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Continuous and accurate ceilometer measurements can provide the sky-condition such as cloud base height (CBH), cloud vertical structure (CVS), and cloud cover at around the sites of meteorological stations. In this study, ceilometer measurement data over a period of 3 years (January 2017 to December 2019) were analyzed to compare the characteristics of CBH at inland and coastal stations sharing the same climate characteristics in Korea. The annual averaged frequency of cloud occurrence between 0 and 7750 m at the first CBH is similar in both inland (41.8 ± 10.2%) and coastal (40.3 ± 9.5%) areas. However, there are differences in monthly and seasonal trends. The maximum cloud occurrence appears in summer (winter) of 64.3% (60.1%) in inland (coastal) areas, while the minimum of 25.6% (21.9%) shows in transient seasons of spring and autumn. In winter, the cold surge of northwest wind tends to increase the cloud occurrence from the ocean at coastal rather than in the inland area. It is shown that monthly cloud occurrence in each station is closely related to its monthly precipitation variation. The CVS frequency calculated from the total number of CBH with 250 m vertical bins shows the maximum between 500 to 1500 m (0 to 1000 m) in inland (coastal) areas, indicating more frequent occurrence at a lower height in the coastal area. It is mainly caused by the seasonal variability of the low-level clouds in the coastal region, which occurs two to three times higher in spring and summer than in other seasons. The study implies that long-term measurements of ceilometer would provide a better understanding of the characteristics of cloud behaviors in inland and coastal areas.

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.

Six previously undescribed meroterpenoids, penicianstinoids F-K (1-6), together with four known analogues, dehydroaustinol (7), dehydroaustin (8), penicianstinoid A (9), and furanoaustinol (10), were isolated from the cultures of the algicolous fungus Penicillium sp. RR-DL-1-7, derived from the red alga Rhodomela confervoides. Their structures and relative configuration were established by detailed spectroscopic analysis of NMR and HR-MS experiments, and the absolute configurations were assigned by X-ray diffraction and ECD spectral analysis. None of the isolates showed obvious growth inhibitory effects against five plankton and four bacteria species tested., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2023. Published by Elsevier B.V.)

One new lanostane-type triterpenoid, 3 β -acetoxy-7,11-dioxolanosta-8,24-dien-21-oic acid ( 1 ), together with six known analogues ( 2 - 7 ), were isolated from the cultures of a marine fungus Ceriporia lacerata CD7-5, which was derived from the shellfish Ostrea denselamellosa . Their structures were determined by detailed analysis of spectroscopic data and comparison with the literature reported. The biological activities of these lanostane triterpenoids against marine-derived microalgae, zooplankton, and pathogenic bacteria were also evaluated in this study.

Marine-derived fungi of the genus Trichoderma have been surveyed for pharmaceuticals and agrochemicals since 1993, with various new secondary metabolites being characterized from the strains of marine animal, plant, sediment, and water origin. Chemical structures and biological activities of these metabolites are comprehensively reviewed herein up to the end of 2022 (covering 30 years). More than 70 strains that belong to at least 18 known Trichoderma species have been chemically investigated during this period. As a result, 445 new metabolites, including terpenes, steroids, polyketides, peptides, alkaloids, and others, have been identified, with over a half possessing antimicroalgal, zooplankton-toxic, antibacterial, antifungal, cytotoxic, anti-inflammatory, and other activities. The research is highlighted by the molecular diversity and antimicroalgal potency of terpenes and steroids. In addition, metabolic relevance along with co-culture induction in the production of new compounds is also concluded. Trichoderma strains of marine origin can transform and degrade heterogeneous molecules, but these functions need further exploration., (© 2024. The Author(s).)

Further investigation of secondary metabolites of a marine-alga-derived fungus Aspergillus sp. RR-YLW-12 led to isolate one new ophiobolin-type sesterterpenoid (1), four new drimane-type sesquiterpenoids (2-5) and one natural occurring compound (6), together with seven known compounds (7-13). Their structures and stereochemistry were elucidated by extensive spectroscopic analysis of NMR and HRMS experiments, and by comparison with the literature data. All isolates were evaluated for growth inhibition of five marine harmful microalgae. The new compounds exhibited significant to moderate inhibitory effects towards all tested microalgae species with IC 50 values ranging from 5.8 to 54.5 μg/mL., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2023. Published by Elsevier B.V.)

One new diterpene, harziaketal A (1), and one new highly degraded sterol, trichosterol A (2), along with three known compounds, including one diterpene, harzianone (3), and two steroids, (22E,24R)-5α,6α-epoxy-ergosta-8(14),22-dien-3β,7α-diol (4) and isoergokonin B (5), were isolated from the culture of the marine-alga-epiphytic fungus Trichoderma sp. Z43 by silica gel column chromatography (CC), Sephadex LH-20 CC, and preparative thin-layer chromatography (TLC). Their structures and relative configurations were assigned by nuclear magnetic resonance (NMR) and high resolution electrospray ionisation mass spectrometry (HR-ESI-MS) data, and the absolute configuration of 1 was established by X-ray diffraction. Compound 1 features a hemiketal unit situated at the four-membered ring of harziane-type diterpenes for the first time, while 2 represents the rare occurrence of sterols with rings A and B being degraded. Compounds 1 and 2 displayed weak inhibition against the tested phytoplankton (Amphidinium carterae, Heterocapsa circularisquama, Heterosigma akashiwo, and Prorocentrum donghaiense) with half maximal inhibitory concentration (IC 50 ) ranging from 14 to 53 μg/mL., (© 2023 Wiley-VHCA AG, Zurich, Switzerland.)

Five new lipids, tricholixins A-E ( 1 - 5 ), and two known terpenoids, brasilane A ( 6 ) and harzianone A ( 7 ), were discovered from a deep-sea strain (R22) of the fungus Trichoderma lixii isolated from the cold seep sediments of the South China Sea. Their structures and relative configurations were identified by meticulous analysis of MS and IR as well as NMR data. The absolute configuration of 5 was ascertained by dimolybdenum-induced ECD data in particular. Compounds 1 and 2 represent the only two new butenolides from marine-derived Trichoderma , and they further add to the structural diversity of these molecules. Although 6 has been reported from a basidiomycete previously, it is the first brasilane aminoglycoside of Trichoderma origin. During the assay against wheat-pathogenic fungi, both 1 and 2 inhibited Fusarium graminearum with an MIC value of 25.0 μg/mL, and 6 suppressed Gaeumannomyces graminis with an MIC value of 12.5 μg/mL. Moreover, the three isolates also showed low toxicity to the brine shrimp Artemia salina .

Six new lipids, trichoderols B-G ( 1 - 6 ), along with a known one, triharzianin B ( 7 ), were isolated from the culture of Trichoderma sp. Z43 obtained from the surface of the marine brown alga Dictyopteris divaricata . Their structures and relative configurations were identified by interpretation of 1D/2D NMR and MS data. Compounds 1 - 7 were assayed for inhibiting the growth of three phytopathogenic fungi ( Fusarium graminearum , Gaeumannomyces graminis , and Glomerella cingulata ), four marine phytoplankton species ( Amphidinium carterae , Heterocapsa circularisquama , Heterosigma akashiwo , and Prorocentrum donghaiense ), and one marine zooplankton ( Artemia salina ). Compounds 1 , 4 , and 7 exhibited weak antifungal activities against three phytopathogenic fungi tested with MIC ≥ 64 μg/mL. All compounds displayed moderate antimicroalgal activity with IC 50 ≥ 15 μg/mL and low toxicity to the brine shrimp Artemia salina .

Eight myrochromanol analogues, including three pairs of epimers at C-2 with the myrochromanol scaffold and two examples of myrochromanol with sugar moiety linked at C-4, together with twelve trichothecene derivatives were isolated from the cultures of a shellfish-derived fungus Albifimbria verrucaria CD1-4. Among them, eight compounds named 2-epi-myrochromanol, ent-myrochromanol B, 4-epi-myrochromanol B, 2-epi-myrochromanol A, myrochromanosides A and B, 6',7'-erythro-(2'E,4'Z)-trichoverrol B, 3R,8S-dihyroxyroridin H were previously undescribed fungal metabolites. Their planar structures and relative configurations were established by 1D and 2D NMR, and HR-MS data analysis, and their absolute configurations were determined using the modified Mosher's method and electronic circular dichrosim calculations. Almost all isolates were evaluated for growth rate inhibition of three marine harmful microalgae Chattonella marina, Heterosigma akashiwo, and Prorocentrum donghaiense, and lethal activity to one marine zooplankton, Artemia salina. Myrochromanosides A and B exhibited obvious inhibitory against three tested microalgae with IC 50 values in the range of 9.2-108.9 μM. 8α-Hydroxyroridin H, roridin A and verrucarin A exhibited significant inhibition against P. donghaiense with IC 50 values of 6.1, 5.8, and 6.0 μM and toxicity against brine shrimp larvae with LC 50 values of 1.4, 2.8, and 0.26 μM, respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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.

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.

Four new carotane sesquiterpenoids, byssocarotins A-D ( 1 - 4 ), two new nor-sesquiterpenoids, byssofarnesin ( 5 ) and byssosesquicarin ( 6 ), and three new polyketides, byssoketides A and B ( 7 and 8 ) and (8 R )-paecilocin A ( 9a ), were obtained from a macroalga-associated strain (RR-dl-2-13) of the fungus Byssochlamys spectabilis . These isolates were identified by a combination of spectroscopic methods, including mass spectroscopy, nuclear magnetic resonance, electronic circular dichroism, and X-ray diffraction. Compounds 1 - 4 greatly contribute to the diversity of rarely occurring 2,15-epoxycarotane sesquiterpenoids, while 5 and 6 are degradation products of farnesane and sesquicarane precursors, respectively. Compound 7 is a structurally unique furan fatty acid derivative that possesses an aldehyde group and a large conjugated unit, and 8 features a hemiketal group. During antimicrobial assays, 8 showed antagonism against the phytopathogenic fungi Glomerella cingulata , Fusarium oxysporum f. sp. cucumerium , and F. oxysporum f. sp. cubense and the marine-derived bacteria Vibrio parahaemolyticus and V. harveyi with MIC values of 13 to 50 μg/mL.

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., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Six new sesquiterpenoids including three bisabolane derivatives, trichobisabolins O 1 , O 2 , and P (1-3), two nerolidol derivatives, trichonerolins A and B (4 and 5), one acorane, trichoacorin A (6), along with one new steroid, isoergokonin B (7), were isolated from the culture of Trichoderma brevicompactum A-DL-9-2 obtained from the inner tissue of the red alga Chondria tenuissima. Their structures and relative configurations were assigned by interpretation of 1D/2D NMR and MS data. As acyclic sesquiterpenoids, compounds 4 and 5 were discovered from Trichoderma for the first time. Compounds 1-7 were evaluated for the inhibition of some marine-derived organisms, in which, 3 and 4/5 exhibited potent inhibition against Amphidinium carterae and Chattonella marina with IC 50 of 1.8 μg/mL and 1.2 μg/mL, respectively. In addition, compound 7 could inhibit the growth of Pseudoalteromonas citrea with an MIC value of 64 μg/mL., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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, 3 S -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 IC 50 values of 10.5, 5.2, and 3.1 μg/mL, respectively.

One new proharziane and three new harziane derivatives ( 1 - 4 ) together with six known ones ( 5 - 10 ) were isolated from the marine-alga-derived ascomycete Trichoderma asperelloides RR-dl-6-11. Their structures and relative configurations were determined via spectroscopic techniques, and the absolute configurations were ascertained by analysis of ECD curves. This is the first report on the secondary metabolites of T. asperelloides , and the new isolates ( 1 - 4 ), especially seco -harziane 4 , greatly add to the structural diversity of harziane diterpenes as well as their precursors and catabolites. Compounds 1 - 5 inhibited four marine phytoplankton species, and the structure-activity relationship of harziane derivatives is analyzed.

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 7 β -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.

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.

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 IC 50 values being 4.0 and 0.82 μg/mL, respectively.

Three new phenylhydrazones, penoxahydrazones A-C (compounds 1 - 3 ), and two new quinazolines, penoxazolones A (compound 4 ) and B (compound 5 ), with unique linkages were isolated from the fungus Penicillium oxalicum obtained from the deep sea cold seep. Their structures and relative configurations were assigned by analysis of 1D/2D NMR and mass spectroscopic data, and the absolute configurations of 1 , 4 , and 5 were established on the basis of X-ray crystallography or ECD calculations. Compound 1 represents the first natural phenylhydrazone-bearing steroid, while compounds 2 and 3 are rarely occurring phenylhydrazone tautomers. Compounds 4 and 5 are enantiomers that feature quinazoline and cinnamic acid units. Some isolates exhibited inhibition of several marine phytoplankton species and marine-derived bacteria.

Eight cadinane derivatives, trichocadinins H - N (1-7) and methylhydroheptelidate (8), and two carotane derivatives, 14-O-methyltrichocarotin G (9) and 14-O-methyl CAF-603 (10), including eight new ones (1-6, 9, and 10), were isolated from the culture of Trichoderma virens RR-dl-6-8 obtained from the organohalogen-enriched marine red alga Rhodomela confervoides. Their structures and relative configurations were established by analysis of NMR and mass spectroscopic data, and the absolute configurations were assigned on the basis of ECD curves, highlighted by the ECD diversity of carboxylic acid derivatives. Among the isolates, 1 with a halogen atom and 8, a new naturally occurring compound, are 2,3-seco-cadinane sesquiterpenes, and the epimeric 2 and 3 feature a 2-nor-cadinane skeleton. A commercially-sourced compound with the same planar structure as that of 7 has been reported in a patent, but its configuration was not given. Compounds 1-10 exhibited growth inhibition of some marine phytoplankton species., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A new sordarin derivative, trichosordarin A ( 1 ), with a unique norditerpene aglycone was isolated from the culture of a marine-sediment-derived fungal strain, Trichoderma harzianum R5. Its structure and relative configuration were unequivocally identified by a combination of 1D/2D NMR, IR, and mass spectrometric methods. Compound 1 was assayed to be toxic to the marine zooplankton Artemia salina .

Two new cyclonerane sesquiterpenes, (10E)-isocyclonerotriol (1) and (10Z)-isocyclonerotriol (2), and one new isocoumarin derivative, trichophenol A (3), were isolated from Trichoderma citrinoviride A-WH-20-3, an endophyte from the marine red alga Laurencia okamurai. Their structures and relative configurations were assigned by spectroscopic techniques, highlighted by using Sarotti's DP4+ sheet to confirm the cyclopentane ring. The absolute configuration of 1 was established by comparison of experimental and calculated specific rotation data. Compounds 1 and 2 represent the first occurrence of ring-isomerized cycloneranes. Compound 3 is the first 3-phenylisocoumarin derivative from Trichoderma and features inhibition of several marine-derived bacteria and phytoplankton species., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Three cyclonerane sesquiterpenoids, including the known cyclonerodiol ( 1 ), together with its new derivatives, (10 E )-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.

An examination of the endophytic fungus Trichoderma asperellum A-YMD-9-2 obtained from the marine red alga Gracilaria verrucosa led to the isolation of seven new chromanoid norbisabolane derivatives, trichobisabolins I-L (1-4) and trichaspsides C-E (5-7). Their structures and relative configurations were established on the basis of spectroscopic techniques, mainly including 1D/2D NMR and MS, and the absolute configuration of 1 was assigned by X-ray crystallographic analysis using Cu Kα radiation. All of these isolates feature a 1,9-epoxy ring system, and 5-7 represent the second occurrence of norbisabolane aminoglycosides. Compounds 1-7 exhibited potent inhibition of several marine phytoplankton species., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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, 7,10 S -epoxycycloneran-3,15-diol, 7,10 R -epoxycycloneran-3,15-diol, and (10 Z )-15-acetoxy-10-cycloneren-3,7-diol, were isolated in addition to the known (10 Z )-cyclonerotriol, (10 E )-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.

Eight new bisabolane derivatives, trichobisabolins A-H, along with two known ones, (3R,6R,7R)-1,10-bisaboladien-3-ol (9) and (3R,6R,7S)-1,10-bisaboladien-3,6-diol (10) were isolated from the culture of Trichoderma asperellum Y6-2, obtained from the surface of the marine red alga Chondrus ocellatus. Their structures and relative configurations were identified by interpretation of 1D/2D NMR and MS data. Compounds 1-8 were assayed for inhibiting the growth of some marine-derived organisms, including four marine phytoplankton species, one marine zooplankton species, and five pathogenic bacteria. All of them exhibited inhibition against the marine phytoplanktons with IC 50 values ranging from 2.1-78 μg/mL, compounds 4 and 8 showed weak lethality to the marine zooplankton, and none of them had inhibition against the five pathogenic bacteria., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Correction for 'The value of universally available raw NMR data for transparency, reproducibility, and integrity in natural product research' by James B. McAlpine et al., Nat. Prod. Rep., 2018, DOI: .

Covering: up to 2018With 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.

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., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Six new terpenes, including one harziane diterpene, 3 R-hydroxy-9 R,10 R-dihydroharzianone (1), one proharziane diterpene, 11 R-methoxy-5,9,13-proharzitrien-3-ol (2), three cyclonerane sesquiterpenes, 11-methoxy-9-cycloneren-3,7-diol (3), 10-cycloneren-3,5,7-triol (4), and methyl 3,7-dihydroxy-15-cycloneranate (5), and one acorane sesquiterpene, 8-acoren-3,11-diol (6), were isolated from the culture of Trichoderma harzianum X-5, an endophytic fungus obtained from the marine brown alga Laminaria japonica. Their structures and relative configurations were established by analysis of 1D/2D NMR, HREIMS, and IR data, and the absolute configurations were assigned on the basis of ECD curves or biogenetic considerations. These terpenes possess four different carbon skeletons, and compound 2, with a rarely occurring bicyclic framework, represents a possible precursor of tetracyclic harzianes. Compounds 1-6 exhibited growth inhibition of some marine phytoplankton species.

Two new tricycloalternarene-type meroterpenes, 17-O-methyltricycloalternarene D (1) and methyl nortricycloalternarate (4), and two known congeners, TCA D (2) and TCA 1b (3), were isolated from the culture of a marine red alga-epiphytic fungal strain (k21-1) of Alternaria alternata. The planar structures and relative configurations of these two new compounds were unequivocally identified by a combination of 1D/2D NMR, UV, IR, and mass spectra and by comparison with literature data, and the absolute configurations were assigned by analysis of ECD spectra. Compounds 1-4 were evaluated for growth inhibition of four marine plankton species, but they appeared weak or moderate to inhibit them.

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.

One new bisabolane sesquiterpene, bisabolan-1,10,11-triol ( 1 ), one new norbisabolane sesquiterpene, 12-nor-11-acetoxybisabolen-3,6,7-triol ( 2 ), two new naturally occurring monoterpenes, (7 S )- and (7 R )-1-hydroxy-3- p -menthen-9-oic acids ( 3 and 4 ), one new naturally occurring trichodenone, dechlorotrichodenone C ( 5 ), one new chlorine-containing trichodenone, 3-hydroxytrichodenone C ( 6 ), one new diketopiperazine, methylcordysinin A ( 7 ), and one new naturally occurring oxazole derivative, 4-oxazolepropanoic acid ( 8 ), were isolated from the culture of a marine brown alga-endophytic strain (cf44-2) of Trichoderma asperellum . Their structures and relative configurations were determined by extensive 1D/2D NMR and mass spectrometric data, and the absolute configurations of 3 ⁻ 6 were assigned by analysis of the ECD spectra aided by quantum chemical computations. Compounds 1 , 2 , 5 , and 6 showed growth inhibition of some marine phytoplankton species and pathogenic bacteria.

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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.

To date, no medication is proven to be effective in treating core symptoms of autism spectrum disorder (ASD). Psychotropic medications are widely used to target emotional and behavioural symptoms in ASD. This article reviewed evidence for pharmacotherapy, novel therapeutic agents, and Complementary and Alternative Medicine (CAM) in children and adolescents with ASD. Currently, only risperidone and aripiprazole have been approved by the US Food and Drug Administration (FDA) for treatment of irritability associated with ASD in children and adolescents. However, associated metabolic side-effects are concerning. Evidence supports use of methylphenidate and atomoxetine for attention deficit hyperactivity disorder (ADHD) symptoms and clonidine and guanfacine ER appear to be helpful. SSRIs are poorly tolerated and lack evidence in reducing restricted repetitive behaviours (RRB), anxiety, and depression. Buspirone shows promise in the treatment of RRB. The evidence is inconsistent for the effectiveness of anti-epileptic medications. Recent studies of glutamatergic, Gamma-aminobutyric acid (GABA)ergic, and cholinergic agents and oxytocin show inconsistent results. Despite wide use of CAM agents, the evidence is inconclusive. Melatonin can be helpful in reducing sleep problems. Overall, the evidence is limited for pharmacotherapy in children with ASD, and side-effects with long-term use can be burdensome.

Hymerhabdrin A (1), a diterpenoid possessing a novel 6/6/5 fused-ring skeleton, together with four known sterols were isolated from an intertidal marine sponge Hymerhabdia sp. Their structures were elucidated by extensive spectroscopic methods, and the relative and absolute configurations of 1 were determined by NOESY analysis and electronic circular dichrosim calculations, respectively. Hymerhabdrin A (1) exhibited significant antifouling activity against Balanus amphitrite larval with LC 50 (lethal concentration 50) value of 3.6 μg ml -1 .

A new sesterterpene, sesteralterin (1), four new meroterpenes, tricycloalterfurenes A-D (2-5), and a known meroterpene, TCA-F (6), were obtained from the culture extract of an Alternaria alternata strain (k21-1) isolated from the surface of the marine red alga Lomentaria hakodatensis. The structures and relative/absolute configurations of these compounds were identified by spectroscopic analyses, mainly including 1D/2D NMR, ECD, and mass spectra and quantum chemical calculations. Compound 1 represents the first nitidasane sesterterpene naturally produced by fungi, and 2-5 feature a tetrahydrofuran unit rarely occurring in tricycloalternarenes. Compounds 1-6 were assayed for inhibition of the growth of four marine plankton and one marine alga-pathogenic bacterium.

In order to expand the application range of the model for a single kind of fruits in the portable near infrared instrument, this paper comes up with a new method for the soluble solid content (SSC) model transfer between different kinds of fruits. This method is focusing on the idea of model transfer between different instruments. Based on the similar physical and chemical properties of apples, peaches and pears, such as the range of SSC content, fruit size and the thickness of peel, a simple Slope/Bias algorithm is applied to the transfer of apple SSC partial least square (PLS) model. After that, it can be used to predict pear & peach SSC value with very little extra samples. It’s more convenient and costs less by using this method. For pear samples, by using extra 35 standard samples to transfer apple SSC model, RMSEP reduced from 1.009 °Brix to 0.565 °Brix. For peaches, extra 40 standard samples led to a significant reduce of RMSEP from 1.726 °Brix to 0.677 °Brix after model transfer. To validate the feasibility of this model transfer method, both pear and peach SSC models were tested using the same Slope/Bias algorithm model transfer respectively. A pear SSC model was firstly set up and then transferred with Slope/Bias method. Taking 30 standard apples as samples, RMSEP value reached 0.597°Brix, while taking 40 standard peaches as samples, RMSEP value reached 0.689°Brix. The peach SSC model was transferred in the same way. For apples, using 35 standard samples, RMSEP value reached 0.654°Brix, and for pears, using 30 standard samples, RMSEP value reached 0.439°Brix. These results show that slope/bias algorithm can be used to transfer model between similar kinds of fruits such as apples, pears and peaches. The paper provides innovative ideas for the model transfer among similar kinds of materials, so that the portable near infrared instruments can be used more conveniently and widely.

Citrinovirin (1), a novel norditerpene with an unprecedented carbon skeleton along with three known compounds, cyclonerodiol (2), 3-(2-hydroxypropyl)-4-(hexa-2E,4E-dien-6-yl)furan-2(5H)-one (3), and 5-hydroxy-3-hydroxymethyl-2-methyl-7-methoxychromone (4), was isolated from the culture of a marine brown alga-endophytic strain (cf-27) of Trichoderma citrinoviride. The structure and relative configuration of 1 were identified by spectroscopic methods, including 1D/2D NMR and MS. Its absolute configuration was established by analysis of ECD spectrum, aided by quantum chemical calculations. A plausible biogenetic pathway is proposed for 1, and it was evaluated to be active against Staphylococcus aureus., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Genome mining of the fungus Mucor irregularis (formerly known as Rhizomucor variabilis) revealed the presence of various gene clusters for secondary metabolite biosynthesis, including several terpene-based clusters. Investigation into the chemical diversity of M. irregularis QEN-189, an endophytic fungus isolated from the fresh inner tissue of the marine mangrove plant Rhizophora stylosa, resulted in the discovery of 20 structurally diverse indole-diterpenes including six new compounds, namely, rhizovarins A-F (1-6). Among them, compounds 1-3 represent the most complex members of the reported indole-diterpenes. The presence of an unusual acetal linked to a hemiketal (1) or a ketal (2 and 3) in an unprecedented 4,6,6,8,5,6,6,6,6-fused indole-diterpene ring system makes them chemically unique. Their structures and absolute configurations were elucidated by spectroscopic analysis, modified Mosher's method, and chemical calculations. Each of the isolated compounds was evaluated for antitumor activity against HL-60 and A-549 cell lines.

One new diterpene, trichocitrin (1), and four known secondary metabolites, nafuredin (2), 5-hydroxy-2,3-dimethyl-7-methoxychromone (3), 24-methylenecycloartanol (4) and citrostadienol (5), were isolated from the culture of marine brown alga-endophytic Trichoderma citrinoviride cf-27. Trichocitrin (1) represents the first Trichoderma-derived and furan-bearing fusicoccane diterpene, and its structure and relative configuration were identified by analysis of 1D/2D NMR and mass spectroscopic data. Compounds 1 and 2 exhibited 8.0- and 9.5-mm inhibition zones, respectively, against Escherichia coli at 20 μg/disc and 54.1 and 36.7% growth inhibition, respectively, of Prorocentrum donghaiense at 80 μg/mL.

Purpose of Review: Psychotropic medications are commonly prescribed to people with intellectual disability. We reviewed current evidence-based pharmacotherapy options and recent updates to guide clinicians in their medication management plans., Recent Findings: Antipsychotics, particularly risperidone, appear to be effective in reducing problem behaviors in children with intellectual disability. Evidence in adults is inconclusive. Methylphenidate appears to be effective, and α-agonists appear promising in reducing attention-deficit hyperactivity disorder symptoms. Lithium might be effective in reducing aggression. Evidence is limited to support the use of antiepileptic drugs, anxiolytics, and naltrexone for management of problem behaviors. Antidepressants may be poorly tolerated and might not be effective in reducing repetitive/stereotypic behaviors.In recent trials, glutamatergic and GABAergic agents for fragile X syndrome, and acetylcholinesterase inhibitors for Down's syndrome, failed to show efficacy. Growth hormone treatment might improve cognition and behavior in Prader-Willi syndrome population. Results from oxytocin trials on social behaviors are inconclusive albeit promising. Melatonin appears to improve sleep. Most trials of dietary supplements did not show benefits., Summary: Evidence-based pharmacotherapy options in people with intellectual disability are limited, and many agents can cause substantial adverse events. For this reason, clinicians should consider pharmacotherapy as only a part of comprehensive treatment, and regularly assess drug effects, adverse events, and the feasibility of decreasing dose or withdrawing medications.