Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform
Based on current structural and statistical calculations, thousands of microcystins (MCs) can exist; yet, to date, only 246 MCs were identified and only 12 commercial MC standards are available. Standard mass spectrometry workflows for known and unknown MCs need to be developed and validated for bas...
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-11-01
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| Series: | Toxins |
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| Online Access: | https://www.mdpi.com/2072-6651/11/11/653 |
| _version_ | 1811300990158110720 |
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| author | Johnna A. Birbeck Nicholas J. Peraino Grace M. O’Neill Julia Coady Judy A. Westrick |
| author_facet | Johnna A. Birbeck Nicholas J. Peraino Grace M. O’Neill Julia Coady Judy A. Westrick |
| author_sort | Johnna A. Birbeck |
| collection | DOAJ |
| description | Based on current structural and statistical calculations, thousands of microcystins (MCs) can exist; yet, to date, only 246 MCs were identified and only 12 commercial MC standards are available. Standard mass spectrometry workflows for known and unknown MCs need to be developed and validated for basic and applied harmful algal bloom research to advance. Our investigation focuses on samples taken in the spring of 2018 from an impoundment fed by Oser and Bischoff Reservoirs, Indiana, United States of America (USA). The dominant cyanobacterium found during sampling was <i>Planktothrix agardhii</i>. The goal of our study was to identify and quantify the MCs in the impoundment sample using chemical derivatization and mass spectrometry. Modifying these techniques to use online concentration liquid chromatography tandem mass spectrometry (LC−MS/MS), two untargeted MCs have been identified, [<span style="font-variant: small-caps;">d</span>-Asp<sup>3</sup>, Dhb<sup>7</sup>]-MC-LR and [Dhb<sup>7</sup>]-MC-YR. [Dhb<sup>7</sup>]-MC-YR is not yet reported in the literature to date, and this was the first reported incidence of Dhb MCs in the United States. Furthermore, it was discovered that the commercially available [<span style="font-variant: small-caps;">d</span>-Asp<sup>3</sup>]-MC-RR standard was [<span style="font-variant: small-caps;">d</span>-Asp<sup>3</sup>, Dhb<sup>7</sup>]-MC-RR. This study highlights a workflow utilizing online concentration LC−MS/MS, high-resolution MS (HRMS), and chemical derivatization to identify isobaric MCs. |
| first_indexed | 2024-04-13T07:00:44Z |
| format | Article |
| id | doaj.art-33a0896c54c649cc9a3673117119a9b0 |
| institution | Directory Open Access Journal |
| issn | 2072-6651 |
| language | English |
| last_indexed | 2024-04-13T07:00:44Z |
| publishDate | 2019-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Toxins |
| spelling | doaj.art-33a0896c54c649cc9a3673117119a9b02022-12-22T02:57:07ZengMDPI AGToxins2072-66512019-11-01111165310.3390/toxins11110653toxins11110653Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS PlatformJohnna A. Birbeck0Nicholas J. Peraino1Grace M. O’Neill2Julia Coady3Judy A. Westrick4Department of Chemistry, Wayne State University, Detroit, MI 48202, USADepartment of Chemistry, Wayne State University, Detroit, MI 48202, USADepartment of Chemistry, Wayne State University, Detroit, MI 48202, USADepartment of Chemistry, Wayne State University, Detroit, MI 48202, USADepartment of Chemistry, Wayne State University, Detroit, MI 48202, USABased on current structural and statistical calculations, thousands of microcystins (MCs) can exist; yet, to date, only 246 MCs were identified and only 12 commercial MC standards are available. Standard mass spectrometry workflows for known and unknown MCs need to be developed and validated for basic and applied harmful algal bloom research to advance. Our investigation focuses on samples taken in the spring of 2018 from an impoundment fed by Oser and Bischoff Reservoirs, Indiana, United States of America (USA). The dominant cyanobacterium found during sampling was <i>Planktothrix agardhii</i>. The goal of our study was to identify and quantify the MCs in the impoundment sample using chemical derivatization and mass spectrometry. Modifying these techniques to use online concentration liquid chromatography tandem mass spectrometry (LC−MS/MS), two untargeted MCs have been identified, [<span style="font-variant: small-caps;">d</span>-Asp<sup>3</sup>, Dhb<sup>7</sup>]-MC-LR and [Dhb<sup>7</sup>]-MC-YR. [Dhb<sup>7</sup>]-MC-YR is not yet reported in the literature to date, and this was the first reported incidence of Dhb MCs in the United States. Furthermore, it was discovered that the commercially available [<span style="font-variant: small-caps;">d</span>-Asp<sup>3</sup>]-MC-RR standard was [<span style="font-variant: small-caps;">d</span>-Asp<sup>3</sup>, Dhb<sup>7</sup>]-MC-RR. This study highlights a workflow utilizing online concentration LC−MS/MS, high-resolution MS (HRMS), and chemical derivatization to identify isobaric MCs.https://www.mdpi.com/2072-6651/11/11/653microcystinscyanotoxins(2<i>s</i>,3<i>s</i>,4<i>e</i>,6<i>e</i>,8<i>s</i>,9<i>s</i>)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (adda)-elisalc–ms/mshrms |
| spellingShingle | Johnna A. Birbeck Nicholas J. Peraino Grace M. O’Neill Julia Coady Judy A. Westrick Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform Toxins microcystins cyanotoxins (2<i>s</i>,3<i>s</i>,4<i>e</i>,6<i>e</i>,8<i>s</i>,9<i>s</i>)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (adda)-elisa lc–ms/ms hrms |
| title | Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform |
| title_full | Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform |
| title_fullStr | Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform |
| title_full_unstemmed | Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform |
| title_short | Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform |
| title_sort | dhb microcystins discovered in usa using an online concentration lc ms ms platform |
| topic | microcystins cyanotoxins (2<i>s</i>,3<i>s</i>,4<i>e</i>,6<i>e</i>,8<i>s</i>,9<i>s</i>)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (adda)-elisa lc–ms/ms hrms |
| url | https://www.mdpi.com/2072-6651/11/11/653 |
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