Breaking cycles : saponification‐enhanced NMR fingerprint matching for the identification and stereochemical evaluation of cyclic lipodepsipeptides from natural sources
- Author
- Penthip Muangkaew (UGent) , Durga Prasad (UGent) , Vic De Roo, Yentl Verleysen, Lu Zhou (UGent) , René De Mot, Monica Höfte (UGent) , Annemieke Madder (UGent) , Niels Geudens (UGent) and José Martins (UGent)
- Organization
- Project
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- Sensitivity Upgrade at High Magnetic Field for NMR Based Science in the Next Decade.
- Magnetische resonantieapparatuur voor gevorderd materiaalonderzoek: moleculaire karakterisering van vaste, zachte, homogene en heterogene materie in de ontwikkeling van geavanceerde functionele materialen en chemische katalyse
- Routine NMR Analysis Equipment for Small Molecule Characterisation.
- Cofunding core facility - NMR Expertise Centre
- Ecological roles of cyclic lipopeptides from plant-beneficial rhizobacteria: a chemical-biology approach to decipher primary functions of secondary metabolites.
- A multifaceted approach to boost the biosynthesis of bioactive mycin- and peptin-type cyclic lipopeptides in Pseudomonas
- MEMCLIP: A comprehensive chemical-biology approach to understand the bioactivity of Pseudomonas cyclic lipopeptides on eukaryotic membranes
- Abstract
- We previously described NMR based fingerprint matching with peptide backbone resonances as a fast and reliable structural dereplication approach for Pseudomonascyclic lipodepsipeptides (CLiPs). In combination with total synthesis of a small library of configurational CLiP congeners this also allows unambiguous determination of stereochemistry, facilitating structure‐activity relationship studies and enabling three‐dimensional structure determination. However, the on‐resin macrocycle formation in the synthetic workflow brings considerable burden and limits universal applicability. This drawback is here removed altogether by also transforming the native CLiP into a linearized analogue by controlled saponification of the ester bond. This eliminates the need for macrocycle formation, limiting the synthesis effort to linear peptide analogues. NMR fingerprints of such linear peptide analogues display a sufficiently distinctive chemical shift fingerprint to act as effective discriminators. The approach is developed using viscosin group CLiPs and subsequently demonstrated on putisolvin, leading to a structural revision, and tanniamide from Pseudomonas ekonensis COR58, a newly isolated lipododecapeptide that defines a new group characterized by a ten‐residue large macrocycle, the largest to date in the Pseudomonas CLiP portfolio. These examples demonstrate the effectiveness of the saponification‐ enhanced approach that broadens applicability of NMR fingerprint matching for the determination of the stereochemistry of CLiPs.
- Keywords
- cyclic lipopeptides, Pseudomonas, SPPS, NMR spectroscopy, cyclic lipodepsipeptides, stereochemistry, dereplication, PSEUDOMONAS, LIPOPEPTIDES, BIOSYNTHESIS
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-01J4NVXTW7RJZZ1CSWEFXF9PX5
- MLA
- Muangkaew, Penthip, et al. “Breaking Cycles : Saponification‐enhanced NMR Fingerprint Matching for the Identification and Stereochemical Evaluation of Cyclic Lipodepsipeptides from Natural Sources.” CHEMISTRY-A EUROPEAN JOURNAL, vol. 30, no. 49, 2024, doi:10.1002/chem.202400667.
- APA
- Muangkaew, P., Prasad, D., De Roo, V., Verleysen, Y., Zhou, L., De Mot, R., … Martins, J. (2024). Breaking cycles : saponification‐enhanced NMR fingerprint matching for the identification and stereochemical evaluation of cyclic lipodepsipeptides from natural sources. CHEMISTRY-A EUROPEAN JOURNAL, 30(49). https://doi.org/10.1002/chem.202400667
- Chicago author-date
- Muangkaew, Penthip, Durga Prasad, Vic De Roo, Yentl Verleysen, Lu Zhou, René De Mot, Monica Höfte, Annemieke Madder, Niels Geudens, and José Martins. 2024. “Breaking Cycles : Saponification‐enhanced NMR Fingerprint Matching for the Identification and Stereochemical Evaluation of Cyclic Lipodepsipeptides from Natural Sources.” CHEMISTRY-A EUROPEAN JOURNAL 30 (49). https://doi.org/10.1002/chem.202400667.
- Chicago author-date (all authors)
- Muangkaew, Penthip, Durga Prasad, Vic De Roo, Yentl Verleysen, Lu Zhou, René De Mot, Monica Höfte, Annemieke Madder, Niels Geudens, and José Martins. 2024. “Breaking Cycles : Saponification‐enhanced NMR Fingerprint Matching for the Identification and Stereochemical Evaluation of Cyclic Lipodepsipeptides from Natural Sources.” CHEMISTRY-A EUROPEAN JOURNAL 30 (49). doi:10.1002/chem.202400667.
- Vancouver
- 1.Muangkaew P, Prasad D, De Roo V, Verleysen Y, Zhou L, De Mot R, et al. Breaking cycles : saponification‐enhanced NMR fingerprint matching for the identification and stereochemical evaluation of cyclic lipodepsipeptides from natural sources. CHEMISTRY-A EUROPEAN JOURNAL. 2024;30(49).
- IEEE
- [1]P. Muangkaew et al., “Breaking cycles : saponification‐enhanced NMR fingerprint matching for the identification and stereochemical evaluation of cyclic lipodepsipeptides from natural sources,” CHEMISTRY-A EUROPEAN JOURNAL, vol. 30, no. 49, 2024.
@article{01J4NVXTW7RJZZ1CSWEFXF9PX5,
abstract = {{We previously described NMR based fingerprint matching with peptide backbone resonances as a fast and reliable structural dereplication approach for Pseudomonascyclic lipodepsipeptides (CLiPs). In combination with total synthesis of a small library of configurational CLiP congeners this also allows unambiguous determination of stereochemistry, facilitating structure‐activity relationship studies and enabling three‐dimensional structure determination. However, the on‐resin macrocycle formation in the synthetic workflow brings considerable burden and limits universal applicability. This drawback is here removed altogether by also transforming the native CLiP into a linearized analogue by controlled saponification of the ester bond. This eliminates the need for macrocycle formation, limiting the synthesis effort to linear peptide analogues. NMR fingerprints of such linear peptide analogues display a sufficiently distinctive chemical shift fingerprint to act as effective discriminators. The approach is developed using viscosin group CLiPs and subsequently demonstrated on putisolvin, leading to a structural revision, and tanniamide from Pseudomonas ekonensis COR58, a newly isolated lipododecapeptide that defines a new group characterized by a ten‐residue large macrocycle, the largest to date in the Pseudomonas CLiP portfolio. These examples demonstrate the effectiveness of the saponification‐ enhanced approach that broadens applicability of NMR fingerprint matching for the determination of the stereochemistry of CLiPs.}},
articleno = {{e202400667}},
author = {{Muangkaew, Penthip and Prasad, Durga and De Roo, Vic and Verleysen, Yentl and Zhou, Lu and De Mot, René and Höfte, Monica and Madder, Annemieke and Geudens, Niels and Martins, José}},
issn = {{0947-6539}},
journal = {{CHEMISTRY-A EUROPEAN JOURNAL}},
keywords = {{cyclic lipopeptides,Pseudomonas,SPPS,NMR spectroscopy,cyclic lipodepsipeptides,stereochemistry,dereplication,PSEUDOMONAS,LIPOPEPTIDES,BIOSYNTHESIS}},
language = {{eng}},
number = {{49}},
pages = {{13}},
title = {{Breaking cycles : saponification‐enhanced NMR fingerprint matching for the identification and stereochemical evaluation of cyclic lipodepsipeptides from natural sources}},
url = {{http://doi.org/10.1002/chem.202400667}},
volume = {{30}},
year = {{2024}},
}
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