Impact of a Stereocentre Inversion in Cyclic Lipodepsipeptides from the Viscosin Group: A Comparative Study of the Viscosinamide and Pseudodesmin Conformation and Self‐Assembly |
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Authors: | Niels Geudens Matthias De Vleeschouwer Dr Krisztina Fehér Dr Hassan Rokni‐Zadeh Dr Maarten G K Ghequire Prof Dr Annemieke Madder Prof Dr René De Mot Prof Dr José C Martins Dr Davy Sinnaeve |
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Affiliation: | 1. NMR and Structure Analysis Unit, Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4, 9000 Ghent (Belgium);2. Organic and Biomimetic Chemistry Research Group, Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4, 9000 Ghent (Belgium);3. Centre for Microbial and Plant Genetics, Faculty of Bioscience Engineering, KU Leuven, Kasteelpark Arenberg 20, 3001 Heverlee–Leuven (Belgium);4. Present address: Department of Biotechnology and Molecular Medicine, Zanjan University of Medical Sciences, Zanjan (Iran) |
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Abstract: | The viscosin group covers a series of cyclic lipodepsipeptides (CLPs) produced by Pseudomonas bacteria, with a range of biological functions and antimicrobial activities. Their oligopeptide moieties are composed of both L ‐ and D ‐amino acids. Remarkably, the Leu5 amino acid—centrally located in the nonapeptide sequence—is the sole residue found to possess either an L or D configuration, depending on the producing strain. The impact of this D /L switch on the solution conformation was investigated by NMR‐restrained molecular modelling of the epimers pseudodesmin A and viscosinamide A. Although the backbone fold remained unaffected, the D /L switch adjusted the segregation between hydrophobic and hydrophilic residues, and thus the amphipathicity. It also influenced the self‐assembly capacity in organic solvents. Additionally, several new minor variants of viscosinamide A from Pseudomonas fluorescens DR54 were identified, and an NMR assay is proposed to assess the presence of either an L ‐ or D ‐Leu5. |
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Keywords: | conformational analysis cyclic lipopeptides natural products self‐assembly structure– activity relationships |
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