Search

Two new compounds, cladospolides I (1) and J (2), together with two new naturally occurring ones, methyl 11-hydroxy-4-oxododecanoate (3) and 11-hydroxy-4-oxododecanoic acid (4), were isolated from the culture extract of the cold-seep sediment-derived fungus Cladosporium cladosporioides 8-1. Their structures and configurations were established by analysis of 1D/2D NMR, MS, ECD, and specific optical rotation data. Compound 3 was possibly formed by methyl esterification of 4 during the purification process due to the utilization of methanol. All compounds were evaluated for inhibition of four marine phytoplankton species and five marine-derived bacteria.

One new lanostane-type triterpenoid, 3

Two new bisabolane derivatives, trichobisabolins M (1) and N (2), one new steroid derivative, 4-(p-hydroxyphenethoxy)demethylincisterol A3 (3), and one new lauric acid derivative, methyl 3,5-dihydroxydodecanoate (4), as well as (3R,5R)-3-hydroxy-5-dodecanolide (5) were isolated from the marine-alga-endophytic Trichoderma atroviride RR-dl-3−9. Their structures and relative configurations were assigned mainly by NMR and mass spectroscopic techniques, and their absolute configurations were confirmed on the basis of specific optical rotation, ECD, and X-ray crystallographic data. Compounds 1 and 2 represent the first occurrence of bisabolane derivatives from this species. The five isolates were assayed for inhibiting four marine phytoplankton and five marine-derived bacteria, and the two lauric acid derivatives showed antibacterial activities with MIC values ranging from 13 to 50 μg/mL.

A new highly transformed sorbicillinoid derivative, trichoreesin A (1), and four known monomeric sorbicillinoids, sorbicillin (2), 2',3'-dihydrosorbicillin (3), 3-demethylsorbicillin (4), and sohirnone A (5), were discovered from Trichoderma reesei Z56-8, an epiphyte from the marine brown alga Sargassum sp. The structure and relative configuration of 1 were determined by interpretation of UV, IR, NMR, and MS signals, and its absolute configuration was assigned by analysis of ECD data aided by quantum chemical calculations. This is the first survey of metabolites from marine algicolous T. reesei. Compound 1 represents the first bicyclic vertinolide derivative, and it possesses inhibition of several marine phytoplankton species.

Two new cyclonerane sesquiterpenes, 5-hydroxyepicyclonerodiol oxide (1) and 4-hydroxyepicyclonerodiol oxide (2), and one new naturally occurring halogenated trichothecane derivative, trichodermol chlorohydrin (3), were isolated from Trichoderma hamatum Z36−7, an epiphytic fungal strain obtained from the marine red alga Grateloupia sp. Their structures and relative configurations were assigned on the basis of spectroscopic techniques, including 1D/2D NMR and IR as well as MS. Compound 2 features an unusual 4-hydroxy group on the five-membered ring of cycloneranes, and 3 is the first natural isolate of halogenated trichothecanes. These isolates represent the first occurrence of terpenes in T. hamatum and exhibit growth inhibition of several bacteria and phytoplankton species.

Two new meroterpenoids, aspermeroterpenes D and E (1 and 2), two new ophiobolin-type sesterterpenoids, the C-18 epimers of 18,19-dihydro-18-methoxy-19-hydroxyophiobolin P (6 and 7), and two new drimane-type sesquiterpenoids, 3S-hydroxystrobilactone A (8) and 6-epi-strobilactone A (9), along with 11 known terpenoids (3-5 and 10-17) were isolated from the cultures of the algicolous fungus Aspergillus sp. RR-YLW-12, derived from the red alga Rhodomela confervoides. The structures and relative configurations of new compounds were established by detailed spectroscopic analysis of NMR and HRMS experiments, and the absolute configurations were assigned by X-ray diffraction experiments and comparison of their experimental and calculated ECD spectra. Compound 1 features a rare 6/6/6/6/5 pentacyclic system with a meroterpenoid skeleton, and the structure of terretonin E (3) was revised in this study. Compound 4 showed significant inhibitory activities against three microalgae, Prorocentrum donghaiense, Heterosigma akashiwo, and Chattonella marina, with IC50 values of 10.5, 5.2, and 3.1 μg/mL, respectively.

Eight new trichothecene derivatives, trichodermarins G-N (1-8), and two new cuparene derivatives, trichocuparins A (9) and B (10), as well as six known trichothecenes (11-16) were isolated from the fungal strain Trichoderma brevicompactum A-DL-9-2 obtained from the inner tissue of the marine red alga Chondria tenuissima. The structures and relative configurations of 1-10 were assigned by NMR and MS data, and the absolute configurations of 1, 2, and 9 were established by X-ray diffraction. Compound 8 features an aminosugar unit bond to the trichothecene framework for the first time, while 9 and 10 represent the first occurrence of cuparene sesquiterpenes in Trichoderma. All the isolates were assayed for growth inhibition of five phytopathogenic fungi (Botrytis cinerea, Cochliobolus miyabeanus, Fusarium oxysporum f. sp. cucumerium, Fusarium oxysporum f. sp. niveum, and Phomopsis asparagi) and four marine phytoplankton species (Amphidinium carterae, Heterocapsa circularisquama, Heterosigma akashiwo, and Prorocentrum donghaiense). Several of them exhibited significant inhibitory activities against the fungi and phytoplankton tested of which trichodermin (12) showed the highest antifungal and antimicroalgal activities with MIC and IC50 values being 4.0 and 0.82 μg/mL, respectively.

Four new carotane sesquiterpenoids, byssocarotins A-D (

International audience; With contributions from the global natural product (NP) research community, and continuing the Raw Data Initiative, this review collects a comprehensive demonstration of the immense scientific value of disseminating raw nuclear magnetic resonance (NMR) data, independently of, and in parallel with, classical publishing outlets. A comprehensive compilation of historic to present-day cases as well as contemporary and future applications show that addressing the urgent need for a repository of publicly accessible raw NMR data has the potential to transform natural products (NPs) and associated fields of chemical and biomedical research. The call for advancing open sharing mechanisms for raw data is intended to enhance the transparency of experimental protocols, augment the reproducibility of reported outcomes, including biological studies, become a regular component of responsible research, and thereby enrich the integrity of NP research and related fields.

As one of the most productive species, Trichoderma asperellum, especially isolated from marine algae, has contributed a number of new terpenes and nitrogen-bearing compounds, encouraging our continuous efforts to further explore them. Consequently, three new nitrogen-containing secondary metabolites, including cyclo(L-5-MeO-Pro-L-5-MeO-Pro) (1), 5′-acetoxy- deoxycyclonerin B (2), and 5′-acetoxy-deoxycyclonerin D (3) were isolated from the marine alga-derived endophytic fungus Trichoderma asperellum A-YMD-9-2. Their structures and relative configurations were fully elucidated through spectroscopic techniques, mainly including 1D/2D NMR and MS. The absolute configurations of 1 and 2 were ascertained on the basis of X-ray diffraction (Cu Kα radiation) and ECD data, respectively. The isolation of these new nitrogen-bearing compounds adds to the structural diversity of marine algicolous Trichoderma spp., and they display potent inhibition against some marine phytoplankton species.

A new highly transformed sorbicillinoid derivative, trichoreesin A (

A new cyclopentenone derivative, 4-hydroxyhypocrenone A, and a new naturally-occurring wickerol derivative, 8-acetoxywickerol A, as well as two known compounds, hypocrenone A and wickerol B, were purified from

Two new meroterpenoids, aspermeroterpenes D and E (

In addition to the known harziandione (1), one new diterpenoid, 3S-hydroxyharzianone (2), and two new sesquiterpenoids, 4-cadinen-11,12-diol (3) and 4-cadinen-11,13-diol (4), were isolated from the culture of Trichoderma asperellum A-YMD-9-2, an endophytic fungal strain from the marine red alga Gracilaria verrucosa. The structures and relative configurations of new isolates were established by analysis of spectroscopic techniques, including 1D/2D NMR, IR, and MS, and their absolute configurations, except for those at C-11 of 3 and 4, were assigned by comparison of the ECD curve or specific optical rotation data with those of analogues. Compound 2 may be an intermediate in the biosynthesis of harziandione from harzianone, while 3 and 4 represent the second occurrence of cadinane sesquiterpenoids in Trichoderma. Compounds 2−4 exhibited potent inhibition of several marine phytoplankton species.

Three metabolites deoxytrichodermaerin (a new harziane lactone), harzianol A and harzianone were obtained from Trichoderma longibrachiatum A-WH-20-2, an endophyte from marine red alga Laurencia okamurai. Their structures and relative configurations were unequivocally assigned by spectroscopic techniques, and the absolute configuration of deoxytrichodermaerin was established by analysis of the ECD curve aided by quantum chemical calculations. Deoxytrichodermaerin represents the second harziane lactone with an ester linkage between C-10 and C-11. Harzianol A occurs as a natural product of Trichoderma for the first time. Harzianone has been previously discovered from T. longibrachiatum cf-11. These isolates exhibited potent inhibition of some marine plankton species.

Cyclonerins A (1) and B (2) along with seven new congeners, deoxycyclonerins A–D (3–6), cyclonerinal (7), cyclonerizole (8), and cyclonerpyranol (9), were isolated from the culture of a marine algicolous strain (A-YMD-9-2) of Trichoderma asperellum. Their structures and absolute configurations were established by spectroscopic techniques, such as 1D/2D NMR, MS, ECD, and X-ray diffraction. Compounds 1–8, highlighted by the presence of an isoxazole ring in sesquiterpene 8, represent the first occurrence of nitrogenous cyclonerane derivatives, with 1 and 2 belonging to an unprecedented family of hydroxamic acids. The new isolates 1–9 exhibited potent inhibition of one or more marine phytoplankton species tested, and it is interesting that the ferric complexes of 1 and 2 feature higher activities than themselves.

In addition to CAF-603, 14-hydroxy CAF-603 (trichocarane B), 7-β-hydroxy CAF-603, and trichocarane A, eight new carotane sesquiterpenes, trichocarotins A-H, and one new cadinane sesquiterpene, trichocadinin A, were isolated from the culture of Trichoderma virens Y13-3, obtained from the surface of a marine red alga. Their structures and relative configurations were unambiguously assigned by interpretation of 1D/2D NMR and MS data, and their absolute configurations were established by X-ray diffraction or ECD spectra aided by quantum chemical calculations. These compounds represent two rarely occurring sesquiterpene types from filamentous fungi, and six of them feature potent inhibition against some marine plankton species.

Red tide occurrs frequently and causes significant damage to the environment and human health. As a result, development of new efficient and environment friendly red-tide microalgae inhibitors has gained increasing attention in recent times. Algicolous endophytic fungi with unique habitats are promising sources for active agents owing to their abundant secondary metabolites and distinguished activities. In this study, the algicidal activities of 49 marine macroalgal-derived endophytic fungi against phytoplankton Alexandrium tamarense, Prorocentrum donghaiense, Heterosigma akashiwo, and Chattonella marina were examined using 96-well microplate. Four fungal strains, including Aspergillus wentii (pt-1), A. ustus (cf-42), and A. versicolor (dl-29, pt-20), exhibited potent algicidal activities. A total of 32 pure compounds isolated from these fungi were noted to possess different degrees of algicidal activities. Of those, 11 compounds comprising five anthraquinones, two terpenoids, and four steroids showed high 24-h inhibition rates for the four red tide algae, with EC 50(24 h) values ranging from 0.01 to 14.29 μg/mL. Among them, compound 1 (1,5-dihydroxy-3-methoxy-7-methylanthraquinone) presented the strongest activity against H. akashiwo, and could decrease its chlorophyll a (Chl a ) and superoxide dismutase contents and increase the soluble protein, malondialdehyde, and peroxidase contents. These results suggested that the identified anti-algal compound might inhibit the growth of red tide algae by weakening photosynthesis (reducing Chl a content), destroying cell membrane, and damaging the antioxidant system.

To explore the metabolic responses of marine-derived Trichoderma fungi to environmental stresses, the survivability, metabolism, and antagonism of ten marine isolates have been examined. Their survival in both freshwater and seawater indicates them to be facultative marine fungi, but they are more adaptable to marine environment. Most of them feature strain-specific and positive metabolic responses to seawater, which also usually result in the higher proportions of heteroatom-bearing and unsaturated units in mycelial constituents. Seawater factors can promote many strains to produce bioactive metabolites, including plant pathogen- and marine phytoplankton-inhibitory and marine animal-toxic ones, but the effects of NaCl are often weak or negative. The inhibition of marine phytoplankton corresponds to the intracellular accumulation of heteroatom-bearing and unsaturated units under seawater condition, and the varied toxicities to marine animals further signify the divergences of lipophilic exudates under different conditions. The results may contribute to further understanding and mining the structural diversity and biological activity of secondary metabolites from marine-derived Trichoderma fungi.

Three cyclonerane sesquiterpenoids, including the known cyclonerodiol (1), together with its new derivatives, (10E)-12-acetoxy-10-cycloneren-3,7 -diol (2) and 12-acetoxycycloneran-3,7-diol (3) were isolated from the cultures of marine-sediment-derived fungus Trichoderma harzianum P1-4. The structures of the new compounds (2 and 3) were elucidated based on extensive spectroscopic methods (1D/2D NMR and HR-MS) and optical rotation analysis.

One new proharziane and three new harziane derivatives (

Carotane sesquiterpenes are commonly found in plants but are infrequently reported in the fungal kingdom. Chemical investigation of Trichoderma virens QA-8, an endophytic fungus associated with the inner root tissue of the grown medicinal herb Artemisia argyi H. Lév. and Vaniot, resulted in the isolation and characterization of five new carotane sesquiterpenes trichocarotins I–M (1–5), which have diverse substitution patterns, and seven known related analogues (6–12). The structures of these compounds were established on the basis of a detailed interpretation of their NMR and mass spectroscopic data, and the structures including the relative and absolute configurations of compounds 1–3, 5, 9, and 10 were confirmed by X-ray crystallographic analysis. In the antibacterial assays, all isolates exhibited potent activity against Escherichia coli EMBLC-1, with MIC values ranging from 0.5 to 32 µg/mL, while 7β-hydroxy CAF-603 (7) strongly inhibited Micrococcus luteus QDIO-3 (MIC = 0.5 µg/mL). Structure-activity relationships of these compounds were discussed. The results from this study demonstrate that the endophytic fungus T. virens QA-8 from the planted medicinal herb A. argyi is a rich source of antibacterial carotane sesquiterpenes, and some of them might be interesting for further study to be developed as novel antibacterial agents.

A new cyclopentenone derivative, 4-hydroxyhypocrenone A, and a new naturally-occurring wickerol derivative, 8-acetoxywickerol A, as well as two known compounds, hypocrenone A and wickerol B, were purified from Trichoderma atroviride A-YMD-9-4, an endophytic fungus isolated from the marine red alga Gracilaria verrucosa. The structures and relative configurations of two new isolates were established by a combination of 1 D/2D NMR, IR, and mass spectroscopic methods, and the absolute configuration of 1 was assigned on the basis of ECD data analyzed by quantum chemical calculations. Compounds 1 and 2 exhibited weak inhibition of one or two marine phytoplankton species.

Eight new trichothecene derivatives, trichodermarins G-N (

Two new naturally occurring sulfurated diketopiperazines, dehydroxymethylbis(dethio)bis(methylthio)gliotoxin (1) and (3S,6R)-6-(para-hydroxybenzyl)-1,4-dimethyl-3,6-bis(methylthio)piperazine-2,5-dione (2), along with three known analogues (3–5) were isolated from the culture extract of Trichoderma virens Y13-3, obtained from the surface of the marine red alga Gracilaria vermiculophylla. The structures and relative configurations of 1 and 2 were determined by extensive 1D/2D NMR, MS, and IR spectroscopic data, and their absolute configurations were established by analysis of ECD spectra aided by quantum chemical calculations. Compounds 1–5 were evaluated for the inhibition of some marine-derived organisms.

Tricholumin A (1) with an unprecedented carbon skeleton was isolated from the fungus Trichoderma asperellum cf44-2, an endophyte from the marine brown alga Sargassum sp. Its structure and relative configuration were identified by extensive 1D/2D NMR and mass spectrometric data, and the absolute configuration was assigned by X-ray diffraction and ECD calculations. Compound 1 represents a highly transformed ergosterol derivative, and it exhibited inhibition of some pathogenic microbes and marine phytoplankton species.

Three undescribed bisabolane derivatives, trichaspin, trichaspsides A and B, three undescribed cyclonerane sesquiterpenes, 9-cycloneren-3,7,11-triol, 11-cycloneren-3,7,10-triol, and 7,10-epoxycycloneran-3,11,12-triol, and one undescribed harziane diterpene, 11-hydroxy-9-harzien-3-one, were obtained from the culture of Trichoderma asperellum cf44-2, an endophyte of the marine brown alga Sargassum sp. Their structures and relative configurations were assigned by analysis of 1D/2D NMR and MS data, and their absolute configurations were established by ECD or specific optical rotation data. Trichaspin features an unprecedented ethylated bisabolane skeleton, while trichaspsides A and B represent the first aminoglycosides of bisabolane and norbisabolane sesquiterpenes, respectively. Nine of the compounds were evaluated for inhibition of five marine-derived pathogenic bacteria and toxicity to a marine zooplankton.

Three novel polyketide-like metabolites, trichorenins A-C (1-3), with a unique tetracyclic carbon skeleton were obtained from the culture of Trichoderma virens Y13-3, an epiphyte of the marine red alga Gracilaria vermiculophylla. Their structures and relative configurations were established by analysis of 1D/2D NMR and MS data, and their absolute configurations were unequivocally assigned by X-ray diffraction and ECD spectra aided by quantum chemical calculations. Compounds 1-3 exhibited potent inhibition against two marine phytoplankton species, Chattonella marina and Karlodinium veneficum.

Two new meroterpenoids, named tricycloalternarenes K ( 1 ) and L ( 2 ), together with one known analog ( 3 ) were isolated from the marine-derived fungus Alternaria alternata ICD5-11, which was obtained from marine isopod Ligia exotica . Their structures and relative/absolute configurations were elucidated by extensive spectroscopic methods, including 1D/2D NMR, CD, and mass spectra and by comparison with literature data. The antimicrobial activities of two new compounds were also tested.

Ten new bisabolane derivatives, trichobisabolins Q–Z (1–10), one new cadinane derivative, cadin-4-en-11-ol (11), and three new cyclonerane derivatives, cycloner-3-en-7,11-diol (12), isoepicyclonerodiol oxide (13), and norepicyclonerodiol oxide (14), were isolated from the endophytic fungal strain RR-dl-6–11 of Trichoderma asperelloides that was obtained from a marine alga. Their structures along with relative configurations were established mainly by NMR and IR as well as MS techniques, and the absolute configurations of 10 and 11 were assigned by ECD and X-ray diffraction data, respectively. Sesquiterpenes from the fungus T. asperelloides are reported for the first time. It is interesting that half of the bisabolane derivatives are demethylated. Compound 12 represents the first the occurrence of cyclopentenyl-bearing cycloneranes, and 14 seems a cyclopentyl-degrading cyclonerane derivative. Several isolates feature potent inhibition of marine phytoplankton species.

In this paper, we report chemical modifications of inulin by seven kinds of aromatic Schiff bases, which are different from their substituent groups. The obtained inulin derivatives were confirmed by FTIR, 1H NMR, and 13C NMR. Then, we studied their antifungal activity against four kinds of plant pathogens involving Botrytis cinerea, Fusarium oxysporum f. sp. cucumerium Owen, Fusarium oxysporum f. sp. niveum, and Phomopsis asparagi by the mycelium growth rate method. The results revealed that all inulin derivatives were endowed with significant antifungal activity compared to inulin. Among them, 6-amino-(N-4-chlorobenzylidene)-6-deoxy-3,4-di-O-acetyl inulin (4CBSAIL) and 6-amino-(N-3,4-dichlorobenzylidene)-6-deoxy-3,4-di-O-acetyl inulin (3,4DCBSAIL), which were synthesized from p-chlorobenzaldehyde and 3,4-dichlorobenzaldehyde, could completely inhibit the growth of the test fungi at 1.0 mg/mL. The inhibitory indices of the inulin derivatives were related to the type, position, and number of substituent groups (halogens) on the Schiff bases. The results confirmed that it was feasible to chemically modify inulin with Schiff bases to confer high antifungal activity to inulin. The products described in this paper have great potential as alternatives to some harmful pesticides used for plant disease control.

Seven previously unreported cyclonerane derivatives, namely, 3,7,11-trihydroxycycloneran-10-one, cycloneran-3,7,10,11-tetraol, cycloneran-3,7,11-triol, 11,12,15-trinorcycloneran-3,7,10-triol, 7,10S-epoxycycloneran-3,15-diol, 7,10R-epoxycycloneran-3,15-diol, and (10Z)-15-acetoxy-10-cycloneren-3,7-diol, were isolated in addition to the known (10Z)-cyclonerotriol, (10E)-cyclonerotriol, catenioblin C, and chokol E from the culture of Trichoderma asperellum A-YMD-9-2, an endophytic fungus obtained from the marine red alga Gracilaria verrucosa. The structures of previously unreported compounds were established by spectroscopic techniques, including 1D/2D NMR, MS, and IR. The isolation of these new cyclonerane derivatives greatly adds to the structural diversity of unusual cyclonerane sesquiterpenes, and several isolates exhibit potent inhibition against some marine phytoplankton species.