Volatile compounds from interdigital gland of male white-tailed deer (Odocoileus virginianus)

Interdigital secretions were collected from eight male white-tailed deer of various ages. Analysis of volatiles was performed by gas chromatography-mass spectrometry with a modified headspace technique. Forty-six volatile compounds were found including alkanes, arenes, aldehydes, ketones, aliphatic acids, esters, pyrroles, furans, and sulfur compounds. Eleven occurred in higher concentrations (P0.10) in dominant (3.5-year-old) than in subordinate (1.5-year-old) animals. Dominant males typically have higher serum testosterone levels, and fatty acids and esters fluctuate with sebum production, which is under hormonal control. Therefore, these compounds may reflect testosterone levels and act as chemical signals indicating the presence of a dominant male. Interdigital volatiles also may act as generalized scent trail markers.     

Marking urine and preputial gland secretion of male bank voles (Clethrionomys glareolus L.) chemical analyses and behavioral tests

Urine and preputial gland secretion of male bank voles were analyzed by gas chromatography (GC) and mass spectrometry (MS) (selected ion monitoring, SIM). GC-MS analyses showed the presence of hexadecyl acetate in preputial gland secretion and in marking urine but not in metabolic urine. Female bank voles responded more strongly to marking urine of males than to metabolic urine, and they responded more to preputial gland secretion (pure or added to urine) than to metabolic urine. Dominant males spent more time and marked more frequently in response to hexadecyl acetate-enriched urine than to urine alone. The opposite reaction was shown by subordinate males. The results suggest that the acetate functions in the bank voles' dominance interactions.     

Linalool in mandibular gland secretion ofColletes bees (Hymenoptera: Apoidea)

Uinalool was identified as the main component of the mandibular gland secretion in females and males of four species ofColletes bees, viz.,C. cunicularius, C. daviesanus, C. impunctatus andC. succinctus. It was also shown to be the dominant volatile compound in the same gland in maleC. floralis (the female of this species has not yet been investigated). Further, in another species,C. similis, linalool is present in the mandibular gland secretions of females and males, but the dominant volatile component in these secretions is geranial, together with neral. Females of the speciesC. fodiens seem to lack monoterpenes altogether; nonadecane is the dominant volatile compound of the cephalic secretion (based on analysis of a single individual). When linalool is put out in the area of nest aggregation ofC. cunicularius, where the males are patrolling, a distinct increase in flight activity is noted. The function of linalool is discussed on the basis of field observations.This report forms part XXI in the series Studies on Natural Odoriferous Compounds.     

Dufour's gland secretion in the cell linings of bees (Hymenoptera: Apoidea)

The volatile chemicals, detectable by coupled capillary gas chromatography-mass spectrometry, in the nest cell linings of four species in the bee generaColletes, Andrena, andLasioglossum are identical with, and limited to, the volatile components present in the Dufour's gland of females, suggesting this source for some of their cell-lining constituents. The extractable material that lines the cells ofTrachusa byssina, in contrast, is derived fromPinus resin, to which it can be chemically traced.Contribution number 1738 from the Department of Entomology, University of Kansas, Lawrence.     

Leaf-cutting antAtta laevigata (Formicidae: Attini) marks its territory with colony-specific dufour gland secretion

The workers of the leaf-cutting antAtta laevigata were found to mark a territory around their nest and along trunk trails. Elsewhere, we reported that the territorial mark had orientation and agonistic functions. The presence of this mark induced an alarm behavior in intruder workers and stimulated the residents' aggressiveness. Of the parts of the body tested, only the extracts from gaster or Dufour gland were able to induce the same agonistic behavior. The compoundsn-heptadecane, (Z)-9-nonadecene, 8,11-nonadecadiene, and (Z)-9-tricosene, secreted by Dufour gland were identified on foraging trails in the field as components of the territorial odor.     

Volatile components of anal gland secretion of aardwolf (Proteles cristatus)

Volatile constituents of the anal gland secretion and of scent marks of the aardwolf were identified using dynamic solvent effect sampling, capillary gas-liquid chromatography, and mass spectrometry. Both scent marks and gland contents consisted mainly of short- to medium-chain fatty acids, a complex series of medium- and long-chain esters, indole, and hexanol. There were marked individual differences in the relative concentrations of the various components.     

Anal gland secretion of the ferret (Mustela putorius formaFuro)

2,2-Dimethylthietane(1),trans-2,3-dimethylthietane(2),cis-2,3-dimethylthietane(3), 2-propylthietane(4), 3,3-dimethyl-1,2-dithiolane(5),trans-3,4-dimethyl-1,2-dithiolane(6),cis-3,4-dimethyl-1,2-dithiolane(7), 2-pentylthietane (8), 3-propyl-1,2-dithiolane(9), quinoline(10), and indole(11) have been identified as components of the anal gland secretion of the ferret,Mustela putorius formafuro. Male and female ferret secretions were indistinguishable except during the breeding season.     

Identification of the major components in the secretion from the rectal pheromone glands of the queensland fruit fliesDacus tryoni andDacus neohumeralis (Diptera: Tephritidae)

The secretion from the rectal pheromone glands of maleDacus tryoni andDacus neohumeralis is largely a mixture of six aliphatic amides. In order of decreasing quantity these areN-3-methylbutylpropanamide,N-3-methylbutylacetamide,N-(3-methylbutyl-2-methylpropanamide,N-2-methylbutylpropanamide,N-2-methylbutylacetamide, andN-(2-methylbutyl)-2-methylpropanamide. The proportions of the various amides in the two species are similar.     

Chemical composition and efficacy of cephalic gland secretion ofArmitermes chagresi (Isoptera: Termitidae)

Soldiers of the neotropical humivorous termiteArmitermes chagresi have large ice-tong-like mandibles for mechanical defense and a moderate length nasus from which cephalic gland defensive secretions are discharged. Soldiers do not eject secretion, but ooze droplets which are held at the nasus tip by hairs. The chemical secretion is composed of C₂₂–C₂₆ macrocyclic lactones, including C₂₄ and C₂₆ and - and -hydroxylated lactones, with C₂₄ macrolides predominating. The cephalic gland secretion has no pheromonal properties and does not induce alarm or attraction in soldiers or workers. Upon application, the secretion repels and is irritating to ants, but does not appear to act as an antihealant. The defensive behavior and chemistry ofA. chagresi is discussed in light of termite ecology and evolution.     

An investigation of human apocrine gland secretion for axillary odor precursors

Recently completed studies from our laboratories have demonstrated that the characteristic human male axillary odors consist of C₆ to C₁₁ normal, branched, and unsaturated aliphatic acids, with (E)-3-methyl-2-hexenoic acid being the most abundant. To investigate the mechanism by which the odor is formed, it is necessary to determine the nature of the odorless precursor(s) found in the apocrine secretion which is converted by the cutaneous microorganisms to the characteristic axillary odor. Pooled apocrine secretion was obtained from several male volunteers by intracutaneous injection of epinephrine. Partitioning this secretion into aqueous and organic soluble fractions was followed by hydrolysis of each fraction with NaOH or incubation with axillary microorganisms (cutaneous lipophilic corynebacterium). Analysis by gas chromatography/mass spectrometry (GC/MS) revealed the presence of (E)- and (Z)-3-methyl-2-hexenoic acid in the aqueous phase hydrolysate and aqueous phase incubated with bacteria; however, only a trace amount was seen in the resultant organic phase mixtures. These results suggest that a water-soluble precursor(s) is converted by the axillary flora to the characteristic axillary odors.     

Some chemical constituents of the secretion from the temporal gland of the African elephant (Loxodonta africana)

The temporal glands of African elephants were examined macroscopically and histologically, and were found to be modified apocrine sweat glands. The secretion from these glands was analyzed by gas chromatography and mass spectrometry, and some of the major volatile components have been identified as phenol andm- andp-cresol.A portion of this research was funded by the University of California, Los Angeles, Research Grant 1795, to Dr. C.S. Foote.     

Chemical constituents of the chest gland secretion of the thick-tailed galago (Galago crassicaudatus)

The naturally exuded chest gland secretions of adult male and female thick-tailed bush babies were collected directly in capillary tubes. The pure secretion was subjected to GC-MS analysis which revealed three major components. These were identified by comparison with the appropriate standard compounds: benzyl cyanide,p-hydroxybenzyl cyanide, and 2-(p-hydroxyphenyl)ethanol. Analysis of a male and a female secretion indicated that some sexual dimorphism in the relative concentrations of these components may exist.     

Dufour's gland and its role in secretion of nest cell lining in bees of the genusColletes (Hymenoptera: Colletidae)

The liquid secretion of the Dufour's gland in mated females comprises a mixture of macrocyclic lactones, straight chain mono- and dicarboxylic acids, together with trace amounts of di- and trihydroxy monocarboxylic acids and a series ofn-alkanes. Polymerization of the liquid to form the membranous nest cell lining, which also contains alanine and glutamic acid as major constituents, may be mediated by an enzyme from the thoracic salivary gland and voided via the mouth. The composition and structure of the cell linings are similar to those of Wigglesworth's cuticulin.     

Ultrastructure of exocrine prothoracic gland ofDatana ministra (Drury) (Lepidoptera: Notodontidae) and the nature of its secretion

Datana ministra larvae possess a gland situated in the ventral anterior portion of the prothorax. The gland consists of a single sac and is only charged with secretion in the last instar. Its orifice, a simple slit, opens into a transverse invagination of the integument in the cervical margin of the prosternite. The components of the gland have been identified by GC and GCMS and have been shown to be dodecanol, dodecyl acetate, and dodecyl formate. The morphology of the gland and the chemistry of the secretion are discussed in relation to other notodontid larvae which have been investigated. It is conjectured that the secretion is not defensive in nature but may function as a dispersal pheromone.Contribution No 443 Department of Biology, Laval University     

Mandibular gland components of european and africanized honey bee queens (Apis mellifera L.)

The composition of the five-component honey bee queen mandibular gland pheromone (QMP) of mated European honey bee queens was compared to those of virgin and drone-laying (i.e., laying only haploid unfertilized eggs that develop into males), European queens and Africanized mated queens. QMP of mated European queens showed significantly greater quantities of individual components than all queen types compared, except for a significantly greater quantity of 9-hydroxy-(E)-2-decenoic acid (9-HDA) found in Africanized queens. Glands of European drone-laying queens contained quantities intermediate between virgin and mated queens, reflecting their intermediate reproductive state and age. QMP ontogeny shifts from a high proportion of 9-keto-(E)-2-decenoic acid (ODA) in young unmated queens to roughly equal proportions of ODA and 9-HDA in mated queens. A biosynthetic shift occurs after mating that results in a greater proportion of 9-HDA, methylp-hydroxybenzoate (HOB), and 4-hydroxy-3-methoxyphenylethanol (HVA) production, accompanied by a decreased proportion of ODA. Africanized QMP proportions of ODA and 9-HDA were significantly different from European queens. A quantitative definition of a queen equivalent of QMP is proposed for the various queen types, and a standard queen equivalent for mated European honeybee queen mandibular gland pheromone is adopted as 200µg ODA, 80µg 9-HDA, 20µg HOB, and 2 µg HVA.     

Volatile secretion of dufour gland of workers of an army ant,Dorylus (Anomma) molestus

The Dufour glands of workers ofDorylus (Anomma) molestus contain chiefly linear alkenes and alkanes, with (Z)-9-tricosene and tricosane representing over 70%. The glands are relatively small with some indication of very small (nanogram or less) amounts of dihydrofarnesol. Minima, medium, and major workers ofDorylus (Anomma) nigricans contain a similar spectrum of compounds.Dedicated to Professor J.K.A. van Boven on his seventy-sixth birthday.     

Mammalian pheromones VIII Chemical characterization of preorbital gland secretion of grey duiker,Sylvicapra grimmia (Artiodactyla: Bovidae)

Using gas chromatography-mass spectrometry 33 constituents of the preorbital gland of the grey duiker,Sylvicapra grimmia, were identified as unbranched alkanes, 2-alkanones, alkanals, alkanoic acids, alkan-4-olides, as well as 3-methyl-3-buten-1-ol, (Z)-9-octadecenoic acid, benzyl cyanide, diethyl sulfoxide, 2-isobutyl-1,3-thiazole, 2-isobutyl-4,5-dihydro-1,3-thiazole, and 3,4-epoxy-2-dodecanone. Determination of the relative concentrations of these components in a limited number of secretion samples taken from males and females revealed that in these samples the two thiazole derivatives and the epoxy ketone were present in consistently and significantly higher concentrations in male than in female secretions. This suggests that they could act as sex recognition cues.Mammalian pheromones VII: Burger, B.V., Pretorius, P.J., and Stander, J. 1988.Z. Naturforsch. 43c:731–736.     

Chemistry of the defensive secretion of the caddisflyPycnopsyche scabripennis (Trichoptera: Limnephilidae)

From a pair of exocrine glands located on the fifth abdominal sternite, the caddisflyPycnopsyche scabripennis secretes a defensive exudate which containsp-cresol, indole, and skatole. This secretion effectively repels invertebrate predators such as ants. The probable significance of this secretion in the biology of these caddisflies is discussed.     

Sticky secretion from two pairs of defensive glands of rove beetleDeleaster dichrous (Grav.) (Coleoptera: Staphylinidae)

The phylogenetically primitive rove beetleDeleaster dichrous (Grav.) (Oxytelinae) has been shown for the first time to possess two pairs of neighboring abdominal glands which are depleted simultaneously on molestation. The morphology of these glands is described. The defensive constituents of theDeleaster glands were elucidated directly from the mixtures by gas chromatographic-mass spectroscopic methods and microchemical reactions. The paired whitish glands secrete iridodial, which polymerizes on exposure to air to form an adhesive that probably deters small predatory arthropods. The red gland system ofD. dichrous contains the toxicp-toluquinone and a variety of isopropyl andsec-butyl esters. Artificial quinoid ester mixtures simulating the secretion ofD. dichrous showed only weak effects on mortality ofLucilia larvae in comparison with more effective secretions of phyiogenetically derived Oxytelinae. The secretion of the primitive genusDeleaster is characterized chemotaxonomically by , -unsaturated C₁₂ acids and esters, which are postulated as precursors for the characteristic defensive compounds of the derived species, thus indicating a clear evolutionary trend at the micromolecular level.     

Macrocyclic lactones and isopentenyl esters in the Dufour's gland secretion of halictine bees (Hymenoptera: Halictidae)

The volatile components of the Dufour's gland secretion of female halictid bees have been examined in 18 Nearctic species belonging toAgapostemon, Augochlora, Augochlorella, Augochloropsis, Dialictus, Evylaeus, Halictus, andLasioglossum. Nine saturated and unsaturated macrocyclic lactones ranging from C₁₈ to C₂₆ have been identified. Four of these compounds, the saturated C₂₆ and the unsaturated C₂₀, C₂₂, and C₂₄ lactones, are new natural products reported for halictine bees. A series of eight esters containing branched C₅-alkenols and fatty acids has been identified in several species. The cell linings and pollen ball inAugochlora pura pura contain the same major lactones as the Dufour's gland. A discussion of the significance of the Dufour's gland secretion for apoid systematics and its function in the Halictidae is presented.