Tanniamide

General info

Original publication	Muangkaew, 2024
Original source	Pseudomonas ekonensis COR58
Other known sources (non-putative)	n.a.
Stereochemistry determined by	NMR fingerprint matching (Muangkaew, 2024)

Chemical properties

CAS	n.a.
Molecular formula	Tanniamide A: C74H126N14O22 Tanniamide B: C74H126N14O22 Tanniamide C: C74H128N14O22
Molecular weight	Tanniamide A: 1563.8980 g/mol Tanniamide B: 1563.8980 g/mol Tanniamide C: 1565.9140 g/mol
Mono-isotopic mass	Tanniamide A: 1562.9171 Da Tanniamide B: 1562.9171 Da Tanniamide C: 1564.9328 Da
Solubility	MeOH, acetonitrile/water, DMF
CMC	n.d.
Minimal surface tension	n.d.
3D conformation	n.d.
NMR data available in literature	Muangkaew, 2024

Introduction

Tanniamide is a cyclic lipodepsipeptide produced by Pseudomonas ekonensis COR58. It was first described in a study describing a novel methodology for the stereochemical elucidation of cyclic lipodepsipeptides. (Muangkaew, 2024) Before it actual structural characterization, the lipopeptides was putatively named N4. (Oni, 2019; Oni, 2020)

Its producing bacterium, Pseudomonas ekonensis COR58, was initially isolated from the rhizosphere of red cocoyam in Cameroon. The name of the CLiP refers to ‘tannia’, the common local term for cocoyam, a staple crop in Cameroon.

Chemical structure

The structure of tanniamide A was elucidated by means of NMR spectroscopy and mass spectrometry. The stereochemistry of the lipopeptide was established using a saponification enhanced NMR fingerprint matching protocol and chemical synthesis. (Muangkaew, 2024) The structure of tanniamide A is (R,Z)-3-hydroxydodec-5-enoic acid – D-Leu – D-Asp – D-aThr – D-aIle – L-Leu – D-Gln – L-Leu – D-Ser – L-Leu – D-Gln – L-Ile – L-Glu.

Tanniamide B and C could also be purified and characterized as minor compounds from the crude extract of P. ekonensis COR58. Featuring a mass of 1563.92 Da (isobaric) and 1565.94 Da (+2 Da), NMR analysis allowed to identify these minors as tanniamide A homologues, featuring Leu11 in place of Ile11, and a saturated C12:0 acyl chain respectively. These three compounds represent new CLiPs that cannot be placed in any of the existing Pseudomonas CLiP groups as defined by their (l:m) tag. Therefore, they make up a novel Pseudomonas group that we will denote as the Tanniamide (12:10) group.

While having the same number of amino acids in its sequence as putisolvin, the macrocycle of tanniamides encompass 10 amino acids rather than 4, representing the largest macrocycle reported to date for the more than 130 reported Pseudomonas CLiPs.

References

De Roo, et al. “An Nuclear Magnetic Resonance Fingerprint Matching Approach for the Identification and Structural Re-Evaluation of Pseudomonas Lipopeptides.” Microbiology Spectrum10, 4 (2022): https://dx.doi.org/doi:10.1128/spectrum.01261-22.

Muangkaew, et al. “Stereomeric Lipopeptides from a Single Non-Ribosomal Peptide Synthetase as an Additional Source of Structural and Functional Diversification in Pseudomonas Lipopeptide Biosynthesis.” International Journal of Molecular Sciences 24, 18 (2023). https://www.mdpi.com/1422-0067/24/18/14302.

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 (2024): https://dx.doi.org/https://doi.org/10.1002/chem.202400667.

Oni, et al. “Fluorescent Pseudomonas and cyclic lipopeptide diversity in the rhizosphere of cocoyam (Xanthosoma sagittifolium).” Environmental Microbiology (2019): https://dx.doi.org/doi:10.1111/1462-2920.14520.

Oni, et al. “Cyclic lipopeptide-producing Pseudomonas koreensis group strains dominate the cocoyam rhizosphere of a Pythium root rot suppressive soil contrasting with P. putida prominence in conducive soils.” Environmental Microbiology 22, 12 (2020): https://dx.doi.org/10.1111/1462-2920.15127.