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In recent years, the search for novel natural compounds with bioactive properties has received a remarkable boost in view of their possible pharmaceutical exploitation. In this respect the sea is entitled to hold a prominent place, considering the potential of the manifold animals and plants interacting in this ecological context, which becomes even greater when their associated microbes are considered for bioprospecting. This is the case particularly of fungi, which have only recently started to be considered for their fundamental contribution to the biosynthetic potential of other more valued marine organisms. Also in this regard, strains of species which were previously considered typical terrestrial fungi, such as Penicillium and Talaromyces, disclose foreground relevance. This paper offers an overview of data published over the past 25 years concerning the production and biological activities of secondary metabolites of marine strains belonging to these genera, and their relevance as prospective drugs. [ABSTRACT FROM AUTHOR]

Complexation of dissolved organic matter (DOM) plays a crucial role in regulating the fate and risk of agrochemicals. Here, taking a toxic herbicide MCPA (4-chloro-2- methylphenoxyacetic acid) as the target, the effect of land conversion on complexation behavior of DOM to agrochemicals was investigated in paddy soil. Furthermore, the mechanisms were explored in a new perspective of DOM chemodiversity. Soil DOMs were selected from four long-term cropping systems, including paddy field (PF), vegetable field (VF), rice-vegetable rotation (RV) and abandoned land (AL). The results showed that the DOMs in PF and AL were rich in hydrophilic substances (e.g., carbohydrates or protein-like molecules) with low aromaticity. However, after converting PF to VF and RV, abundant aromatic macromolecules and aliphatic alkanes were observed in DOM. Due to those changes in DOM chemodiversity, the binding site and capability of DOM were highest in VF and RV, and were positively correlated with DOM aromaticity, MW, humus and polar groups (e.g., amino). This was because the complexation of "DOM-MCPA" was static binding via ligand exchange and H-bonding among polar groups and hydrophobic interaction among aromatic skeletons. The EEM-PARAFAC confirmed that microbial humic-like substances dominated the complexation of DOM rather than terrestrial humic-like and tryptophan-like matters. The 2D-COS analysis further revealed that the complexation of DOM preferentially occurred in amino, polysaccharide C–O and aliphatic C–H for PF and AL, but in aromatic C=C, amide C=N for RV and VF. In summary, these findings provide molecular insight into the effect of land conversion on DOM complexation activity, which highlight the importance of DOM chemodiversity. These results will contribute to the risk assessments of agrochemicals in paddy soil. [Display omitted] • DOM-MCPA complexation was static binding through specific and nonspecific forces. • Land conversion altered the binding activity, site and order of DOM-MCPA in soil. • The complexation activity of soil DOM was stronger in VF and RV, but weaker in AL. • The complexation depended on DOM chemodiversity, including MW, humus and polar group. [ABSTRACT FROM AUTHOR]

Isolates of Aspergillus species are able to produce a large number of secondary metabolites. The profiles of biosynthetic families of secondary metabolites are species specific, whereas individual secondary metabolite families can occur in other species, even those phylogenetically and ecologically unrelated to Aspergillus. Furthermore, there is a high degree of chemo-consistency from isolate to isolate in a species even though certain metabolite gene clusters are silenced in some isolates. Genome sequencing projects have shown that the diversity of secondary metabolites is much larger in each species than previously thought. The potential of finding even further new bioactive drug candidates in Aspergillus is evident, despite the fact that many secondary metabolites have already been structure elucidated and chemotaxonomic studies have shown that many new secondary metabolites have yet to be characterized. The genus Aspergillus is cladistically holophyletic but phenotypically polythetic and very diverse and is associated to quite different sexual states. Following the one fungus one name system, the genus Aspergillus is restricted to a holophyletic clade that include the morphologically different genera Aspergillus, Dichotomomyces, Phialosimplex, Polypaecilum and Cristaspora. Secondary metabolites common between the subgenera and sections of Aspergillus are surprisingly few, but many metabolites are common to a majority of species within the sections. We call small molecule extrolites in the same biosynthetic family isoextrolites. However, it appears that secondary metabolites from one Aspergillus section have analogous metabolites in other sections (here also called heteroisoextrolites). In this review, we give a genus-wide overview of secondary metabolite production in Aspergillus species. Extrolites appear to have evolved because of ecological challenges rather than being inherited from ancestral species, at least when comparing the species in the different sections of Aspergillus. Within the Aspergillus sections, secondary metabolite pathways seem to inherit from ancestral species, but the profiles of these secondary metabolites are shaped by the biotic and abiotic environment. We hypothesize that many new and unique section-specific small molecule extrolites in each of the Aspergillus will be discovered. [ABSTRACT FROM AUTHOR]

This paper reports a pharmacophylogenetic study of a medicinal plant family, Ranunculaceae , investigating the correlations between their phylogeny, chemical constituents, and pharmaceutical properties. Phytochemical, ethnopharmacological, and pharmacological data were integrated in the context of the systematics and molecular phylogeny of the Ranunculaceae . The chemical components of this family included several representative metabolic groups: benzylisoquinoline alkaloids, ranunculin, triterpenoid saponin, and diterpene alkaloids, among others. Ranunculin and magnoflorine were found to coexist in some genera. The pharmacophylogenetic analysis, integrated with therapeutic information, agreed with the taxonomy proposed previously, in which the family Ranunculaceae was divided into five sub-families: Ranunculoideae, Thalictroideae, Coptidoideae, Hydrastidoideae, and Glaucidioideae. It was plausible to organize the sub-family Ranunculoideae into ten tribes. The chemical constituents and therapeutic efficacy of each taxonomic group were reviewed, revealing the underlying connections between phylogeny, chemical diversity, and clinical use, which should facilitate the conservation and sustainable utilization of the pharmaceutical resources derived from the Ranunculaceae . [ABSTRACT FROM AUTHOR]

Phytoextraction is widely used for the reclamation of degraded sites, particularly to remove trace metals from contaminated soils. Whereas this technique demonstrates several advantages, the biomass resulting from phytoextraction processes is highly enriched in metallic elements and constitutes therefore a problematic waste. We show here that this biomass can be used for the preparation of novel polymetallic extracts, with high potential as catalysts or reagents in organic synthesis. This new concept of ecocatalysis constitutes an innovative recycling of metallic elements whose current known reserves could be exhausted in the coming decades. The ecocatalysts Eco-Zn and Eco-Ni prepared respectively from Zn and Ni hyperaccumulating plants display two distinct chemical reactivities, starting from the same substrates. Eco-Zn led to the formation of esters of commercial interest for the fragrance industry, following a hydro-acyloxy-addition reaction pathway. In contrast, Eco-Ni afforded chlorinated products thank to the hydrochlorination of alkenes. Both ecocatalysts allowed the synthesis of valuable products in high yields through methodologies in line with the spirit of sustainable chemistry. [ABSTRACT FROM AUTHOR]

Aspergillus, Penicillium, and Talaromyces are among the most chemically inventive of all fungi, producing a wide array of secondary metabolites (exometabolites). The three genera are holophyletic in a cladistic sense and polythetic classes in an anagenetic or functional sense, and contain 344, 354, and 88 species, respectively. New developments in classification, cladification, and nomenclature have meant that the species, series, and sections suggested are natural groups that share many extrolites, including exometabolites, exoproteins, exocarbohydrates, and exolipids in addition to morphological features. The number of exometabolites reported from these species is very large, and genome sequencing projects have shown that a large number of additional exometabolites may be expressed, given the right conditions ("cryptic" gene clusters for exometabolites). The exometabolites are biosynthesized via shikimic acid, tricarboxylic acid cycle members, nucleotides, carbohydrates or as polyketides, non-ribosomal peptides, terpenes, or mixtures of those. The gene clusters coding for these compounds contain genes for the biosynthetic building blocks, the linking of these building blocks, tailoring enzymes, resistance for own products, and exporters. Species within a series or section in Aspergillus, Penicillium, and Talaromyces have many exometabolites in common, seemingly acquired by cladogenesis, but some the gene clusters for autapomorphic exometabolites may have been acquired by horizontal gene transfer. Despite genome sequencing efforts, and the many breakthroughs these will give, it is obvious that epigenetic factors play a large role in evolution and function of chemodiversity, and better methods for characterizing the epigenome are needed. Most of the individual species of the three genera produce a consistent and characteristic profile of exometabolites, but growth medium variations, stimulation by exometabolites from other species, and variations in abiotic intrinsic and extrinsic environmental factors such as pH, temperature, redox potential, and water activity will add significantly to the number of biosynthetic families expressed in anyone species. An example of the shared exometabolites in a natural group such as Aspergillus section Circumdati series Circumdati is that most, but not all species produce penicillic acids, aspyrones, neoaspergillic acids, xanthomegnins, melleins, aspergamides, circumdatins, and ochratoxins, in different combinations. [ABSTRACT FROM AUTHOR]

As privileged structures, natural products often display potent biological activities. However, the discovery of novel bioactive scaffolds is often hampered by the chemical complexity of the biological matrices they are found in. Large natural extract collections are thus extremely valuable for their chemical novelty potential but also complicated to exploit in the frame of drug-discovery projects. In the end, it is the pure chemical substances that are desired for structural determination purposes and bioactivity evaluation. Researchers interested in the exploration of large and chemodiverse extract collections should thus establish strategies aiming to efficiently tackle such chemical complexity and access these structures. Establishing carefully crafted digital layers documenting the spectral and chemical complexity as well as bioactivity results of natural extracts collections can help prioritize time-consuming but mandatory isolation efforts. In this note, we report the results of our initial exploration of a collection of 1,600 plant extracts in the frame of a drug-discovery effort. After describing the taxonomic coverage of this collection, we present the results of its liquid chromatography high-resolution mass spectrometric profiling and the exploitation of these profiles using computational solutions. The resulting annotated mass spectral dataset and associated chemical and taxonomic metadata are made available to the community, and data reuse cases are proposed. We are currently continuing our exploration of this plant extract collection for drug-discovery purposes (notably looking for novel antitrypanosomatids, anti-infective and prometabolic compounds) and ecometabolomics insights. We believe that such a dataset can be exploited and reused by researchers interested in computational natural products exploration., (© The Author(s) 2023. Published by Oxford University Press GigaScience.)

• FT-ICR MS was applied to successfully track molecular changes of DOM. • DOM molecules became more diverse as dissolved oxygen decreased. • Reduced, unsaturated HMW compounds accumulated as oxygen depleted. • Oxygen depletion selectively protected otherwise bioavailable compounds. Ocean deoxygenation could potentially trigger substantial changes in the composition and reactivity of dissolved organic matter (DOM) pool, which plays an important role in the global carbon cycle. To evaluate links between DOM dynamics and oxygen availability, we investigated the DOM composition under varying levels of oxygen in a seasonally hypoxic fjord through a monthly time-series over two years. We used ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize DOM on a molecular level. We find a clear trend both in diversity and molecular composition of the DOM along the oxygen gradient. As oxygen decreased, the chemodiversity was significantly increased, along with accumulation of relatively high-molecular-weight, reduced and unsaturated compounds enriched with carboxyl-group structures, which were also thermodynamically less favorable to biodegradation. Our results suggested that oxygen depletion selectively protected otherwise bioavailable compounds from decomposition and may promote the accumulation of a larger recalcitrant DOM pool in the global ocean, which could provide negative feedback to the ocean carbon sequestration and climate change. [Display omitted] [ABSTRACT FROM AUTHOR]

Early plants began colonizing the terrestrial earth approximately 450 million years ago. Their success on land has been partially attributed to the evolution of specialized metabolic systems from core metabolic pathways, the former yielding structurally and functionally diverse chemicals to cope with a myriad of biotic and abiotic pressures. Over the past two decades, functional genomics, primarily focused on flowering plants, has begun cataloging the biosynthetic players underpinning assorted classes of plant specialized metabolites. However, the molecular mechanisms enriching specialized metabolic pathways during land plant evolution remain largely unexplored. Selaginella is an extant lycopodiophyte genus representative of an ancient lineage of tracheophytes. Notably, the lycopodiophytes diverged from euphyllophytes over 400 million years ago. The recent completion of the whole-genome sequence of an extant lycopodiophyte, Selaginella moellendorffii, provides new genomic and biochemical resources for studying metabolic evolution in vascular plants. 400 million years of independent evolution of lycopodiophytes and euphyllophytes resulted in numerous metabolic traits confined to each lineage. Surprisingly, a cadre of specialized metabolites, generally accepted to be restricted to seed plants, have been identified in Selaginella. Initial work suggested that Selaginella lacks obvious catalytic homologues known to be involved in the biosynthesis of well-studied specialized metabolites in seed plants. Therefore, these initial functional analyses suggest that the same chemical phenotypes arose independently more commonly than anticipated from our conventional understanding of divergent evolution of metabolism. Notably, the emergence of analogous and homologous catalytic machineries through convergent and parallel evolution, respectively, seems to have occurred repeatedly in different plant lineages.

Marine micro- and macroorganisms are well known to produce metabolites with high biotechnological potential. Nearly 40 years of systematic prospecting all around the New Caledonia archipelago and several successive research programs have uncovered new chemical leads from benthic and planktonic organisms. After species identification, biological and/or pharmaceutical analyses are performed on marine organisms to assess their bioactivities. A total of 3582 genera, 1107 families and 9372 species have been surveyed and more than 350 novel molecular structures have been identified. Along with their bioactivities that hold promise for therapeutic applications, most of these molecules are also potentially useful for cosmetics and food biotechnology. This review highlights the tremendous marine diversity in New Caledonia, and offers an outline of the vast possibilities for natural products, especially in the interest of pursuing collaborative fundamental research programs and developing local biotechnology programs.

In recent years, the search for novel natural compounds with bioactive properties has received a remarkable boost in view of their possible pharmaceutical exploitation. In this respect the sea is entitled to hold a prominent place, considering the potential of the manifold animals and plants interacting in this ecological context, which becomes even greater when their associated microbes are considered for bioprospecting. This is the case particularly of fungi, which have only recently started to be considered for their fundamental contribution to the biosynthetic potential of other more valued marine organisms. Also in this regard, strains of species which were previously considered typical terrestrial fungi, such as Penicillium and Talaromyces, disclose foreground relevance. This paper offers an overview of data published over the past 25 years concerning the production and biological activities of secondary metabolites of marine strains belonging to these genera, and their relevance as prospective drugs.

UV-C radiation is known to induce metabolic modifications in plants, particularly to secondary metabolite biosynthesis. To assess these modifications from a global and untargeted perspective, the effects of the UV-C radiation of the leaves of three different model plant species, Cissus antarctica Vent. (Vitaceae), Vitis vinifera L. (Vitaceae) and Cannabis sativa L. (Cannabaceae), were evaluated by an LC-HRMS-based metabolomic approach. The approach enabled the detection of significant metabolite modifications in the three species studied. For all species, clear modifications of phenylpropanoid metabolism were detected that led to an increased level of stilbene derivatives. Interestingly, resveratrol and piceid levels were strongly induced by the UV-C treatment of C. antarctica leaves. In contrast, both flavonoids and stilbene polymers were upregulated in UV-C-treated Vitis leaves. In Cannabis, important changes in cinnamic acid amides and stilbene-related compounds were also detected. Overall, our results highlighted phytoalexin induction upon UV-C radiation. To evaluate whether UV-C stress radiation could enhance the biosynthesis of bioactive compounds, the antioxidant activity of extracts from control and UV-C-treated leaves was measured. The results showed increased antioxidant activity in UV-C-treated V. vinifera extracts. [ABSTRACT FROM AUTHOR]

The ecologically and economically important genus Chrysanthemum contains around 40 species and many hybrids and cultivars. The dried capitulum of Chrysanthemum morifolium (CM) Ramat. Tzvel, i.e., Flos Chrysanthemi , is frequently used in traditional Chinese medicine (TCM) and folk medicine for at least 2,200 years. It has also been a popular tea beverage for about 2,000 years since Han Dynasty in China. However, the origin of different cultivars of CM and the phylogenetic relationship between Chrysanthemum and related Asteraceae genera are still elusive, and there is a lack of comprehensive review about the association between biodiversity and chemodiversity of Chrysanthemum . This article aims to provide a synthetic summary of the phylogeny, biodiversity, phytometabolites and chemodiversity of Chrysanthemum and related taxonomic groups, focusing on CM and its wild relatives. Based on extensive literature review and in light of the medicinal value of chrysanthemum, we give some suggestions for its relationship with some genera/species and future applications. Mining chemodiversity from biodiversity of Chrysanthemum containing subtribe Artemisiinae, as well as mining therapeutic efficacy and other utilities from chemodiversity/biodiversity, is closely related with sustainable conservation and utilization of Artemisiinae resources. There were eight main cultivars of Flos Chrysanthemi , i.e., Hangju, Boju, Gongju, Chuju, Huaiju, Jiju, Chuanju and Qiju, which differ in geographical origins and processing methods. Different CM cultivars originated from various hybridizations between multiple wild species. They mainly contained volatile oils, triterpenes, flavonoids, phenolic acids, polysaccharides, amino acids and other phytometabolites, which have the activities of antimicrobial, anti-viral, antioxidant, anti-aging, anticancer, anti-inflammatory, and closely related taxonomic groups could also be useful as food, medicine and tea. Despite some progresses, the genetic/chemical relationships among varieties, species and relevant genera have yet to be clarified; therefore, the roles of pharmacophylogeny and omics technology are highlighted., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Hao, Song, Xiao, Zhong, Wu and Xu.)

In contrast to China where vegatation is predominantly herbaceous, vegetation in Brazil is commonly arboreous. This fact may explain why Chinese drugs are usually acetate derived, while actual and potential natural therapeutic agents from Brazil are mostly shikimate derived. Only relatively few compounds isolated from Brazilian plants have been submitted to adequate pharmacological testing

[Display omitted] • Multivariate analysis was applied to explore the chemical profiles of eight OEOs. • The chemical compositions of OEOs were affected by cultivar. • Carvacrol-, thymol-, and sesquiterpene-rich groups were identified by PLS-DA. • Core antibacterial components were analyzed using a correlation network. Numerous species of Origanum (Lamiaceae) have been widely used as spices to extend the shelf life of foods. Essential oils extracted from this genus have attracted much attention owing to their potential applications as bactericides. Here, we evaluated the chemical compositions of eight oregano essential oils (OEOs) using gas chromatography-mass spectrometry and assessed their antibacterial activities. The chemical compositions of OEOs were affected by the cultivar factor, and seven common compounds, including carvacrol, were identified among eight OEOs. Partial least squares discriminant analysis enabled the distinction of three groups among these OEOs, as characterized by the proportions of carvacrol, thymol, and sesquiterpenes. OEOs effectively inhibited Escherichia coli and Staphylococcus aureus with varying antibacterial activities. Spearman correlation network highlighted core antibacterial contributors in the chemical profiles of OEOs. Our results revealed that the bacteriostatic effects of OEOs could be explained by core compounds and their synergistic effects. [ABSTRACT FROM AUTHOR]

• New family of antimicrobial cyclolipopeptides • The marine genus Pseudoalteromonas as a producer of high chemodiversity of alterins • Investigation of alterin structure using UPLC-HRMS Five strains of Pseudoalteromonas , isolated from oyster haemolymph, have exhibited antibacterial activity against several Gram-negative bacteria. Bioactive compounds have been identified in their cell-free supernatant and characterised as alterins, which are cyclolipopeptides comprising a heptapeptidic ring connected to a fatty acid chain. Using ultra-performance liquid chromatography–high-resolution mass spectrometry, this paper describes 37 structural analogues differing from each other by one or more amino acid residue, the length of the fatty acid chain, its hydroxylation and the presence of unsaturation. [ABSTRACT FROM AUTHOR]

Abstract: Leucojum aestivum, an industrial source of the acetylcholinesterase inhibitor galanthamine, shows a great chemodiversity in its alkaloid synthesis. Samples from various geographically distinct populations from Bulgaria and the Balearic Islands were studied by GC–MS. The alkaloid pattern of the plants of L. aestivum (subsp. pulchellum) from the Balearic Islands were dominated by crinine type compounds. Populations of homolycorine chemotype were distributed along the Danube river in the north part of Bulgaria, which is separated from the south part by the Balkan mountains. Populations with high accumulation of lycorine were found in East Bulgaria near the sea coast, while the south populations were dominated by galanthamine type synthesis. The average of the galanthamine content was found to vary from 0.003 to 0.08% (referred to dry weight) in the north, and up to 0.42% in the southern Bulgarian populations. Some individuals showed up to 0.65% galanthamine. The galanthamine content of the plants from the Balearic island was 0.1% of DW. The galanthamine percentage in the total alkaloid mixture ranged from 0.2 to 95% of the total alkaloids. Our study demonstrated that the geographic isolation of the populations of L. aestivum has led to divergation in the alkaloid biosynthesis and consequently to the occurrence of different chemotypes. This chemodiversity in both alkaloid patterns and galanthamine content provides an opportunity for further selection work toward a galanthamine-rich crop, on the one hand, and makes the species an excellent biological system for molecular studies leading to further improvement of the galanthamine production, which is a valuable alkaloid used in medicine for the treatment of Alzheimer''s disease. [Copyright &y& Elsevier]

Salvia L. is the largest genus in the family Lamiaceae, with about 1,000 species and a nearly cosmopolitan distribution. Salvia species are used in both traditional and conventional medicines, and other numerous industries, such as spices and perfumes. The number of papers dealing with Salvia exceeds 12,000 and mostly investigates their chemical composition and bioactive properties. A smaller proportion of papers however consider environmental factors, mostly on the effects of microclimate conditions on its geographic distribution along an altitudinal or longitudinal gradient, and very few studies can be found on the effects of emerging stressors on the commercial production of sages of medicinal and economical importance. Here, we summarize available data on the essential oil composition of three economically important sages from the Mediterranean area, that is, Salvia officinalis , Salvia officinalis subsp. lavandulifolia , and Salvia fruticosa , and the effects of climate-related environmental stressors on their chemical profiles. Environmental stress factors, such as an increase in soil salinity and aridity, and changes in annual average temperatures, are going to impose a serious risk on the commercial production of sage essential oils, which are commercially produced in many European countries. This review highlights the already confirmed effects of these stressors on three selected Salvia species and consequently the importance of mitigating the effects of climate change on the commercial production of these essential oils., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Karalija, Dahija, Tarkowski and Ćavar Zeljković.)

As extremely active sites processing terrestrially derived dissolved organic matter (DOM), lakes deserve sufficient attention. Because of high-complexity interactions between DOM and the surrounding environment, the natural and anthropogenic drivers controlling the composition and chemodiversity of DOM molecules in lakes remain unclear. Here, 13,952 DOM molecules were identified and assessed in 45 lakes across China via ultrahigh-resolution mass spectrometry. Furthermore, the effects of both natural and anthropogenic factors on the DOM composition, DOM chemodiversity, and greenhouse gas emissions were investigated. The majority of the variations in DOM chemical composition could be attributed to the differences in the hydrology and nutrient concentrations of the lakes, and human activities also played a role, mainly through atmospheric pollution. Environmental factors mainly influenced DOM chemodiversity in the form of S-containing compounds. N-containing compounds exhibited a positive correlation with CO 2 emissions, while N- and S-free compounds exhibited a positive correlation with N 2 O emissions. These results facilitate a comprehensive understanding of the interactions between lake DOM and the surrounding environment, thereby providing a reference for the formulation of strategies aimed at the harmonious development of human and natural environments.

Abstract: Sch-642305 is produced by the endophytic fungi Phomopsis sp. CMU-LMA and exhibits both antimicrobial and cytotoxic activities. The incubation of Sch-642305 with Aspergillus niger ATCC 16404 resting cells leads to two unexpected thio conjugates. Compound (1) is formed by the addition of the cysteine metabolite 3-mercaptolactate to the double bond of Sch-642305. Compound (1) undergoes an intramolecular rearrangement to give compound (2), which contains two rings: a five-membered hydroxylactone ring and a five-membered thiophene ring. The absolute configuration of compound (1) is similar to that of the parent compound, but the configuration of the mercaptolactate side-chain was not determined. The absolute configuration of compound (2) was deduced from the crystal structure and confirmed by the anomal effect of the sulfur atom. To the best of our knowledge, this is the first time such a conjugation rearrangement reactions were observed. The biological significance and the reaction mechanisms are discussed. Compound (1) exhibits a weak antimicrobial activity against Gram-positive bacteria, whereas derivatives (1) and (2) showed an IC50 of 1 and 1.2μM, respectively, against colonic epithelial cancer cells. [Copyright &y& Elsevier]

Fungi can be found in almost all sorts of habitats competing with an even higher number of other organisms. As a consequence fungi developed a number of strategies for protection and communication with other organisms. This review focuses on the increasing number of volatile sesquiterpenes found to be produced by fungal species. The remarkable diversity of this type of volatile organic compound (VOC) within the kingdom fungi is presented and their benefits for the fungi are discussed. The majority of these compounds are hydrocarbons comprising several dozens of carbon skeletons. Together with oxygenated sesquiterpenes they include compounds unique to fungi. Only in recent years the interest shifted from a mere detection and characterization of compounds to their biological function. This review reveals highly diverse ecological functions including interactions with bacteria, other fungi, insects and plants. VOCs act as autoinducer, defend against competing species and play essential roles in attracting pollinators for spreading fungal spores. For many sesquiterpene VOCs sophisticated responses in other organisms have been identified. Some of these interactions are complex involving several partners or transformation of the emitted sesquiterpene. A detailed description of ecological functions of selected sesquiterpenes is given as well as their potential application as marker molecules for detection of mould species. Structures of all described sesquiterpenes are given in the review and the biosynthetic routes of the most common skeletons are presented. Summarizing, this article provides a detailed overview over the current knowledge on fungal sesquiterpene VOCs and gives an outlook on the future developments. [ABSTRACT FROM AUTHOR]

Several aromatic plant species are well known for their high intraspecific variation in terpene composition. Within these species, different chemotypes can be distinguished, which are characterised by one major metabolite and distinct satellite compounds in lower abundance. Such intraspecific differences in plant quality should have major effects on herbivorous insects but may also be partly shaped by their feeding activities. In the present study, the effects of selected Tanacetum vulgare L. chemotypes on herbivore presence and preferences were investigated, and the naturally occurring diversity of T. vulgare was explored at a small spatial scale. A distinct distribution pattern of aphids and miners was found on different chemotypes of different origin of T. vulgare, with species-specific preferences of different herbivorous species. Larvae of two generalist noctuid species performed worse on most chemotypes of T. vulgare than on other plant species. Furthermore, the specific terpene composition of T. vulgare influenced larval development of these two generalist species. The naturally occurring chemical diversity of T. vulgare plants in an area smaller than 3 km was extremely high, exhibiting 14 different chemotypes. Several individual patches of T. vulgare consisted of more than one chemotype. In conclusion, the existing chemotypical pattern of T. vulgare plants leads to a species-specific distribution of herbivores but may in turn be the result of contrasting selection pressures of various specialist and generalist herbivores. [ABSTRACT FROM AUTHOR]

Abstract: Sch-642305 is the major compound produced by the endophytic fungi Phomopsis sp. CMU-LMA. Incubation of Sch-642305 with Aspergillus ochraceus ATCC 1009 resting cells leads to three new derivatives through an oxido-reduction of the six-membered ring of the molecule. Reduction of the double bound leads to compound (1), which subsequently undergoes carbonyl reduction to (2) and ring hydroxylation to (3). According to the previously solved crystal structure of Sch-642305 coupled with 1H NMR NOE correlation and the crystal structure of compound 1, the absolute configurations of the new derivatives were established. In contrast to the parent compound Sch-642305, compound (1) exhibits antimicrobial activity against Gram-negative bacteria. Furthermore, while all derivatives exhibit cytotoxic activity against various cancer cell lines, compound (2) achieved an IC50 of 4nM against human myelogenous leukemia K 562, compared to 20nM for the parent Sch-642305. [Copyright &y& Elsevier]

Abstract: Various pyranocoumarins, calophyllolide, inophyllums B, C, G1, G2 and P, from Calophyllum inophyllum (Clusiaceae) leaves of French Polynesia (Austral, Marquesas, Society and Tuamotu archipelagos) have been determined in 136 leaf extracts using a high pressure liquid chromatography-UV-diode array detection (HPLC–UV-DAD) technique. Results show a wide range in chemical composition within trees growing on eighteen islands. The use of multivariate statistical analyses (PCA) shows geographical distribution of inophyllums and indicate those rich in HIV-1 active (+)-inophyllums. Inophyllum B and P contents (0.0–39.0 and 0.0–21.8mgkg−1, respectively) confirm the chemodiversity of this species within the large area of French Polynesia. The study suggests the presence of interesting chemotypes which could be used as plant source for anti-HIV-1 drugs. [Copyright &y& Elsevier]

A novel butenoate derivative, methyl ( Z )-4-{[( Z )-1-(hydroxymethyl)-2-phenyl-1-ethenyl] amino}-4-oxo-2-butenoate (1), was isolated from the fermentation broth of an Aspergillus niger strain Ta1. The structure (1) was elucidated by spectral analysis. Bioassays showed that compound 1 had a weak antioxidant activity. [ABSTRACT FROM AUTHOR]

Several newly studied species and further accessions of the Lamiaceae have been analyzed for their exudate flavonoid profiles. The principal compounds accumulated were flavones and their 6-methoxy derivatives, whereas flavonols were rarely encountered. The chemodiversity observed was relatively low, with only some 15 derivatives being found. The new data are discussed in relation to published data, and chemosystematic aspects are briefly addressed. Of the studied species, Salvia arizonica yielded only a rare diterpene quinone, demethylfruticulin A. Glandular hair diversification and different qualities of their secretions are briefly discussed. [Copyright &y& Elsevier]