 preparation from Rhodospirillum rubrum grown on 2 μM Cu2+; and Figure S2, measurement of a [Cd]-Chl standard (PDF)

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    Cited By

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    This article is cited by 24 publications.

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    Analytical Chemistry

    Cite this: Anal. Chem. 2019, 91, 17, 10961–10969
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.analchem.9b00222
    Published August 2, 2019
    Copyright © 2019 American Chemical Society

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