Chemical Ecology of Cave-Dwelling Millipedes: Defensive Secretions of the Typhloiulini (Diplopoda, Julida, Julidae)

Cave animals live under highly constant ecological conditions and in permanent darkness, and many evolutionary adaptations of cave-dwellers have been triggered by their specific environment. A similar "cave effect" leading to pronounced chemical interactions under such conditions may be assumed, but the chemoecology of troglobionts is mostly unknown. We investigated the defensive chemistry of a largely cave-dwelling julid group, the controversial tribe "Typhloiulini", and we included some cave-dwelling and some endogean representatives. While chemical defense in juliform diplopods is known to be highly uniform, and mainly based on methyl- and methoxy-substituted benzoquinones, the defensive secretions of typhloiulines contained ethyl-benzoquinones and related compounds. Interestingly, ethyl-benzoquinones were found in some, but not all cave-dwelling typhloiulines, and some non-cave dwellers also contained these compounds. On the other hand, ethyl-benzoquinones were not detected in troglobiont nor in endogean typhloiuline outgroups. In order to explain the taxonomic pattern of ethyl-benzoquinone occurrence, and to unravel whether a cave-effect triggered ethyl-benzoquinone evolution, we classed the "Typhloiulini" investigated here within a phylogenetic framework of julid taxa, and traced the evolutionary history of ethyl-benzoquinones in typhloiulines in relation to cave-dwelling. The results indicated a cave-independent evolution of ethyl-substituted benzoquinones, indicating the absence of a "cave effect" on the secretions of troglobiont Typhloiulini. Ethyl-benzoquinones probably evolved early in an epi- or endogean ancestor of a clade including several, but not all Typhloiulus (basically comprising a taxonomic entity known as "Typhloiulus sensu stricto") and Serboiulus. Ethyl-benzoquinones are proposed as novel and valuable chemical characters for julid systematics.Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3085

Quinones and non-quinones from the defensive secretion of unciger transsilvanicus (Verhoeff, 1899) (diplopoda, julida, julidae), from Serbia

A complex mixture of compounds was identified from the secretion of specimens of Unciger transsilvanicus. Phenol and p-cresol were detected for the first time in the family Julidae, and for the second time in the order Julida. Thirteen quinones were identified, with a great relative abundance of toloquinone and 2-methoxy-3-methyl- 1,4-benzoquinone. Hydroquinone was detected for the first time in the order Julida. Besides these compounds, isopentyl hexacosatetraenoate and isopentyl esters of saturated and unsaturated fatty acids with chain lengths from C-14 to C(20)were identified. The most abundant non-quinone compound was isopentyl eicosenoate. The relative abundance of quinone and non-quinone in the defensive fluid of U transsilvanicus was 77% and 23%, respectively. The phylogenetic importance of the registered compounds is briefly discussed

Supplementary data for article: Makarov, S. E.; Bodner, M.; Reineke, D.; Vujisić, L. V.; Todosijević, M. M.; Antić, D. Ž.; Vagalinski, B.; Lučić, L. R.; Mitić, B. M.; Mitov, P.; et al. Chemical Ecology of Cave-Dwelling Millipedes: Defensive Secretions of the Typhloiulini (Diplopoda, Julida, Julidae). Journal of Chemical Ecology 2017, 43 (4), 317–326. https://doi.org/10.1007/s10886-017-0832-1

Supplementary material for: [https://doi.org/10.1007/s10886-017-0832-1]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2450

An Insight into Fatty Acid Composition of Calliergonella cuspidata

The fatty acid composition of the moss Calliergonella cuspidata (Hedw.) Loeske (Amblystegiaccae) was preliminary analyzed by gas chromatography (GC FID) and gas chromatography-mass spectrometry (GC-MS). Six fatty acids were identified in its chloroform-methanol extract 1/1: palmitic acid (66.83 %), stearic acid (11.73%), oleic acid (8.21 %), linolenic acid (6.01 %), alpha-linolenic acid (3.95 %) and arachidic acid (3.26 %). Arachidonic acid and cis-5,8,11,14,17-eicosapentaenoic acid, typical long-chain polyunsaturated fatty acids for many mosses, were not detected in Calliergonella cuspidata

Sesquiterpene lactones from plant species Centaurea solstitialis L.

The identification of nine known guaianolides, i.e., solstitialin A, its 13-acetate, linichlorin B, cynaropicrin, centaurepensin (chlorohyssopifolin A), 17-epi-centaurepensin, 19-desoxychlorojanerin, 11 beta,13-dihydrodesacylcynaropicrin and 8-desacylcentaurepensin-8-O-(4-hydroxy)tiglate in the aerial parts of Centaurea solstitialis is reported. The last four lactones were isolated for the first time from this species. Other compounds detected in this extract, not found before in C. solstitialis. were syringaresinol (lirioresinol B) and arctigenin (the known lignans)

Sesquiterpene lactones from plant species Centaurea solstitialis L.

The identification of nine known guaianolides, i.e., solstitialin A, its 13-acetate, linichlorin B, cynaropicrin, centaurepensin (chlorohyssopifolin A), 17-epi-centaurepensin, 19-desoxychlorojanerin, 11 beta,13-dihydrodesacylcynaropicrin and 8-desacylcentaurepensin-8-O-(4-hydroxy)tiglate in the aerial parts of Centaurea solstitialis is reported. The last four lactones were isolated for the first time from this species. Other compounds detected in this extract, not found before in C. solstitialis. were syringaresinol (lirioresinol B) and arctigenin (the known lignans)

A new lichen depsidone from l obaria pulmonaria

The continuation of our phytochemical survey of Lobaria pulmonaria (L.) Hoffm. (Lobariaceae), has led to the isolation and identification of a new lichen depsidone (1) characterised by the normal analytical and spectroscopic techniques. Unlike previously isolated depsidone (2) from the same species, the compound 1 has not showed activity in the acetylcholinesterase inhibition test on Thin-layer chromatography plate

Fatty acid composition of seed oil of Phlomis fruticosa growing in Montenegro

Ministry of Science of the Republic of Serbia [143041, 143049

Antimutagenic activity of essential oil and crude extract of Phlomis fruticosa

The present study was carried out to investigate the antimutagenic activity of essential oil and crude extract of Phlomis fruticosa. This species belongs to the family Lamiaceae which includes a number of species with medical and pharmaceutical properties. The Escherichia coli K12 reversion assay for identifying antimutagens was used. The number of spontaneous and UV-induced Arg(+) revertants, as well as cell survival was monitored in the presence of non-toxic concentrations of the essential oil. The number of UV-induced revertants was slightly increased in the presence of essential oil. The ethanol extract demonstrated a significant effect on viable cells. Study on pharmacological and phytochemical activities as well as antimutagenetic potential against some chemical mutagens of the essential oils, total extract and their different fractions and constituents of Ph. fruticosa is in progress.nul

The HPLC determination of the content of magnoflorine in Epimedium alpinum L.

The aporphine alkaloid magnoflorine, known as a constituent of Asian Epimedium species, was isolated for the first time from the wild growing European species, Epimedium alpinum L. Identification was done by comparison with literature data. The HPLC method was applied for the determination of the content of the alkaloid in methanolic extracts of plant material. The underground part of E. alpinum contains 1–2 % of magnoflorine, while its content in methanolic extracts was 9.2–11.8 %. The aerial part of the plant contains less alkaloid (0.06–0.12 %), while the magnoflorine content in methanolic extracts of the aerial part was 0.4–0.8 %. Probably, the high content of magnoflorine in the methanolic extracts of underground parts of E. alpinum influences its dose-dependent cytotoxic activity (300 mg/ml; 39 % survival of cells in an experimental K562 cell culture)