Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011
Application of a miniaturized 24-well plate system for cultivation profiling (MATRIX) permitted optimization of the cultivation conditions for the marine-derived fungus <i>Talaromyces</i> sp. CMB-TU011, facilitating access to the rare cycloheptapeptide talarolide A (<b>1</b>)...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-09-01
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| Series: | Marine Drugs |
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| Online Access: | https://www.mdpi.com/1660-3397/21/9/487 |
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| author | Angela A. Salim Waleed M. Hussein Pradeep Dewapriya Huy N. Hoang Yahao Zhou Kaumadi Samarasekera Zeinab G. Khalil David P. Fairlie Robert J. Capon |
| author_facet | Angela A. Salim Waleed M. Hussein Pradeep Dewapriya Huy N. Hoang Yahao Zhou Kaumadi Samarasekera Zeinab G. Khalil David P. Fairlie Robert J. Capon |
| author_sort | Angela A. Salim |
| collection | DOAJ |
| description | Application of a miniaturized 24-well plate system for cultivation profiling (MATRIX) permitted optimization of the cultivation conditions for the marine-derived fungus <i>Talaromyces</i> sp. CMB-TU011, facilitating access to the rare cycloheptapeptide talarolide A (<b>1</b>) along with three new analogues, B–D (<b>2</b>–<b>4</b>). Detailed spectroscopic analysis supported by Marfey’s analysis methodology was refined to resolve <i>N</i>-Me-<span style="font-variant: small-caps;">l</span>-Ala from <i>N</i>-Me-<span style="font-variant: small-caps;">d</span>-Ala, <span style="font-variant: small-caps;">l</span>-<i>allo</i>-Ile from <span style="font-variant: small-caps;">l</span>-Ile and <span style="font-variant: small-caps;">l</span>-Leu, and partial and total syntheses of <b>2</b>, and permitted unambiguous assignment of structures for <b>1</b> (revised) and <b>2</b>–<b>4</b>. Consideration of diagnostic ROESY correlations for the hydroxamates <b>1</b> and <b>3</b>–<b>4</b>, and a calculated solution structure for <b>1</b>, revealed how cross-ring H-bonding to the hydroxamate moiety influences (defines/stabilizes) the cyclic peptide conformation. Such knowledge draws attention to the prospect that hydroxamates may be used as molecular bridges to access new cyclic peptide conformations, offering the prospect of new biological properties, including enhanced oral bioavailability. |
| first_indexed | 2024-03-10T22:30:54Z |
| format | Article |
| id | doaj.art-42f42ea2be534df994531dff6bea61a8 |
| institution | Directory Open Access Journal |
| issn | 1660-3397 |
| language | English |
| last_indexed | 2024-03-10T22:30:54Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Marine Drugs |
| spelling | doaj.art-42f42ea2be534df994531dff6bea61a82023-11-19T11:42:16ZengMDPI AGMarine Drugs1660-33972023-09-0121948710.3390/md21090487Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011Angela A. Salim0Waleed M. Hussein1Pradeep Dewapriya2Huy N. Hoang3Yahao Zhou4Kaumadi Samarasekera5Zeinab G. Khalil6David P. Fairlie7Robert J. Capon8Institute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaInstitute for Molecular Bioscience, The University of Queensland, St. Lucia, QLD 4072, AustraliaApplication of a miniaturized 24-well plate system for cultivation profiling (MATRIX) permitted optimization of the cultivation conditions for the marine-derived fungus <i>Talaromyces</i> sp. CMB-TU011, facilitating access to the rare cycloheptapeptide talarolide A (<b>1</b>) along with three new analogues, B–D (<b>2</b>–<b>4</b>). Detailed spectroscopic analysis supported by Marfey’s analysis methodology was refined to resolve <i>N</i>-Me-<span style="font-variant: small-caps;">l</span>-Ala from <i>N</i>-Me-<span style="font-variant: small-caps;">d</span>-Ala, <span style="font-variant: small-caps;">l</span>-<i>allo</i>-Ile from <span style="font-variant: small-caps;">l</span>-Ile and <span style="font-variant: small-caps;">l</span>-Leu, and partial and total syntheses of <b>2</b>, and permitted unambiguous assignment of structures for <b>1</b> (revised) and <b>2</b>–<b>4</b>. Consideration of diagnostic ROESY correlations for the hydroxamates <b>1</b> and <b>3</b>–<b>4</b>, and a calculated solution structure for <b>1</b>, revealed how cross-ring H-bonding to the hydroxamate moiety influences (defines/stabilizes) the cyclic peptide conformation. Such knowledge draws attention to the prospect that hydroxamates may be used as molecular bridges to access new cyclic peptide conformations, offering the prospect of new biological properties, including enhanced oral bioavailability.https://www.mdpi.com/1660-3397/21/9/487talarolides<i>Talaromyces</i>cycloheptapeptide<i>N</i>-OH glycineMATRIXGNPS molecular networking |
| spellingShingle | Angela A. Salim Waleed M. Hussein Pradeep Dewapriya Huy N. Hoang Yahao Zhou Kaumadi Samarasekera Zeinab G. Khalil David P. Fairlie Robert J. Capon Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011 Marine Drugs talarolides <i>Talaromyces</i> cycloheptapeptide <i>N</i>-OH glycine MATRIX GNPS molecular networking |
| title | Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011 |
| title_full | Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011 |
| title_fullStr | Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011 |
| title_full_unstemmed | Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011 |
| title_short | Talarolides Revisited: Cyclic Heptapeptides from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. CMB-TU011 |
| title_sort | talarolides revisited cyclic heptapeptides from an australian marine tunicate associated fungus i talaromyces i sp cmb tu011 |
| topic | talarolides <i>Talaromyces</i> cycloheptapeptide <i>N</i>-OH glycine MATRIX GNPS molecular networking |
| url | https://www.mdpi.com/1660-3397/21/9/487 |
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