Structures and possible functions of epoxypukalide and pukalide

Chemical analysis of the eggs spawned by fiveSinularia soft corals (Octocorallia, Alcyoniidae) collected in the central region of the Great Barrier Reef, Australia, revealed the presence of the known cembranoid diterpenes epoxypukalide and/or pukalide in all cases. Examination of the colonies from which the eggs were released one month before spawning and also some time after spawning failed to detect either diterpene in the coral tissue. The three dimensional structures of pukalide and epoxypukalide, as determined by the single-crystal X-ray technique, are reported for the first time. The wide distribution of pukalide and epoxypukalide and of related compounds within the octocorallia is discussed.     

Volatile Components in Dorsal Gland Secretions of the White-Lipped Peccary, Tayassu pecari, from Bolivia

Secretions from the dorsal gland of male and female free-ranging adult white-lipped peccaries (Tayassu pecari) from Bolivia were analyzed by gas chromatography–mass spectrometry. Fifty compounds were identified, some provisionally. Secretions of both sexes contain saturated and unsaturated C₅–C₁₈ carboxylic acids as well as isomers of the diterpene springene. The females' secretions uniquely possess farnesyl esters of C₈ and C₁₀ carboxylic acids, whereas the males' secretions uniquely showed two compounds provisionally identified as monounsaturated C₁₆ lactones. Saturated high-molecular-weight esters of C₁₀ carboxylic acids are more abundant in the females' secretions than in those of the males. The secretions of both sexes also contain monoalkanoate esters of methylhydroquinone as major components.     

Chemistry and Anatomy of the Frontal Gland in Soldiers of the Sand Termite Psammotermes hybostoma

A great diversity of defensive chemicals has been described in termite soldiers equipped with a unique defensive organ, the frontal gland. Along with the functional diversity of these compounds, reflecting the evolutionary history of particular lineages and their defensive strategies, a considerable degree of chemical variability often occurs among species and populations. Thus, the chemistry of termite defense may provide information on the phylogeny and geographic dispersal of species and populations. In this paper, we report on the anatomy of the frontal gland and on the diversity of soldier defensive chemicals in the sand termite, Psammotermes hybostoma, from nine colonies and five different localities in Egypt. Using gas chromatography-mass spectrometry, a total of 30 sesquiterpene hydrocarbons, or their oxygenated derivatives, were detected, and the chemical identity of most of them identified. In addition, a ketone, an ester, and a diterpene were identified in some colonies. Within colonies, the chemical composition was stable and did not differ among soldier size categories. However, there were pronounced quantitative and qualitative differences in frontal gland chemicals among colonies and geographic locations. The findings are discussed in a broader comparison with other termite taxa.     

Antimicrobial terpenes from oleoresin of ponderosa pine treePinus ponderosa: A defense mechanism against microbial invasion

The oleoresin of the ponderosa pine,Pinus ponderosa (Pinaceae) exhibited broad antimicrobial activity. In order to identify the active compounds, the oleoresin was steam distilled to give a distillate and residue. The distillate contained mainly monoterpenes and some sesquiterpenes, while the residue consisted chiefly of four structurally related diterpene acids. An antimicrobial assay with the pure compounds indicated that the monoterpenes were active primarily against fungi, but there was also some activity against gram-positive bacteria. The diterpene acids, in contrast, only exhibited activity against gram-positive bacteria. Although not all of the identified sesquiterpenes could be tested, longifolene showed activity only against gram-positive bacteria. Therefore, it appears that the oleoresin ofP. ponderosa functions as a biochemical defense against microbial invasion.     

(+)-Juniperol and (+)-pimaral: Attractants for the cerambycid beetle,Monochamus alternatus Hope

A sesquiterpene and a diterpene were isolated from sound pines and identified as (+)-juniperol and (+)-pimaral, respectively. The combination of these compounds in a certain ratio induced a significant laboratory flight response by the female cerambycid beetle,Monochamus alternatus Hope. Individual compounds elicited a limited response only.     

Biosynthesis of sesqui- and diterpenes by the gibberellin producer Fusarium fujikuroi

The fungus Fusarium fujikuroi IMI58289 emits a complex pattern of volatile terpenoids including two major compounds, the sesquiterpene alcohol α-acorenol and the diterpene ent-kaurene. ent-Kaurene is the precursor for the phytohormone gibberellic acid (GA(3)) and is produced from geranylgeranyl diphosphate (GGPP) via ent-copalyl diphosphate by the bifunctional ent-copalyl diphosphate/ent-kaurene synthase (CPS/KS). Several structurally related diterpenes were identified as side products of the CPS/KS. Deletion of the cps/ks gene or the whole GA(3) biosynthetic gene cluster resulted in completely abolished diterpene production. Mutants with deletions of the cytochrome P450 monooxygenase gene P450-4, which is responsible for the three oxidation steps from ent-kaurene to ent-kaurenoic acid en route to GA(3), accumulate diterpene hydrocarbons. Feeding with [6,6,6-(2) H(3)] mevalonolactone gave insights into the stereochemistry of the GGPP cyclisation, which operates with a chair-chair-"antipodal" fold. A rational biosynthetic scheme for all identified sesquiterpenes demonstrated their formation from farnesyl diphosphate (FPP) via three alternative initial cyclisations. Genome sequencing revealed the presence of five putative sesquiterpene synthase genes in the F. fujikuroi genome. The structures of several trace compounds from other classes have been identified as new natural products; these were delineated from their mass spectra and unambiguously assigned by comparison to synthetic references.     

Interspecific variation of diterpene composition ofCubitermes soldier defense secretions

Soldiers of the humivorous termite generaCubitermes andCrenetermes (Isoptera: Termitidae: Termitinae) secrete a mixture of unusual diterpene hydrocarbons from the fontanellar opening of the frontal gland. The defense secretions of sixCubitermes species and oneCrenetermes species show species-specific distributions of the five chemically identified major components and 12 unidentified minor components. The secretion is also present with its characteric terpene distribution in white presoldiers and newly molted soldiers, but is completely absent in workers.Fellow of the Alfred P. Sloan Foundation (1981–85) and Camille and Henry Dreyfus Teacher-Scholar (1981–86).     

Tumorpromovierende Diterpen-Fettsäureester aus Euphorbia triangularis und Euphorbia cooperi

Tumor-Promoting Diterpenyl Fatty Acid Esters from Euphorbia triangularis and Euphorbia cooperi Three diterpenic diesters were isolated from milk-juice of Euphorbia triangularis and they were identified as 13-isobutyrate (T₁), 13-tiglate (T₂) and 13-(2-methyl-butyrate) (T₃) of the new diterpene 12-desoxyphorbol. Apart from these, a mixture of corresponding 20-acetates (T₁–T₃) could be isolated and characterized. The known crotophorbolon is obtained by alkali-treatment of 12-desoxyphorbol-13-tiglate under energetic conditions. A diterpene-diester and a diterpene-triester were isolated from milk-juice of Euphorbia cooperi and they were characterized as 13-O-isobutyroyl-16-tiglate and ?20-acetate respectively of the new diterpene 12-desoxyphorbol-16-hydroxyphorbol. All the isolated diterpene esters showed more or less pronounced irritation on mice ear. In general, the 20-esters are less effective than the corresponding esters having the free 20-hydroxyl group. Exact knowledge of the isolated esters is significant from the viewpoint of environmental protection, since some of these compounds might possess co-carcinogenic properties as well.     

Intra- and interindividual variation in flank gland secretions of free-ranging shrewsCrocidura russula

Individual differences in flank gland secretions were examined among males of the monogamous shrewCrocidura russula during the breeding and nonbreeding seasons. Gas chromatography was used to measure intra- and interindividual variation of flank gland secretions of free-ranging shrews from different populations. The number of compounds detected by gas Chromatographic analyses was correlated with body mass, flank gland size, and the presence of blood parasites in individual shrews. Very few compounds were detected from the flank gland area of juvenile males. After they reached sexual maturity, however, the number of compounds detected from the flank gland secretions increased significantly. At the beginning of the reproductive season 48 different compounds were detected from male flank gland secretions. In the middle of the breeding season 70 compounds were detected, while only 11 compounds were detected during the nonbreeding season. Few compounds were common to all males. There were more volatile compounds in the flank gland secretions of males in the beginning of the breeding season than later in the breeding season. Males from the same population had fewer differences in the elution profile of compounds than males from different populations indicating that individuals from a distinct population have similar elution profiles of compounds and that each population has its own type of elution profile. No correlations were found between the number of compounds detected by gas chromatography for each male and the male's body mass or flank gland size. Blood parasites (trypanosomes,Trypanosoma crocidurae) were found in only three of 30 males investigated.     

Species-specific natural products of adult male leaf-footed bugs (Hemiptera: Heteroptera)

The 7–8th ventral abdominal gland secretions from 6 adult male leaf-footed bugs,Leptoglossus spp., and a related species,Euthochtha galeator, were chemically analyzed by GC-MS. Of the 11 volatile compounds identified, all but one of the compounds (n-octanol) were aromatic, including compounds with the familiar odors of cherries, vanilla, cinnamon, and roses. The preponderance of aromatics in the adult male ventral abdominal gland secretions contrasts sharply with the aliphatic compounds which comprise the metathoracic gland defensive secretions of adult males and females. Also, the male-specific secretions are species-specific, both qualitatively and quantitatively, whereas the metathoracic gland secretions of Coreoidea are only distinctive at the generic level. It is proposed that males were favored as the emitters of attractive signals by sexual selection, whereas the specificity of the signal is the result of natural selection against hybridization.     

烟用香料研究进展简介

本文对近十多年来国外烟用香料的研究作一简介 ,内容包括烟叶中香味成分研究 ,烟用香原料合成 ,二萜化合物的开发 ,Maillard反应产物 ,释放型香料及其它。     

Metapleural Gland Secretion of the Leaf-cutter Ant Acromyrmex octospinosus: New Compounds and Their Functional Significance

Ants of the myrmicine tribe Attini live in symbiosis with a fungus that provides them with food. In return the ants maintain optimal growth conditions for the fungus, weed out competing microorganisms, and inhibit the growth conditions of these competitors by chemical means. We present a comprehensive analysis of metapleural gland secretions of Acromyrmex octospinosus, using a recently developed method for the analysis of polar compounds by gas chromatography and mass spectrometry. We show that the chemical identity and quantitative recovery of different compounds in the metapleural gland secretion depends upon the method used and the type of colony from which the samples are taken. In addition to the two compounds previously recorded in the metapleural gland secretion of Acromyrmex ants (indolacetic acid and myrmicacin), 20 new compounds were detected in the secretion of a random sample of workers from two laboratory colonies and two field colonies. These compounds span the whole range of carboxylic acids from acetic acid to the long-chain fatty acids but comprise also some alcohols, lactones, and keto acids. The possible function of this highly complex secretion mixture is discussed.     

Sex pheromone of the woodbine leafroller moth,Sparganothis sp.

The sex pheromone of the woodbine leafroller,Sparganothis sp., includes (E)-11-tetradecen-1-ol, (Z)-11-tetradecen-1-ol, and (E)-11-tetradecen-1-yl acetate, based on chemical analysis of gland extracts, electroantennogram tests, and field trapping. Highest trap catches were obtained when these compounds were dispensed in the relative proportions observed in the female gland. (Z)-11-Tetradecen-1-yl acetate also was found in gland extracts, but significantly reduced trap catches. The saturated compounds tetradecan-1-ol and tetradecan-1-yl acetate were found in gland extracts as well, but were not tested. The amounts of these compounds per female gland were 127, 93, 17, 20, 25, and 3 ng, in the order named.Lepidoptera: Tortricidae.Supported by National Science Foundation Grant PCM 78-13241.     

Behavioral bioassays of termite trail pheromones

The monocyclic 14-membered ring diterpene, cembrene-A, previously identified as a nasutitermitine trail pheromone, was tested for its effectiveness as a trail pheromone inNasutitermes costalis. Artificial trails prepared from serial dilutions of racemic cembrene-A over a concentration range of 10^–1–10^–6 mg/ml were ineffective in recruiting termites. Serial dilutions of racemic cembrene-A ranging in concentration from 10^–1 to 10^–5 mg/ml produced an orientation effect. Chiral cembrene-A produced recruitment in soldiers at 10^–1 and 10^–3 mg/ml and was less ineffective in recruiting workers. Soldiers always showed a lower and more variable recruitment response to chiral cembrene-A than to sternal gland extracts. The behavioral response to both chiral and racemic cembrene-A was different in quantity and quality from that observed for sternal gland extract. Based on the results of these behavioral tests, cembrene-A appears to be a generalized nasute orientation pheromone which may show recruitment properties at unnaturally high concentrations.     

Volatile communication substances in Dufour's gland of virgin females and old queens of the antFormica polyctena

Dufour's gland, which is present in worker ants ofFormica polyctena as a tiny gland emptying into the short duct from the poison reservoir, was found to be very enlarged in virgin females. In egg-laying queens the gland lobes were reduced in size to slender tubes. The glandular secretion was analyzed by capillary gas chromatography and mass spectrometry. Seventy-four percent of the gland secretion from virgin females consisted of undecane, but this compound was less than 1% in queens. Decane and nonane, making up 3.5% in virgin females, were not found in queens. About 74% of their secretion consisted of the lower hydrocarbons: tridecane, pentadecane, heptadecane, and a nonadecene with tridecane dominating to 50%. Apart from these characteristic differences, almost the same compounds were present in virgin females and queens. Thirty-three compounds were identified from the secretion of virgin females and 38 from queens. An additional compound present in trace amounts in the secretion from queens has not been identified. All the compounds were hydro-carbons with the exception of dodecanol, present in trace amounts in virgin females. The compounds are homologous series of saturated, aliphatic hydrocarbons from nonane to tricosane and corresponding series of monounsaturated and methyl-branched hydrocarbons. Geranylgeraniol and geranyl-geranyl acetate, present in worker ants together with some other alcohols and acetates, were absent in females.     

Composition of tall oil pitch

Compositions of six grades of tall oil pitch (TOP), four of finnish and two of U.S. origin were investigated. The pitch samples contained 34.6–51.6% free acids, 23.2–37.8% esterified acids, and 25.3–34.4% unsaponifiable neutral compounds. Each of the above fractions was analyzed by high resolution gas chromatography-mass spectrometry. Approximately 60% of the weight fraction in TOP consisted of high molecular components of which about half were acidic compounds. The low molecular free acids were mainly dehydroabietic, abietic, and other resin acids. The esterified acids consisted chiefly of oleic and linoleic acids. Unsaponifiable fractions were composed of diterpene alcohols, fatty alcohols, sterols, and dehydrated sterols. The alcohol components were almost completely esterified.     

Volatile Compounds from Anal Glands of the Wolverine, <Emphasis Type="Italic">Gulo gulo</Emphasis>

Dichloromethane extracts of wolverine (Gulo gulo, Mustelinae, Mustelidae) anal gland secretion were examined by gas chromatography–mass spectrometry. The secretion composition was complex and variable for the six samples examined: 123 compounds were detected in total, with the number per animal ranging from 45 to 71 compounds. Only six compounds were common to all extracts: 3-methylbutanoic acid, 2-methylbutanoic acid, phenylacetic acid, α-tocopherol, cholesterol, and a compound tentatively identified as 2-methyldecanoic acid. The highly odoriferous thietanes and dithiolanes found in anal gland secretions of some members of the Mustelinae [ferrets, mink, stoats, and weasels (Mustela spp.) and zorillas (Ictonyx spp.)] were not observed. The composition of the wolverine’s anal gland secretion is similar to that of two other members of the Mustelinae, the pine and beech marten (Martes spp.).     

Comparative survey of abdominal gland secretions of the ant subfamily Ponerinae

The chemical contents of three abdominal glands were investigated in representative species of the ponerine ants. The Dufour glands of 14 species show a wide variety of contents. In Mystrium camillae and Proceratium itoi, no volatile substances were found in either the Dufour or venom glands. In Ectatomma sp., Diacamma ceylonense, Diacamma indicum, Pachycondyla obscuricornis, and Pachycondyla striata, volatile chemicals were found in the venom glands as well as in the Dufour glands. Platythyrea punctata was examined, but unusually it does not have a Dufour gland and its venom gland contained no volatile substances. Epoxides were found in ants for the first time in the Dufour glands of Amblyopone reclinata. Venom glands of Pachycondyla tarsata were also found to contain volatile material, including bitter-tasting cyclic dipeptides. In all, 16 species have been added to the list of those examined. All of the 27 known analyses of Dufour glands, 21 analyses of venom glands, and 4 of pygidial glands of workers of ponerine ant species have been brought together in order to seek some pattern in the type of glandular contents. Although the great majority of species produce hydrocarbons in their worker Dufour glands, and some have terpenes, there is no observable pattern for this gland on a tribe or genus level. Volatile compounds have been found in the venom glands of some species of the tribe Ponerini only. The information on pygidial glands is still too fragmentary for any conclusions.     

Hydrocarbons and other weakly polar unsaponifiables in some vegetable oils

The hydrocarbon fractions obtained from sunflower, olive, soybean, rapeseed and pumpkin seed oils by fractionation of unsaponifiable matter were composed of n-paraffins, isoprenoidal polyolefins, squalene, diterpene and triterpene hydrocarbons and compounds with oxygen. Iso-, anteiso- and other branched hydrocarbons were not identified in any of investigated oils. Possible compounds with oxygen are aliphatic and alicyclic ketones, conjugated steroid ketones, esters and lactones. The differences in the hydrocarbon fractions of investigated oils suggest they may be used for characterization.     

Chemical and behavioral studies on dufour gland contents ofManica rubida (Hymenoptera: Formicidae)

The Dufour gland ofManica rubida contains a simple mixture of (Z, E)-α-farnesene and (Z, E)-α-homofarnesene with tiny amounts of other faraesene, homofarnesene, and bishomofarnesene isomers. The gland also contains a mixture of very volatile compounds, chiefly acetone, with smaller amounts of acetaldehyde, ethanol, propanol, isobutyraldehyde, butenone, and butanone. The workers ofM. rubida are not attracted to these highly volatile compounds as are workers ofMyrmica species, butM. rubida workers show a strong increase of linear speed when stimulated by a freshly isolated gland. This response of increased speed of bothM. rubida andM. trubra to their own or each other's Dufour gland secretion is consistent with the presence of the farnesenes in them both.