Ultratrace Metal Speciation Analysis by Coupling of Sector-Field ICP-MS to High-Resolution Size Exclusion and Reversed-Phase Liquid Chromatography
| Autor: | Hendrik Küpper, Lyudmila Lyubenova, Syed Nadeem Hussain Bokhari, Elisa Andresen, Noelia Jaime-Pérez, Nermeen Ashraf |
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| Rok vydání: | 2019 |
| Předmět: |
Detection limit
Chromatography Ion exchange Chemistry 010401 analytical chemistry Size-exclusion chromatography Reversed-phase chromatography 010402 general chemistry 01 natural sciences 0104 chemical sciences Analytical Chemistry Metal Matrix (chemical analysis) visual_art visual_art.visual_art_medium Inductively coupled plasma mass spectrometry Macromolecule |
| Zdroj: | Analytical Chemistry. 91:10961-10969 |
| ISSN: | 1520-6882 0003-2700 |
| DOI: | 10.1021/acs.analchem.9b00222 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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