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Plants of the Radula genus are chemically very distinct from the other liverworts since they mainly elaborate bibenzyls including bibenzyl cannabinoids and prenyl bibenzyl derivatives, as well as bis-bibenzyls. Several of these components show biological activities such as psychoactivity, vasopressin antagonist, antimicrobial, antifungal, and NO production inhibitory activity, and cytotoxic activity against human cancer cell lines. While distribution of terpenoids in Radula species is in general very limited, some Portuguese species are rich sources of sesquiterpenoids. Among 679 liverwort species so far examined chemically, 264 species contained α-tocopherol, which may play an important antioxidative role for the constituents of oil bodies of liverworts.

Bryophytes, phylogenetically placed between the algae and pteridophytes, are divided into three classes: mosses, liverworts, and hornworts. Traditional system of medicine throughout the world has been utilizing this group of plants to treat various ailments. One of the outstanding features of these spore forming plants is their chemistry, especially that of the liverworts. Liverworts have yielded a rich array of terpenoids, especially sesqui- and diterpenoids. Many of these compounds are characterized by unprecedented structures, and some have not been found in any other plants, fungi or marine organisms. Among the bryophytes, the chemical constituents of liverworts and their biological activity have been studied in the most detail. In this review the chemistry of the terpenoids found in bryophytes have been presented, and their phytotoxic, antimicrobial, antifungal, cytotoxic, anti-inflammatory, piscicidal, insect repellent, antileishmanial and antitrypanosomal activities., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Background: In the search for novel antidepressive drug candidates, bioguided fractionation of nonpolar constituents present in the oleoresin from ginger rhizomes ( Zingiber officinale Roscoe, Zingiberaceae) was performed. This particular direction of the research was chosen due to the existing reports on the antidepressive properties of ginger total extract. The search for individual metabolites acting as MAO-A inhibitors, which correspond to the apparent effect of the total extract, is the subject of this work., Methods: Hexane extracts from ginger rhizomes were fractionated by using column chromatography (including silica gel impregnated with silver nitrate) and semi-preparative high-performance chromatography. For the activity assessment, an in vitro monoamine oxidase A (MAO-A) inhibition luminescence assay was performed on 10 purified terpenes: 1,8-cineole, α-citronellal, geraniol, β-sesquiphellandrene, γ-terpinen, geranyl acetate, isobornyl acetate, terpinen-4-ol, ( E , E )-α-farnesene, and α-zingiberene., Results: Geraniol and (-)-terpinen-4-ol were found to be the strongest enzyme inhibitors with inhibition of 44.1% and 42.5%, respectively, at a concentration of 125 µg/mL. No differences in the inhibition potential were observed for the different groups of terpenes: sesquiterpenes, monoterpenes, or sesquiterpene alcohols; however, the two most active compounds contained a hydroxyl moiety., Conclusions: Terpene constituents from ginger's extract were found to exhibit moderate inhibitory properties against the MAO-A enzyme in in vitro tests.

Comparatively little attention has been paid to the bryophytes for use in the human diet or medicine in spite of the presence of 23 000 species globally. Several hundred new compounds have been isolated from the liverworts (Marchantiophyta), and more than 40 new carbon skeletons of terpenoids and aromatic compounds were found. Most of the liverworts studied elaborate characteristic odiferous, pungent, and bitter-tasting compounds, of which many show antimicrobial, antifungal, antiviral, allergic contact dermatitis, cytotoxic, insecticidal, anti-HIV, plant growth regulatory, neurotrophic, NO production and superoxide anion radical release inhibitory, muscle relaxing, antiobesity, piscicidal, and nematocidal activities. The biological effects ascribed to the liverworts are mainly due to lipophilic sesqui- and diterpenoids, phenolic compounds, and polyketides, which are the principal constituents of their oil bodies. Some mosses and liverworts produce significant levels of vitamin B 2 and tocopherols, as well as prostaglandin-like highly unsaturated fatty acids. The most characteristic chemical phenomenon of the liverworts is that most of the sesqui- and diterpenoids are enantiomers of those found in higher plants. In this review, the chemical constituents and potential medicinal uses of bryophytes are discussed.

Humulanes, drimanes, ent-kaurane, lupane, cycloartane, flavanone, flavones and quinol derivatives were isolated from Malagasy Cussonia vantsilana, Helichrysum gymnocephalum, Phyllarthron madagascariense, Gomphocarpus fructicosus, Cinnamosma sp. and C. fragrans, and their structures elucidated by using extensive NMR analysis. A mixture of a few flavones and/or lupane triterpene showed antimicrobial activity against Mycobacterium smegmatis and Pseudomonas aeruginosa.

The compositions of terpenoids from the solvent extracts of two silicified wood samples were analyzed using a GC/MS method. Chromatographic analysis showed that several biomolecules were preserved unaltered in the Miocene-aged Japanese wood. These were α-terpineol, α-cedrene, thujopsene, widdrol and ferruginol, among others. In addition to the bioterpenoids, the fossil woods contained a series of geoterpenoids that were generated from their biological precursors before and after burial. These were cadalene, daucalene, pseudowiddrene and cuparene. The chemical composition of both analyzed fossil samples suggest that the silicified woods collected in the Noto Peninsula belong to the Cupressaceae family; this was confirmed by morphological analysis. Both samples were identified as Taxodioxylon cunninghamioides, which is the most common Miocene wood in Japan.

Most liverworts elaborate characteristic odiferous, pungent and bitter tasting compounds many of which show antimicrobial, antifungal, antiviral, allergenic contact dermatitis, cytotoxic, insecticidal, anti-HIV, superoxide anion radical release, plant growth regulatory, neurotrophic, NO production inhibitory, muscle relaxant, antiobesity, piscicidal and nematocidal activities. Several inedible mushrooms produce female spider pheromones, strong antioxidant, and cytotoxic compounds. The present paper is concerned with the extraction and isolation of terpenoids from some bryophytes and inedible fungi and their pungent and bitter taste, and cytotoxic and antiviral activity.

Four unusual terpenylated acylphloroglucinols were isolated from the diethyl ether extract of the scales and rhizomes of the fern Dryopteris wallichiana together with the known compounds albaspidins AA and AB, and filixic acids ABA and ABB. Structures of the isolated compounds were established by extensive spectroscopic analysis and their absolute configuration at C-14″ was determined by comparing their CD spectra with those simulated for the respective isomers. Pure acylphloroglucinols displayed moderate in vitro nematocidal activity against L4 stage larvae of Nippostrongylus brasiliensis (LD₅₀=22-121 μM)., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

A new rosane diterpenoid, 3a-hydroxy-5,15-rosadien-11-one (3), was isolated, together with a known rosane diterpenoid, 5,15-rosadiene-3,11-dione (4), and an aromadendrane sesquiterpenoid, ent-cyclocolorenone (5), from the Et(2)O extract of an unidentified Argentine liverwort Anastrophyllum species. Moreover, four known sesquiterpene lactones 6-9 and two known bibenzyls 10, 11 were isolated from the Et(2)O extracts of Argentine Frullania brasiliensis and Radula voluta, respectively. The structures of compounds 3-11 were determined by the use of NMR techniques.

During the course of screening to discover antitrypanosomal compounds, 24 known plant terpenes (6 sesquiterpenes, 14 sesquiterpene lactones and 4 diterpenes) were evaluated for in vitro antitrypanosomal activity against Trypanosoma brucei brucei. Among them, 22 terpenes exhibited antitrypanosomal activity. In particular, α-eudesmol, hinesol, nardosinone and 4-peroxy-1,2,4,5-tetrahydro-α-santonin all exhibited selective and potent antitrypanosomal activities in vitro. Detailed here in an in vitro antitrypanosomal properties and cytotoxicities of the 24 terpenes compared with two therapeutic antitrypanosomal drugs (eflornithine and suramin). This finding represents the first report of promising trypanocidal activity of these terpenes. Present results also provide some valuable insight with regard to structure-activity relationships and the possible mode of action of the compounds., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Diethylether extracts of New Zealand liverworts Jamesoniella colorata and Bazzania novae-zelandiae were investigated to reveal novel terpenoids. The former extract afforded a new modified clerodane-type diterpenoid, and the latter gave a degraded clerodane (rearranged drimane) type sesquiterpenoid. The structures of those new compounds were established by 2D NMR spectra.

The bryophytes contain the Marchantiophyta (liverworts), Bryophyta (mosses) and Anthocerotophyta (hornworts) among which the Marchantiophyta contain cellular oil body and they produce a number of terpenoids, aromatic compounds and acetogenins, several of which show interesting biological activity such as allergenic contact dermatitis, insecticide, insect antifeedant, cytotoxic, piscicidal, muscle relaxing, plant growth regulatory, anti-HIV, DNA polymerase beta inhibitory, anti-obesity, neurotrophic, NO production inhibitory, antimicrobial and antifungal activities. The isolation and chemical structures of biologically active compounds and their total synthesis are reviewed.

In the course of our investigation on biologically active substances from inedible mushrooms in Japan, Germany, and Vietnam, we studied the chemical constituents of 22 species belonging to five families: Scutigeraceae, Polyporaceae, Xylariaceae, Thelephoraceae, and Paxillaceae. Various types of chemical substances were purified and characterized based on the modern spectroscopic methods and also on chemical reactions. These metabolites have shown a broad activity in many biological systems, such as antimicrobial, nematicidal, inhibition of NO production, anti-human immunodeficiency virus, tumor necrosis factor-alpha, and antioxidant activities. These isolated metabolites did not only show interesting activities, but also are employed as chemical markers supported for chemosystematics of these families. This review paper deals with the chemical constituents of 22 species, their biological activities, and also a discussion on chemosystematics., (Copyright 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.)

A new clerodane- and two new ent-rosane-type diterpenoids have been isolated from the New Zealand liverworts Heteroscyphus billardierii and Plagiochila deltoidea, respectively. The known bisbibenzyl compounds and acetophenones have also been isolated from Schistochila glaucescens and Plagiochila fasciculata. Their structures were established by extensive NMR techniques. Chemosystematics of the Plagiochila species have been discussed.

Three neogrifolin derivatives, 3-hydroxyneogrifolin, 1-formylneogrifolin and 1-formyl-3-hydroxyneogrifolin along with grifolin and neogrifolin were isolated from the Japanese mushroom Albatrellus ovinus belonging to Scutigeraceae. Their structures were established by a combination of two-dimensional NMR spectroscopic analyses and by chemical synthesis. 3-Hydroxyneogrifolin and 1-formyl-3-hydroxy-neogrifolin showed more potent antioxidative activity properties than either alpha-tocopherol or BHA.

Hymenosides G--J were newly isolated from the Japanese fern Hymenophyllum barbatum, in addition to hymenosides A--F. The structures of hymenosides were elucidated by extensive two-dimensional nuclear magnetic resonance and/or chemical evidence. The structures of those aglycones were divided into three types, 1,4-dihydroxy-2-hydroxymethyl-but-2-ene, 1,4-dihydroxy-2-methyl-but-2-ene, and 3-hydroxy-5-hexanolide. The sugar moieties were also established by chemical and spectroscopic methods, which were acylated by phenylacetic acid derivatives. These glycosides had a bitter or weakly pungent taste.

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.

In the course of investigation of the bitter-tasting substances of the Japanese fern Hymenophyllum barbatum belonging to the family Hymenophyllaceae, six new hemiterpene glucosides called hymenosides A-F (1-6) have been isolated from the methanol extract, together with an acyclic bis-bibenzyl derivative, perrottetin H. This paper deals with the structure elucidation of the newly isolated glucosides.

p-Cymene (1) was metabolized in rabbits and the following four optically active metabolites, 2-(p-tolyl)-1-propanol (3': R/S = 65:35), 2-(p-tolyl)propanoic acid (5': R/S = 0:100), p-(2-hydroxy-1-methylethyl)benzoic acid (6': R/S = 91:9) and p-(1-carboxyethyl)benzoic acid (8': R/S = 30:70), were isolated in addition to three optically inactive metabolites, 2-(p-tolyl)-2-propanol (2), p-isopropylbenzoic acid (4'), and p-(1-hydroxy-1-methylethyl)benzoic acid (7'). The presumed metabolic pathways of p-cymene in rabbits were confirmed by the administration of the intermediate metabolites (2, 3', 4', and 5'). The enantiomeric ratios of the metabolites, 3' and 6', suggested that omega-hydroxylations of the isopropyl group in 1 and 4' occurred preferentially at the pro-S methyl group. In the metabolism of 1, the S-isomers are predominant in the propanoic acid derivatives, but the R-isomers are rich in the propanol derivatives. It is of interest that the metabolism of 4', however, produced predominantly the corresponding propanol derivative (6'; R/S = 91:9) and propanoic acid derivative (8'; R/S = 80:20) possessing the same R-configuration. Some optically active p-cymene derivatives were also synthesized as standard compounds.

The biotransformation of (+)-, (-)-, and (+-)-alpha-pinenes, (-)-beta-pinene (nopinene), (-)-cis-pinane, (+)-3-carene, (-)-cis-carane, myrcene, and p-cymene in rabbits was investigated. The major metabolites were as follows: (-)-trans-verbenol from (+)-, (-)-, and (+/-)-alpha-pinenes; (-)-10-pinanol and (-)-1-p-menthene-7,8-diol from (-)-beta-pinene; (-)-alpha-terpineol and (-)-trans-sobrerol from (-)-cis-pinane; (-)-m-mentha-4,6-dien-8-ol, 3-caren-9-ol, (-)-3-carene-9-carboxylic acid, and 3-carene-9,10-dicarboxylic acid from (+)-3-carene; carane-9,10-dicarboxylic acid from (-)-cis-carane; and myrcene-3(10)-glycol, myrcene-1,2-glycol, uroterpenol, and p-cymene-9-carboxylic acid from p-cymene. These metabolisms include allylic oxidation, epoxidation, stereoselective gem-dimethyl hydroxylation and its oxidation, cleavage of a conjugated double bond by epoxidation, and regioselective oxidation, some of which are not found usually in chemical reactions, and due to which various new compounds were determined. This biotransformation of the monoterpene hydrocarbons gave some insect pheromones in high yield.U

1. The metabolism of 1,4-cineole, a monoterpene ether, was studied in the rabbit. 2. Four neutral and one acidic metabolites were isolated from the urine and shown to be 9-hydroxy-1,4-cineole, 3,8-dihydroxy-1,4-cineole, 8,9-dihydroxy-1,4-cineole, 1,4-cineole-8-en-9-ol and 1,4-cineole-9-carboxylic acid.

1. The metabolism of (+)-citronellal, (+-)-7-hydroxycitronellal, citral, (-)-perillaldehyde, (-)-myrtenal, cuminaldehyde, thujone, and (+-)-carvone was studied in rabbits. 2. In (+-)-7-hydroxycitronellal, (-)-perillaldehyde, (-)-myrtenal and cuminaldehydes, both primary alcohols and carboxylic acids were formed. 3. In (-)-citronellal and citral, regioselective oxidation was found and a trans-positioned methyl group was carboxylated in each case. 4. In o-cuminaldehyde, reduction but not oxidation, was found.

The article discusses the study regarding the analysis and identification of terpenoid and steroid components of various liverworts including Porella platyphylla, Scapania nemorosa, and Bazzania japonica. Topics include the isolation and analysis of the chemical compound found in the species, the extraction and the isolation of the species' extracts, and various compound identified including crude extract, sesquiterpene alcohol, and bisabola.