Chemosystematics of the hepaticae

Most liverworts (Hepaticae) contain oil bodies which are composed of lipophilic terpenoids and aromatic compounds. The chemosystematics of 36 families of the Jungermannidae and seven families of the Marchantiidae of the Hepaticae are discussed using terpenoid and aromatic components.     

The Oil Bodies of Liverworts: Unique and Important Organelles in Land Plants

Oil bodies of liverworts are intracellular organelles bounded by a single unit membrane containing lipophilic globules suspended in a proteinaceous matrix. They are a prominent and highly distinctive organelle uniquely found in liverworts. Although they have been widely used in taxonomy and chemosystematics, and many of their secondary metabolites are known to be bioactive and are considered as potential sources of medicines, their origin, development and function still remain poorly understood. Recently, biochemical studies have indicated that the isoprenoid biosynthetic pathways in liverworts are similar to those of the seed plants and that oil bodies of Marchantia polymorpha contain a protein complex immunologically related to plastid and cytosolic enzymes of isoprenoid synthesis. Cytoplasmic lipid droplets lacking a bounding membrane have recently been recognized as important dynamic organelles playing active roles in cell physiology. Structural proteins, covering the surface of the lipid droplets and preventing them coalescing during desiccation, have been found in seed plants and also in the moss Physcomitrella patens. However, whether liverwort oil bodies play a dynamic role in cell metabolism, in addition to their role as sites of essential oil accumulation and sequestration, has not been formally tested. In this review, we present current knowledge on the oil bodies of liverworts on their origin and development, their role in taxonomy, chemosystematics and potential pharmaceutical applications leading to their functional significance, and we also identify avenues for future studies on this important but long-overlooked organelle.     

Recent advances in phytochemistry of bryophytes-acetogenins, terpenoids and bis(bibenzyl)s from selected Japanese, Taiwanese, New Zealand, Argentinean and European liverworts

Bryophytes contain a large number of terpenoids and phenolic compounds. Recent topics relating to the chemical constituents found in 36 Japanese, 3 New Zealand, 2 European, 1 Argentinean and 1 Taiwanese liverworts and 2 Japanese mosses and their biological activity are discussed. The chemosystematics of some liverworts as well as the chemical relationship between liverworts and mosses, and bryophytes and ferns are also discussed.     

Metabolomic fingerprinting using nuclear magnetic resonance and multivariate data analysis as a tool for biodiversity informatics: A case study on the classification of Rosa x damascena

Metabolomics is the comprehensive and simultaneous identification and quantification of metabolites in living cells. The term metabolome is used to describe the observable chemical profile or fingerprint of the metabolites in a whole tissue. Although being a new approach to study natural compounds, metabolomics uses traditional analytical techniques, including extraction methods, which can be followed by nuclear magnetic resonance (NMR) spectroscopy and multivariate data analysis. Although metabolomics has been successfully applied to quality control issues, the examples of its use for chemosystematics are few. Thus, the analysis of four taxa of Rosa x damascena (R. damascena Mill., R. damascenasemperflorens, R. damascenatrigintipetala and R. duchesse of Portland) was carried out by NMR spectroscopy as a tool for their classification. A principal component analysis of the ¹H NMR spectra, based on the metabolites found in organic and aqueous fractions, showed a clear similarity of the samples. In particular, the major contributions from the aqueous fraction, preliminarily considered as a biomarker of R. x damascena group, are the flavonoids kaempferol and quercetin, glycosilated with glucose and rhamnose units. Our analysis demonstrated a close chemotaxonomic correlation among the four taxa, making this method a reliable tool for chemosystematics.     

Triterpenes from Angelica cartilagino-marginata var. foliata Yuan et Shan and their significance as chemosystematic characters

One new and three known triterpenes were isolated from roots of Angelica cartilagino-marginata var. foliata Yuan et Shan. The structures of the new compounds were determined by modern spectroscopic techniques, including 2D NMR experiments. These triterpenes are important characters in chemosystematics of Umbelliferae.     

The biosynthesis of flavonoid glycosides and their importance in chemosystematics

The present article reviews flavonoid O-glycosyltransferases with respect to the historical background, isolation and purification methods, properties of the enzymes involved (especially substrate specificities) and genetic control. The possible biosynthetic pathway leading to the formation of C-glycosides is also discussed. The second part of the article is an attempt to indicate the importance of glycosylation patterns in the field of chemosystematics, especially on the intra- and infra-specific levels. The position and nature of glycosylation are first discussed, and this is followed by examples indicating the importance of glycosylation patterns.     

Sesqui- and diterpenoids from two Japanese and three European liverworts

A new peroxy muurolane-type sesquiterpenoid was isolated from the ether extract of the Belgium liverwort Scapania undulata, together with three known ent-muurolanes. A new lepidozane-type sesquiterpenoid was isolated from the Japanese Porella subobtusa together with a known santalane- and two africane-type sesquiterpenoids. All structures were determined by means of NMR spectroscopic techniques. The chemosystematics of each species are discussed.     

The chemosystematics of Tribulaceae

The chemistry of members of the family Tribulaceae has been studied. Thirty-two flavonoid glycosides were detected in the 22 taxa examinied and found to be based on the aglycones kaempferol, quercetin, isorhamnetin and tricin. The compounds ranged from mono- to tetraglycosides as well as acylated glycosides. The four genera Tribulus, Tribulopis, Kelleronia and Kallstroemia belonging to the subfamily Tribuloideae were studied together with Sisyndite belonging to the subfamily Neoluederitziodeae. The chemosystematics of the Tribulaceae are discussed in relation to the Zygophyllaceae.     

Status and Perspective of Sponge Chemosystematics

In addition to their pharmaceutical applications, sponges are an important source of compounds that are used to elucidate classification patterns and phylogenetic relationships. Here we present a review and outlook on chemosystematics in sponges in seven sections: Secondary metabolites in sponges; Further applications of bioactive compound research in sponges; Sponge chemotaxonomy; Pitfalls of sponge chemotaxonomy; The chemotaxonomic suitability of sponge compounds; Potential synapomorphic markers in sponges; and The future of sponge chemotaxonomy.     

Distribution and variability of cuticular hydrocarbons within the Coleoptera

The cuticular lipids of 37 species of beetles (Coleoptera), 12 of which belong to the suborder Adephaga and 25 to the suborder Polyphaga, were analysed. They were found to consist almost exclusively of hydrocarbons. GLC and MS analyses revealed distinct patterns of hydrocarbons comprising alkanes, alkenes and alkadienes, 2-, 3- and internally branched monomethylalkanes as well as dimethyl-branched alkanes. These patterns depend on the species but exhibit conformity at the super-family or family level. The utility of cuticular hydrocarbons for coleopterous chemosystematics is discussed.     

Chemical constituents of Malagasy liverworts: cyclomyltaylanoids from Bazzania madagassa

Five cyclomyltaylanoids (2-6), together with 1R,5R-diacetoxycyclomyltaylan-10-one (1), (+)-globulol, and ent-4beta,10alpha-dihydroxyaromadendrane have been isolated from the diethyl ether fraction of the Malagasy liverwort, Bazzania madagassa. The structure of 1 was confirmed by X-ray analysis, while those of the compounds were established on the basis of one- and two-dimensional NMR spectroscopic evidence, and comparison with data reported in the literature. The chemosystematics of B. madagassa are discussed.     

Chemosystematics in the Opiliones (Arachnida): a comment on the evolutionary history of alkylphenols and benzoquinones in the scent gland secretions of Laniatores

Large prosomal scent glands constitute a major synapomorphic character of the arachnid order Opiliones. These glands produce a variety of chemicals very specific to opilionid taxa of different taxonomic levels, and thus represent a model system to investigate the evolutionary traits in exocrine secretion chemistry across a phylogenetically old group of animals. The chemically best‐studied opilionid group is certainly Laniatores, and currently available chemical data allow first hypotheses linking the phylogeny of this group to the evolution of major chemical classes of secretion chemistry. Such hypotheses are essential to decide upon a best‐fitting explanation of the distribution of scent‐gland secretion compounds across extant laniatorean taxa, and hence represent a key toward a well‐founded opilionid chemosystematics.     

Fungal phytotoxins: from basic studies to practical use (a review)

Recent materials are summarized, pertaining to classification of fungal phytotoxins, methods of their isolation, and assays for biological activity. Producers of phytotoxic substances have been characterized, and the chemical nature of phytotoxins has been subjected to analysis. The review gives consideration to the mechanisms of action of phytotoxins on susceptible plants and the mechanisms of plant resistance to such agents. Other matters discussed include prospects of utilizing basic knowledge of the nature and mechanisms of action of phytotoxins for developing means of plant protection against diseases and weeds and identifying or classifying fungi (chemosystematics).     

An approach to the chemosystematics of the zygophyllaceae

The Zygophyllaceae occur in arid zones and have been reported to contain, among other compounds, flavonoids and alkaloids. The flavonoids in representatives of three of the seven subfamilies have been studied and their distribution is discussed with respect to their chemosystematic significance. The aglycones identified were kaempferol, quercetin, isorhamnetin, herbacetin and herbacetin-8-O-methyl ether. Glycosidic patterns elucidated range from mono- to tri-glycosides, five of which are novel in plants. Alkaloids were also shown to be present, and the importance of those cited in the literature has been surveyed in relation to the chemosystematics of the Zygophyllaceae.     

Medium molecular weight polar substances of the cuticle as tools in the study of the taxonomy,systematics and chemical ecology of tropical hover wasps (Hymenoptera: Stenogastrinae)

The Stenogastrinae wasps have been proposed as a key group for an understanding of social evolution in insects, but the phylogeny of the group is still under discussion. The use of chemical characters, in particular cuticular hydrocarbons, for insect taxonomy is relatively recent and only a few studies have been conducted on the cuticular polar substances. In this work, we ascertain, by the matrix‐assisted laser desorption ionization‐time of flight mass spectrometry technique, that different species of primitively eusocial hover wasps have different compositions of the epicuticular polar compounds ranging from 900 to 3600 Da. General linear model analysis and discriminant analysis showed that the average spectral profiles of this fraction can be diagnostic for identification of the species. Moreover, for the first time we show population diversification in the medium MW polar cuticular mixtures in insects. In conclusion, the results demonstrate that the chemical characters are consistent with the physical characters and the study support the importance of medium MW polar substances as powerful tools for systematics (chemosystematics) and chemical ecology (fertility signal and population characterization) in a primitively social insect taxon.     

Fern constituents: Including occurrence,chemotaxonomy and physiological activity

A comprehensive survey of the 1966–1984 literature of the chemical constituents in ferns is presented. A table of fern constituents listed by species arranged according to Crabbe et al. (1975) is included. Advances in flavonoid, terpenoid and xanthone fern phytochemistry, including chemosystematics, are summarized. The taxonomic, chemical and pharmaceutical aspects of the phloroglucinols found in ferns are discussed. Developments in the investigation into the structure of the toxic principles of bracken (Pteridium aquilinum), whose consumption leads to cancer in domestic stock and to bracken cattle poisoning, are presented.     

Polyprenylated benzophenone derivatives from Clusia burle-marxii and their chemotaxonomic significance

Six polyprenylated benzophenone derivatives (1–6) with the central bicyclo[3.3.1]nonane-2,4,9-trione core were isolated from Clusia burle-marxii trunks. Despite their highly conserved structural characteristics, this is the very first time that these polyprenylated benzophenone derivatives are isolated from a single plant species, highlighting the biochemical plasticity of Clusia burle-marxii to produce such unique class of bioactive compounds. Compounds 1, 2, and 6 are reported for the first time in Clusia burle-marxii, whereas compounds 3, 4 and 5 are reported for the first time in the Clusiaceae family. Their structures were established by careful analysis of spectroscopic data, including ¹H NMR, ¹³C NMR, and 2D-NMR (COSY, NOESY, HSQC, HMBC). These polyprenylated benzophenone derivatives have the potential to be used as chemosystematics biomarkers for the family Clusiaceae. Their putative biosynthesis pathway is also discussed.     

The flavonoids of theFagonia bruguieri complex (Zygophyllaceae)

Seven flavonol glycosides were identified from the main taxa of theF. bruguieri complex. Of these, kaempferol 3-rhamno-galactoside, Quercetin 3-rhamnogalactoside and Quercetin 3-galactoside are new records for the genusFagonia L. and theZygophyllaceae s. str. The distribution of these flavonoid glycosides is discussed with respect to the morphology, chemosystematics, and possible phylogeny of the complex and the genus.Dedicated to Hofrat Univ.-Prof. DrKarl Heinz Rechinger on the occasion of his 80th birthday.     

A review of fungal phytotoxins: from basic studies to practical use

Recent materials are summarized, pertaining to classification of fungal phytotoxins, methods of their isolation, and assays for biological activity. Producers of phytotoxic substances have been characterized, and the chemical nature of phytotoxins has been subjected to analysis. The review gives consideration to the mechanisms of action of phytotoxins on susceptible plants and the mechanisms of plant resistance to such agents. Other matters discussed include prospects of utilizing basic knowledge of the nature and mechanisms of action of phytotoxins for (1) developing means of plant protection against diseases and weeds and (2) identifying or classifying fungi (chemosystematics).     

Cyclic azaphilones daldinins E and F from the ascomycete fungus Hypoxylon fuscum (Xylariaceae)

Phytochemical examination of the methanolic extract of fruit bodies of the Xylariaceous ascomycete fungus Hypoxylon fuscum led to the isolation of two azaphilone derivatives named daldinins E and F together with two known compounds daldinin C and 4,5,4',5'-tetrahydroxy-1:1'-binaphthyl using a combination of reversed phase HPLC and high performance gel permeation chromatography. Their structures were determined by 2D NMR, MS, IR, UV, and CD spectroscopy. Their antioxidative activities were also estimated by an indication of a 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging effect. The chemosystematics of Hypoxylon is discussed.