| Metal cation detection in positive ion mode electrospray ionization mass spectrometry using a tetracationic salt as a gas-phase ion-pairing agent: Evaluation of the effect of chelating agents on detection sensitivity. | |
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MedLine Citation:
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PMID: 23136019 Owner: NLM Status: In-Data-Review |
Abstract/OtherAbstract:
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RATIONALE: The detection of metal cations continues to be essential in many scientific and industrial areas of interest. The most common electrospray ionization mass spectrometry (ESI-MS) approach involves chelating the metal ions and detecting the organometallic complex in the negative ion mode. However, it is well known that negative ion mode ESI-MS is generally less sensitive than the positive ion mode. To achieve greater sensitivity, it is necessary to examine the feasibility of detecting the chelated metal cations in positive ion mode ESI-MS. METHODS: Since highly solvated native metal cations have relatively low ionization efficiency in ESI-MS, and can be difficult to detect in the positive ion mode, a tetracationic ion-pairing agent was added to form a complex with the negatively charged metal chelate. The use of the ion-pairing agent leads to the generation of an overall positively charged complex, which can be detected at higher m/z values in the positive ion mode by electrospray ionization linear quadrupole ion trap mass spectrometry. RESULTS: Thirteen chelating agents with diverse structures were evaluated in this study. The nature of the chelating agent played as important a role as was previously determined for cationic pairing agents. The detection limits of six metal cations reached sub-picogram levels and significant improvements were observed when compared to negative ion mode detection where the metal-chelates were monitored without adding the ion-pairing reagent (IPR). Also, selective reaction monitoring (SRM) analyses were performed on the ternary complexes, which improved detection limits by one to three orders of magnitude. CONCLUSIONS: With this method it was possible to analyze the metal cations in the positive ion mode ESI-MS with the advantage of speed, sensitivity and selectivity. The optimum solution pH for this type of analysis is 5-7. Tandem mass spectrometry (MS/MS) further increases the sensitivity. Speciation is straightforward making this a broadly useful approach for the analysis of metal ions. Copyright © 2012 John Wiley & Sons, Ltd. |
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Authors:
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Chengdong Xu; Edra Dodbiba; Nilusha L T Padivitage; Zachary S Breitbach; Daniel W Armstrong |
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Publication Detail:
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Type: Journal Article |
Journal Detail:
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Title: Rapid communications in mass spectrometry : RCM Volume: 26 ISSN: 1097-0231 ISO Abbreviation: Rapid Commun. Mass Spectrom. Publication Date: 2012 Dec |
Date Detail:
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Created Date: 2012-11-08 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 8802365 Medline TA: Rapid Commun Mass Spectrom Country: England |
Other Details:
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Languages: eng Pagination: 2885-96 Citation Subset: IM |
Copyright Information:
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Copyright © 2012 John Wiley & Sons, Ltd. |
Affiliation:
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Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, TX, 76019, USA. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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