Cyclodepsipeptides from Beauveria bassiana. Part 2. Beauverolides A to F and their relationship to isarolide

Elsworth, John F.; Grove, John Frederick

doi:10.1039/p19800001795

Cited by 36 publications

(20 citation statements)

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“…brongniartii and C. militaris produce compounds with similar AA residues. Even not being detected in this study, a previous report has indicated that B. bassiana could also produce beauverolide D, E, Ea, F and Fa that all contain a 3-hydroxy FA of HMOA (26).…”

Section: Discussioncontrasting

confidence: 65%

Production of diverse beauveriolide analogs in closely related fungi: a rare case of fungal chemodiversity

Yin

Chen

Song

et al. 2020

Preprint

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ABSTRACTFungal chemodiversity is well known in part due to the production of diverse analogous compounds by a single biosynthetic gene cluster (BGCs). Usually, similar metabolites are produced by closely related fungal species. Here we report a rare case of the production of the cyclodepsipeptide beauveriolides (BVDs) in three insect pathogenic fungi. We found that the more closely-related fungi Beauveria bassiana and B. brongniartii produce structurally distinct analogs of BVDs whereas the rather divergently evolved species B. brongniartii and Cordyceps militaris produce structural analogs in a similar pattern. It was verified that a conserved BGC containing four genes is responsible for BVD biosynthesis in three fungi including a polyketide synthase (PKS) for the production of 3-hydroxy fatty acids (FAs) with chain length variations. In contrast to BVD production patterns, phylogenetic analysis of the BGC enzymes or enzyme domains largely resulted in the congruence relationship with fungal speciation. Feeding assays demonstrated that a FA with a chain length of eight carbon atoms was preferentially utilized whereas a FA with a chain longer than 10 carbon atoms could not be used as a substrate for BVD biosynthesis. We also found that addition of D-type amino acids could not enable B. bassiana to produce those analogs biosynthesized by other two fungi. Insect survival assays suggested that the contribution of BVD to fungal virulence might be associated with the susceptibility of insect species. The results of this study enrich the knowledge of fungal secondary metabolic diversity.IMPORTANCEFungal chemotaxonomy is an approach to classify fungi based on fungal production of natural compounds especially the secondary metabolites. We found an atypical example that could question chemical classification of fungi in this study: the more closely-related entomopathogenic species Beauveria bassiana and B. brongniartii produce structurally different analogs of the cyclodepsipeptide beauveriolides whereas the rather divergent species B. brongniartii and Cordyceps militaris biosynthesize similar analogs under the same growth condition. The conserved BGC containing four genes is present in each species and responsible for beauveriolide production. In contrast to the compound formation profiles, the phylogenies of biosynthetic enzymes or enzymatic domains show associations with fungal speciation relationship. Dependent on insect species, production of beauveriolides may contribute to fungal virulence against insect. The findings in this study augment the diversity of fungal secondary metabolisms.

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Section: Discussioncontrasting

confidence: 65%

Production of diverse beauveriolide analogs in closely related fungi: a rare case of fungal chemodiversity

Yin

Chen

Song

et al. 2020

Preprint

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“…The sublimation procedure helped a bit, but the total amount and purity of the isolated fraction was not sufficient Table 2. (18) 274 (65) 157 (5) 203 (10) 86 (8) (12) 286 (80) 185 (5) 203 (10) 86 ( 546 (7) 536 (60) 451 (20) 433 (6) 304 (22) 286 (62) 276 (25) 258 (49) 157 (5) 279 (28) 86 (8) (10) 297 (41) 157 (8) 279 (29) 86 (8) (17) 371 (8) 353 (35) 343 (3) 325 (21) 185 (5) 279 (20) 86 ( for the complete NMR confirmation. Therefore, the tentative sequence assignment cyclo--C 11 -Val-Ala-Lxx-has been based solely on mass spectral data.…”

Section: New Beauverolidesmentioning

confidence: 97%

Sequencing of new beauverolides by high‐performance liquid chromatography and mass spectrometry

Kuzma

Jegorov²,

Kačer

et al. 2001

J. Mass Spectrom.

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Mass spectrometry (MS) and tandem mass spectrometry (MS(n)) were used for the identification of beauverolides in the fermentation broth of Beauveria bassiana and for evaluation of the purified fraction obtained by sublimation of beauverolides. Besides being a new efficient route for purification of beauverolides, sublimation provided an enrichment of new minor lipophilic beauverolides of lower molecular weight from the original complex mycelial extract. The product ion collision-induced dissociation (CID) spectra obtained on an ion trap (electrospray ionization), the in-source CID mass spectra on a sector instrument (atmospheric-pressure chemical ionization) and the post-source decay matrix-assisted laser desorption/ionization mass spectra of beauverolides were compared and evaluated. All MS(n) experiments started with singly charged precursor ions. The following two new representatives of this group of compounds were identified by high-performance liquid chromatography and MS (HPLC/MS): cyclo-(3-hydroxy-4-methyloctanoyl-valyl-alanyl-leucyl) and cyclo-(3-hydroxy-4-methyloctanoyl-tyrosyl-alanyl-leucyl). Individual structures were confirmed by preparative isolation and nuclear magnetic resonance spectroscopy. The structure of a third novel and minor beauverolide was tentatively assigned by HPLC/MS only as cyclo-(3-hydroxy-4-methyldecanoyl-valyl-alanyl-Lxx), Lxx = leucyl, isoleucyl, or allo-isoleucyl.

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“…Many cyanobacterial macrocycles are peptides and depsipeptides [ 11 ] derived from NRPS or mixed NRPS-PKS genetic architecture and encode proteins with the ability to incorporate l - and d - α -amino acids as well as β -hydroxy fatty acids [ 12 , 13 ]. β -hydroxyacyl incorporation has been observed in several microbial depsipeptides including the beauverolides [ 14 , 15 , 16 ] (3 and 4 residue macrocycles); the unnarmicins [ 17 ], the solonamides [ 18 ], the arthroamides [ 19 ], the turnagainolides [ 20 ], and ngercheumicin C, D and E [ 21 ] (five residue macrocycles); and scytonemide B [ 22 ] and kailuin A-H (six residue macrocycles) [ 23 , 24 ]. These macrocycles have generally displayed antibiotic activity [ 17 ], quorum sensing interference [ 18 ] and weak cytotoxicity [ 24 ].…”

Section: Introductionmentioning

confidence: 99%

Tricholides A and B and Unnarmicin D: New Hybrid PKS-NRPS Macrocycles Isolated from an Environmental Collection of Trichodesmium thiebautii

et al. 2017

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Bioassay-guided isolation of the lipophilic extract of Trichodesmium thiebautii bloom material led to the purification and structure characterization of two new hybrid polyketide-non-ribosomal peptide (PKS-NRPS) macrocyclic compounds, tricholides A and B (1 and 2). A third macrocyclic compound, unnarmicin D (3), was identified as a new depsipeptide in the unnarmicin family, given its structural similarity to the existing compounds in this group. The planar structures of 1–3 were determined using 1D and 2D NMR spectra and complementary spectroscopic and spectrometric procedures. The absolute configurations of the amino acid components of 1–3 were determined via acid hydrolysis, derivitization with Marfey’s reagent and HPLC-UV comparison to authentic amino acid standards. The absolute configuration of the 3-hydroxydodecanoic acid moiety in 3 was determined using a modified Mosher’s esterification procedure on a linear derivative of tricharmicin (4) and additionally by a comparison of 13C NMR shifts of 3 to known depsipeptides with β-hydroxy acid subunits. Tricholide B (2) showed moderate cytotoxicity to Neuro-2A murine neuroblastoma cells (EC50: 14.5 ± 6.2 μM).

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Cyclodepsipeptides from Beauveria bassiana. Part 2. Beauverolides A to F and their relationship to isarolide

Cited by 36 publications

References 0 publications

Production of diverse beauveriolide analogs in closely related fungi: a rare case of fungal chemodiversity

Production of diverse beauveriolide analogs in closely related fungi: a rare case of fungal chemodiversity

Sequencing of new beauverolides by high‐performance liquid chromatography and mass spectrometry

Tricholides A and B and Unnarmicin D: New Hybrid PKS-NRPS Macrocycles Isolated from an Environmental Collection of Trichodesmium thiebautii

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