Electrolyte-induced ionization suppression and microcystin toxins : ammonium formate suppresses sodium replacement ions and enhances protiated and ammoniated ions for improved specificity in quantitative LC-MS-MS
This study examines the effects of electrolytes on microcystin (MC) electrospray ionization (ESI) mass spectrometry and quantitative LC-MS-MS. Sodium replacement ions (SRI) are prominent in MC ESI spectra in protic solvents such as HPLC grade methanol. In a methanol-water-0.006% acetic acid (v/v) gradient, envelopes with up to 11 SRI were apparent in both the +1 and +2 charge states with structures [M + Na(x) - (x-1)H](+) and [M + Na(x) - (x-2)H](+2). The m/z 135 product ion, [Ø-CH(2)-CH=O-CH(3)](+), widely used in tandem LC-MS-MS determination of MC, is a low collision energy fragment of many doubly charged MC precursor ions (e.g., [M+Na+H](+2), [M+Na+NH(4)](+2), M+Na+H+CH(3)OH](+2), [M+2H](+2)). These phenomena impair congener-specific LC-MS-MS detection of MC and degrade quantitative accuracy and precision. Pulse addition experiments established that ammonium formate (AF) strongly suppresses SRI in both +1 and +2 charge states and enhances MH(+) and MNH(4)(+) adducts in neutral MC. Addition of the buffer either post-column or by incorporation in the mobile phase increases specificity for all of the MC which were determined as the MNH(4)(+) > MH(+) and MH(+) > [MH - 134](+) transitions for neutral MC (MCLA, MCLF, MCLW) and [M+2H](+2) > 135(+) and [M+2H](+2) > [M+2H - 135](+) transitions for arginine-containing MC (MCLR, MCYR, MCRR). These findings shed light on mechanisms of electrolyte-induced ionization suppression, and demonstrate beneficial use of a buffer electrolyte for improved specificity and analytical ruggedness in quantitative LC-MS-MS.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2009 |
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| Erschienen: |
2009 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:81 |
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| Enthalten in: |
Analytical chemistry - 81(2009), 10 vom: 15. Mai, Seite 4153-60 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Draper, William M [VerfasserIn] |
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| Links: |
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| Themen: |
0YIW783RG1 |
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| Anmerkungen: |
Date Completed 09.07.2009 Date Revised 25.11.2016 published: Print Citation Status MEDLINE |
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| doi: |
10.1021/ac802735t |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM187890986 |
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| 100 | 1 | |a Draper, William M |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Electrolyte-induced ionization suppression and microcystin toxins |b ammonium formate suppresses sodium replacement ions and enhances protiated and ammoniated ions for improved specificity in quantitative LC-MS-MS |
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| 500 | |a Date Revised 25.11.2016 | ||
| 500 | |a published: Print | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a This study examines the effects of electrolytes on microcystin (MC) electrospray ionization (ESI) mass spectrometry and quantitative LC-MS-MS. Sodium replacement ions (SRI) are prominent in MC ESI spectra in protic solvents such as HPLC grade methanol. In a methanol-water-0.006% acetic acid (v/v) gradient, envelopes with up to 11 SRI were apparent in both the +1 and +2 charge states with structures [M + Na(x) - (x-1)H](+) and [M + Na(x) - (x-2)H](+2). The m/z 135 product ion, [Ø-CH(2)-CH=O-CH(3)](+), widely used in tandem LC-MS-MS determination of MC, is a low collision energy fragment of many doubly charged MC precursor ions (e.g., [M+Na+H](+2), [M+Na+NH(4)](+2), M+Na+H+CH(3)OH](+2), [M+2H](+2)). These phenomena impair congener-specific LC-MS-MS detection of MC and degrade quantitative accuracy and precision. Pulse addition experiments established that ammonium formate (AF) strongly suppresses SRI in both +1 and +2 charge states and enhances MH(+) and MNH(4)(+) adducts in neutral MC. Addition of the buffer either post-column or by incorporation in the mobile phase increases specificity for all of the MC which were determined as the MNH(4)(+) > MH(+) and MH(+) > [MH - 134](+) transitions for neutral MC (MCLA, MCLF, MCLW) and [M+2H](+2) > 135(+) and [M+2H](+2) > [M+2H - 135](+) transitions for arginine-containing MC (MCLR, MCYR, MCRR). These findings shed light on mechanisms of electrolyte-induced ionization suppression, and demonstrate beneficial use of a buffer electrolyte for improved specificity and analytical ruggedness in quantitative LC-MS-MS | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a Research Support, U.S. Gov't, P.H.S. | |
| 650 | 7 | |a Formates |2 NLM | |
| 650 | 7 | |a Ions |2 NLM | |
| 650 | 7 | |a Microcystins |2 NLM | |
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| 650 | 7 | |a Sodium |2 NLM | |
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| 700 | 1 | |a Xu, Dadong |e verfasserin |4 aut | |
| 700 | 1 | |a Perera, S Kusum |e verfasserin |4 aut | |
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