First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC)
Saxitoxin and its analogues, paralytic shellfish toxins (PSTs), are potent and specific voltage-gated sodium channel blockers. These toxins are produced by some species of freshwater cyanobacteria and marine dinoflagellates. We previously identified several biosynthetic intermediates of PSTs, as wel...
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2022-02-01
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| author | Michiru Akamatsu Ryosuke Hirozumi Yuko Cho Yuta Kudo Keiichi Konoki Yasukatsu Oshima Mari Yotsu-Yamashita |
| author_facet | Michiru Akamatsu Ryosuke Hirozumi Yuko Cho Yuta Kudo Keiichi Konoki Yasukatsu Oshima Mari Yotsu-Yamashita |
| author_sort | Michiru Akamatsu |
| collection | DOAJ |
| description | Saxitoxin and its analogues, paralytic shellfish toxins (PSTs), are potent and specific voltage-gated sodium channel blockers. These toxins are produced by some species of freshwater cyanobacteria and marine dinoflagellates. We previously identified several biosynthetic intermediates of PSTs, as well as new analogues, from such organisms and proposed the biosynthetic and metabolic pathways of PSTs. In this study, 12β-deoxygonyautoxin 5 (12α-gonyautoxinol 5 = gonyautoxin 5-12(<i>R</i>)-ol) was identified in the freshwater cyanobacterium, <i>Dolichospermum circinale</i> (TA04), and 12β-deoxysaxitoxin (12α-saxitoxinol = saxitoxin-12(<i>R</i>)-ol) was identified in the same cyanobacterium and in the marine dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) for the first time from natural sources. The authentic standards of these compounds and 12α-deoxygonyautoxin 5 (12β-gonyautoxinol 5 = gonyautoxin 5-12(<i>S</i>)-ol) were prepared by chemical derivatization from the major PSTs, C1/C2, produced in <i>D. circinale</i> (TA04). These standards were used to identify the deoxy analogues by comparing the retention times and MS/MS spectra using high-resolution LC-MS/MS. Biosynthetic or metabolic pathways for these analogues have also been proposed based on their structures. The identification of these compounds supports the α-oriented stereoselective oxidation at C12 in the biosynthetic pathway towards PSTs. |
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| series | Marine Drugs |
| spelling | doaj.art-5c0f1a3144f7460da2afd27e7e77edcc2023-11-30T21:17:44ZengMDPI AGMarine Drugs1660-33972022-02-0120316610.3390/md20030166First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC)Michiru Akamatsu0Ryosuke Hirozumi1Yuko Cho2Yuta Kudo3Keiichi Konoki4Yasukatsu Oshima5Mari Yotsu-Yamashita6Graduate School of Agricultural Science, Tohoku University, Sendai 980-8572, JapanGraduate School of Agricultural Science, Tohoku University, Sendai 980-8572, JapanGraduate School of Agricultural Science, Tohoku University, Sendai 980-8572, JapanGraduate School of Agricultural Science, Tohoku University, Sendai 980-8572, JapanGraduate School of Agricultural Science, Tohoku University, Sendai 980-8572, JapanGraduate School of Life Sciences, Tohoku University, Sendai 980-8577, JapanGraduate School of Agricultural Science, Tohoku University, Sendai 980-8572, JapanSaxitoxin and its analogues, paralytic shellfish toxins (PSTs), are potent and specific voltage-gated sodium channel blockers. These toxins are produced by some species of freshwater cyanobacteria and marine dinoflagellates. We previously identified several biosynthetic intermediates of PSTs, as well as new analogues, from such organisms and proposed the biosynthetic and metabolic pathways of PSTs. In this study, 12β-deoxygonyautoxin 5 (12α-gonyautoxinol 5 = gonyautoxin 5-12(<i>R</i>)-ol) was identified in the freshwater cyanobacterium, <i>Dolichospermum circinale</i> (TA04), and 12β-deoxysaxitoxin (12α-saxitoxinol = saxitoxin-12(<i>R</i>)-ol) was identified in the same cyanobacterium and in the marine dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) for the first time from natural sources. The authentic standards of these compounds and 12α-deoxygonyautoxin 5 (12β-gonyautoxinol 5 = gonyautoxin 5-12(<i>S</i>)-ol) were prepared by chemical derivatization from the major PSTs, C1/C2, produced in <i>D. circinale</i> (TA04). These standards were used to identify the deoxy analogues by comparing the retention times and MS/MS spectra using high-resolution LC-MS/MS. Biosynthetic or metabolic pathways for these analogues have also been proposed based on their structures. The identification of these compounds supports the α-oriented stereoselective oxidation at C12 in the biosynthetic pathway towards PSTs.https://www.mdpi.com/1660-3397/20/3/166saxitoxin<i>Dolichospermum circinale</i><i>Alexandrium pacificum</i>paralytic shellfish toxins12β-deoxygonyautoxin 5 (12α-gonyautoxinol 5)12β-deoxysaxitoxin (12α-saxitoxinol) |
| spellingShingle | Michiru Akamatsu Ryosuke Hirozumi Yuko Cho Yuta Kudo Keiichi Konoki Yasukatsu Oshima Mari Yotsu-Yamashita First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) Marine Drugs saxitoxin <i>Dolichospermum circinale</i> <i>Alexandrium pacificum</i> paralytic shellfish toxins 12β-deoxygonyautoxin 5 (12α-gonyautoxinol 5) 12β-deoxysaxitoxin (12α-saxitoxinol) |
| title | First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) |
| title_full | First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) |
| title_fullStr | First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) |
| title_full_unstemmed | First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) |
| title_short | First Identification of 12β-Deoxygonyautoxin 5 (12α-Gonyautoxinol 5) in the Cyanobacterium <i>Dolichospermum circinale</i> (TA04) and 12β-Deoxysaxitoxin (12α-Saxitoxinol) in <i>D. circinale</i> (TA04) and the Dinoflagellate <i>Alexandrium pacificum</i> (Group IV) (120518KureAC) |
| title_sort | first identification of 12β deoxygonyautoxin 5 12α gonyautoxinol 5 in the cyanobacterium i dolichospermum circinale i ta04 and 12β deoxysaxitoxin 12α saxitoxinol in i d circinale i ta04 and the dinoflagellate i alexandrium pacificum i group iv 120518kureac |
| topic | saxitoxin <i>Dolichospermum circinale</i> <i>Alexandrium pacificum</i> paralytic shellfish toxins 12β-deoxygonyautoxin 5 (12α-gonyautoxinol 5) 12β-deoxysaxitoxin (12α-saxitoxinol) |
| url | https://www.mdpi.com/1660-3397/20/3/166 |
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