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.     

Analysis of characteristic human female axillary odors: Qualitative comparison to males

Odors produced in the human female axillae are of both biological and commercial importance. Several studies have suggested that extracts from female underarm secretions can alter the length and timing of the female menstrual cycle. In addition, more than 1.6 billion dollars are spent annually on products to eliminate or mask the axillary odors. Our recent studies have determined that the characteristic axillary odors in males consist of C₆–C₁₁, saturated, unsaturated and branched acids, with (E)-3-methyl-2-hexenoic acid (3M2H) being the major compound in this mixture. The 3M2H appears to be carried to the skin surface bound to two proteins in the axillary secretions. Data reported here show that the same mixture of odorous compounds is found in female axillary secretions, with several minor qualitative differences. Separation of the female apocrine secretions into aqueous and organic soluble fractions demonstrated that 3M2H, and several other members of the acids in the characteristic odor, are released by hydrolysis with base. Electrophoretic separation of the proteins found in the aqueous phase of female apocrine secretions revealed a pattern identical to that seen in males. The qualitative similarity of the acidic constituents making up the characteristic axillary odors of both females and males as well as the proteins present in the aqueous phase suggest a similar origin for axillary odors in both sexes.     

Structure-activity relationship of unsaturated fatty acids as mosquito ovipositional repellents

Various straight-chain unsaturated fatty acids from C₁₄ to C₂₄ were evaluated for their ovipositional repellency against gravid females of the southern house mosquitoCulex quinquefasciatus Say, and the relationship between the structures of the fatty acids and their ovipositional repellency was determined. A double bond withZ configuration was prerequisite for an unsaturated fatty acid to be highly repellent;E isomers were less active or even inactive. No relationship was found between the repellency and the number of double bonds in the unsaturated fatty acids. In C₁₈ monounsaturated fatty acids, (Z)-9 acid was more active than (Z)-11 and (Z)-6 acids, indicating that a double bond at the 9 position rendered an acid highly repellent. Among (Z)-9-alkenoic acids of different chain lengths, the most repellent was C₁₈ acid which was also more active than (Z)-11-C₂₀, (Z)-13-C₂₂, and (Z)-15-C₂₄ acids. Oleic[(Z)-9-octadecenoic]acid, which met all these criteria, was the most ovipositionally repellent among the unsaturated fatty acids tested.Diptera: Culicidae.     

The structure of polyenoic odd- and even-numbered fatty acids of mullet (Mugil cephalus)

Mullet oil contains more than 25% straight-chain odd-numbered fatty acids. Odd- and even-numbered components of chain lengths C₁₅ to C₂₀ were isolated and their structures determined. The vinylmethane rhythm prevails in all polyun-saturated acids. Numerous homologs have their double bonds in identical positions, relative to the carboxyl group, as for example, 舥^9,12- and 舥^6,9,12-C₁₅, -C₁₆, -C₁₇ and -C₁₈ acids. The terminal structures which are characteristic for oleic, linoleic, etc., families are not found in the unsaturated odd-numbered acids. The results show: that the proximal structure has greater influence than the terminal structure on the biosynthesis of unsaturated odd-numbered acids; that chain lengths of 17 and 18 carbon atoms with double bonds in position 9 are crucial for synthesis of the polyenoic C₁₉ and C₂₀ acids; that chain lengths C₁₅ and C₁₆ with double bonds in position 9 are suitable for desaturation but that they are not suitable for desaturation after elongation. These specifications bring all acids of mullet into a rational order and reflect their possible interconversions. Presently, such classification has only limited predictive value in regard to the physiological properties of polyunsaturated acids. However, the new definitions for grouping the polyunsaturated fatty acids lead to interesting working hypotheses.     

Degradation of combustible shale kerogen from the Dmitrievskoe deposit by ozonolysis

The process characteristics and the composition of products of the ozonolytic degradation of combustible shale kerogen from the Dmitrievskoe deposit (Kuznetsk Basin) in chloroform were studied. The soluble products of combustible shale ozonization mainly consisted of aliphatic C₉-C₂₂ n-monocarboxylic and C₂-C₁₁ dicarboxylic acids. Among the constituents of water-insoluble products, C₇-C₂₅ higher fatty acids were predominant with an impurity of unsaturated and aromatic compounds.     

Secondary amines isolated from venom gland of dolichoderine antTechnomyrmex albipes

A series of unsaturated secondary amines have been isolated from the dolichoderine antTechnomyrmex albipes (F. Smith). The major components of the mixture have been shown by spectroscopic procedures to be dinon-8-enylamine, andN-hept-6-enylnon-8-enamine, and these structural assignments have been confirmed by synthesis. Mass spectrometry indicates the presence of trace amounts of the bis C₁₁ amine and the C₉-C₁₁ amine. The four amines, present in total at approximately 2.8g/ant, are located in the gaster of the insect in a gland that is considered to be the venom gland although it is atypical from a morphological standpoint.     

Synthese ungesättigter C12-C14-Fettalkohole durch Metathese oleochemischer Verbindungen

Synthesis of Unsaturated C₁₂-C₁₄- Fatty Alcohols by Metathesis of Oleochemicals The metathesis of silylated oleyl alcohol with a mixture of isomeric n-hexene leads under chain shortening to a mixture of unsaturated C₁₁-C₁₃- silylethers using Re₂O₇/AI₂O₃ + SnMe₄ as catalyst at 65°C/2 h. In the same way silylated 10-undecenol is converted under chain prolongation to a mixture of C₁₂-C₁₄-silylethers. A conversion of 77% is obtained even at a molar ratio of Re₂O₇: C₁₁-silylether: n-hexenes of 1 : 400 : 800. Terminal unsaturated C₁₂/C₁₄-fatty alcohols are obtained by reductive cleavage of jojoba oil with HAl(i-C₄H₉)₂, silylation of the unsaturated C₂₀/C₂₂-alcohols and following metathesis of the silylethers with ethylene (50 bar, 65°C, 24 h). After cleaving off the silyl protecting group and distillation the over all-yield of the alcohols is 70% of the theory. The composition of the fatty alcohols (62% C₁₂, 25% C₁₄) is quite similar to that of fatty acids deriving from coconut or palm kernel oil.     

Leaf Epicuticular Wax Chemicals of the Japanese Knotweed Fallopia japonica as Oviposition Stimulants for Ostrinia latipennis

Extraction, fractionation, and gas chromatography−mass spectrometry analyses guided by bioassays have shown that n-alkanes and free fatty acids in leaf epicuticular wax of the Japanese knotweed Fallopia (Reynoutria) japonica stimulate oviposition in the Far-Eastern knotweed borer, Ostrinia latipennis (Lepidoptera: Crambidae). n-Alkanes made up 48.1% of the total amount of epicuticular wax, and their carbon chain length was in the C₁₆−C₃₃ range, with n-nonacosane (n-C₂₉) most abundant, followed by n-C₂₇, n-C₂₅, and n-C₃₁. Free fatty acids with C₉−C₂₂ accounted for 22.3%, and hexadecanoic acid was predominant. A mixture of authentic n-alkanes and fatty acids of the composition found in the epicuticular wax, a mixture of n-alkanes, and a mixture of fatty acids significantly enhanced oviposition. Thus, it was demonstrated that both n-alkanes and free fatty acids in leaf epicuticular wax of F. japonica are naturally occurring oviposition stimulants for O. latipennis.     

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.     

Distribution modes and possible origins of sheep wool hydrocarbons

An unusual mode of distribution of low-molecular-weight n-alkanes (C₁₁-C₁₅) with a slight even carbon-number predominance has been observed in the gas Chromatographic analysis of the paraffin fraction which was extracted from the wool of live sheep. This is in addition to the other two modes of medium-, C₁₅-C₂₄, and high-, C₂₄-C₃₃, molecular-weight alkanes usually present in wool wax which have also been found in sheep’s manure. The high-molecular-weight hydrocarbons (predominantly odd carbon-numbered) are presumed to be derived from the diet (pasture plants) whereas the other two hydrocarbon distributions probably result from the combined action of animal and microbial metabolism.     

Hydrogenation of unsaturated fatty acid methyl esters using decalin for hydrogen transfer

A laboratory procedure was developed for hydrogenation of methyl esters of unsaturated fatty acids using decalin as a hydrogen-transfer agent and 10% Pd/C as catalyst. The esters of 10-undecenoic, oleic, elaidic, stearolic, linoleic, cycloaliphatic C₂₁ di-, C₂₂ tri- and C₃₆ dicarboxylic acids, and a mixture of hydrnocarpic, chaulmoogric and gorlic acids were hydrogenated. Chromatographic and spectral analyses showed complete saturation. This procedure is simple, requiring no external source of hydrogen.     

Isolation and identification of constituents of Jasminum auriculatum (Vahl) leaves

Jasminum auriculatum (Vahl) (family: Malvaceae) widely grown in India was analysed for its fatty acids and waxy constituents. Straight-chain hydrocarbons (C₂₀-C₃₄), fatty acids (C₁₄-C₂₃) and fatty alcohols (C₂₁-C₃₂) were found in the 95% aqueous ethanol extract of the leaves of the plant. Malvalic acid was the only cyclic acid identified. Hydrocarbons (C₂₉ and C₃₁), fatty acids (C₁₆, C₁₈, C_18:1, C_18:2, C_18:3 and C₂₂) and fatty alcohols (iso-C₂₆, C₂₈ and C₃₀) were the major components. Four polyalcohols, namely D-mannitol, xylitol, inositol and sorbitol, have also been found in the alcoholic extract of the leaves.     

Aliphatic,Isoprenoid and Aromatic Acids from an Israeli Shale

Normal fatty acids (C₉-C₁₉); isoprenoid acid (C₁₀); aromatic acids (C₁₁-C₁₃) of the general formula C_nH_{2 n-8} O₂, and two aromatic acids (C₁₁, C₁₂) of the formula C_nH_{2 n-14} O₂, were identified in a bitumen obtained from shale of Nebi Musa (near Jericho), using chromatographic (GLC) and spectroscopic (MS) methods.     

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.     

Identifizierung von molekularen Phospholipid-Species aus Schweineherz durch Kombination chromatographischer Techniken

Identification of Molecular Species of Phospholipids from Pig Heart by Combining Chromatographic Techniques. Glycero-phospholipids from subcellular organelles and membranes from pig heart were divided into subclasses. The molecular species within the main subclasses were analyzed. The phosphorus moiety had been removed by phospholipase-C and the acetylated molecules were separated in diacyl-, alkylacyl- and alkenylacyl-glycerols by thin-layer chromatography (TLC). For further identification the subclasses from the first fractionation by TLC were separated by silver ion chromatography according to their polarity. A small portion of the acetylated diradyl-species was transesterified so that the fatty acid composition could be assessed as methyl esters. The acetylated molecular species derived from glycerophospholipids were chromatographed on WCOT fused silica columns with TAP as stationary phase according to molecular weight and unsaturation. Gaschromatography (GC) of fatty acid methyl esters and dimethylacetals from plasmalogens was executed on DEGS-columns or on WCOT fused silica columns with CP-Sil 88 as stationary phase. The distribution of molecular species within a phospholipid class (PC or PE) was rather similar for the diacyl-and the alkenylacyl molecules. But the latter are more volatile. In the case of phosphati-dylcholine the composition of C₁₆-C_18-:1; C₁₆-C_18:2 and C₁₈-C_18:2 was predominant for diacyl- as well as alkenylacyl-species. In the case of phosphatidylethanolamine the fatty acid composition of C₁₈-C_20:4 and C₁₈-C_18:2 were the most important species. The composition of fatty acids in diacyl-and alkenylacyl-species is of special interest as the metabolism of diacyl-glycerophospholipids is quite different from alkenylacyl-glycerophospholipids.     

Ozonolysis of Yakut boghead coal in chloroform

The process of ozonization and the composition of the ozonolytic degradation products of Yakut boghead coal in chloroform were studied. Water-soluble products consisted of C₂-C₁₁ dicarboxylic acids with maximum concentrations of C₄ and C₆ acids.     

Polymorphic behavior of gondoic acid and phase behavior of its binary mixtures with asclepic acid and oleic acid

Molecular properties of polymorphic forms of gondoic acid [cis-C_20:1Δ11ω9 (GOA)] have been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), optical microscopy, and Raman scattering, in comparison to those of six principal unsaturated fatty acids: oleic acid [cis-C_18:1Δ9ω9 (OA)], erucic acid [cis-C_22:1Δ13ω9 (ERA)], petroselinic acid [cis-C_18:1Δ6ω12 (PSA)], asclepic acid [cis-C_18:1Δ11ω7 (APA)], palmitoleic acid [cis-C_16:1Δ9ω7 (POA)], and elaidic acid [trans-C_18:1Δ9ω9 (ELA)]. In addition, phase behavior of binary mixtures of GOA and APA and OA was examined by XRD and DSC. The polymorphic structures of GOA are quite similar to those of APA, ERA, POA, and partly to OA. In particular, DSC and Raman scattering studies have shown that gondoic acid exhibits conformational disordering on heating at the ω-chain, a chain segment between the double bond and CH₃ group, as a transition from all-trans (γ form) to gauche-rich (α form) conformations. A miscible mixing phase was observed in the mixture of GOA and APA, yet eutectic phases were observed in the GOA and OA mixtures. This is a remarkable contrast because the binary mixture systems of varying combinations of cis-unsaturated fatty acids examined so far exhibited either eutectic nature or molecular compound formation. It is expected that specific molecular interactions between GOA and APA that originate from the equivalence of the length of the Δ-chain, the chain segment between the cis-double bond and COOH group, and also from the presence of the γ-α order-disorder transformation would be operating to form the miscible mixing phase.     

Odor composition of preferred (buffalo and ox) and nonpreferred (waterbuck) hosts of some Savanna tsetse flies

A previous study on the feeding responses of tsetse flies, Glossina morsitans morsitans, implicated the existence of allomonal barriers, both volatile and nonvolatile, on the nonpreferred host, waterbuck, Kobus defassa. In the present study, electroantennogram-active compounds in odors from waterbuck were compared with those of two preferred hosts of tsetse flies, buffalo, Syncerus caffer, and ox, Bos indicus. Odors from the three bovids were trapped on activated charcoal and/or reverse-phase (octadecyl bonded) silica and analyzed with a gas chromatography-linked electroantennographic detector (GC-EAD) and, where possible, identified by using gas chromatography-linked mass spectrometry (GC-MS) and chromatographic comparisons with authentic samples. The GC-EAD profiles (with G. m. morsitans antennae) of the odors of the two preferred hosts were comparable, comprising medium-chain, saturated or unsaturated aldehydes and phenols, with buffalo emitting a few more EAG-active aldehydes. Waterbuck odor gave a richer profile, consisting of fewer aldehydes but more phenolic components and a series of 2-ketones (C₈–C₁₃) and -octalactone. This bovid also emits moderate amounts of C₅–C₉ straight-chain fatty acids, some of which were detected in buffalo and ox only in trace amounts. However, these did not elicit significant GC-EAD responses. Waterbuck profiles from the antennae of G. pallidipes showed broad similarity to those from G. m. morsitans, although the composition of aldehydes and ketones was somewhat different, indicating species-specific difference in the detection of host odors. Certain waterbuck-specific EAG-active components, particularly the 2-ketones and lactone, constitute a candidate allomonal blend in waterbuck odor.     

Δ5-Olefinic acids in the seed lipids from four Ephedra species and their distribution between the α and β positions of triacylglycerols. Characteristics common to coniferophytes and cycadophytes

The fatty acid compositions of the seed lipids from four Ephedra species, E. nevadensis, E. viridis, E. przewalskii, and E. gerardiana (four gymnosperm species belonging to the Cycadophytes), have been established with an emphasis on Δ5-unsaturated polymethylene-interrupted fatty acids (Δ5-UPIFA). Mass spectrometry of the picolinyl ester derivatives allowed characterization of 5,9- and 5,11–18∶2; 5,9,12–18∶3; 5,9,12,15–18∶4; 5,11–20∶2; 5,11,14–20∶3; and 5,11,14,17–20∶4 acids. Δ5-UPIFA with a Δ11-ethylenic bond (mostly C₂₀ acids) were in higher proportions than δ5-UPIFA with a δ9 double bond (exclusively C₁₈ acids) in all species. The total δ5-UPIFA content was 17–31% of the total fatty acids, with 5, 11, 14–20∶3 and 5, 11, 14, 17–20∶4 acids being the principal δ5-UPFIA isomers. The relatively high level of cis-vaccenic (11–18∶1) acid found in Ephedra spp. seeds, the presence of its δ5-desaturation product, 5, 11–18∶2 acid (proposed trivial name: ephedrenic acid), and of its elongation product, 13–20∶1 acid, were previously shown to occur in a single other species, Ginkgo biloba, among the approximately 170 gymnosperm species analyzed so far. Consequently, Ephedraceae and Coniferophytes (including Ginkgoatae), which have evolved separately since the Devonian period (≈300 million yr ago), have kept in common the ability to synthesize C₁₈ and C₂₀ δ5-UPIFA. We postulate the existence of two δ5-desaturases in gymnosperm seeds, one possibly specific for unsaturated acids with a δ9-ethylenic bond, and the other possibly specific for unsaturated acids with a δ11-ethylenic bond. Alternatively, the δ5-desaturases might be specific for the chain length with C₁₈ unsaturated acids on the one hand and C₂₀ unsaturated acids on the other hand. The resulting hypothetical pathways for the biosynthesis of δ5-UPIFA in gymnosperm seeds are only distinguished by the position of 11–18∶1 acid. Moreover, ¹³C nuclear magnetic resonance spectroscopy of the seed oil from two Ephedra species has shown that δ5-UPIFA are essentially excluded from the internal position of triacylglycerols, a characteristic common to all of the Coniferophytes analyzed so far (more than 30 species), with the possibility of an exclusive esterification at the sn-3 position. This structural feature would also date back to the Devonian period, but might have been lost in those rare angiosperm species containing δ5-UPIFA.     

Cuticular lipids of the booklouse,Liposcelis bostrychophila: hydrocarbons,aldehydes, fatty acids,and fatty acid amides

The booklouse, Liposcelis bostrychophila, is an increasingly common pest of stored food products worldwide. We report here the cuticular lipid composition of this pest (the first report of the hydrocarbons of any member of the Order Psocoptera and the first report of fatty acid amides as cuticular components for any insect). No unsaturated hydrocarbons were present. A homologous series of n-alkanes (C₂₁–C₃₄), monomethyl alkanes (3-, 4-, 5-, 7-, 9-, 11-, 12-, 13- and 15-methyl-) with a carbon chain range of C₂₈–C₄₂, and dimethyl alkanes (3, 7-; 9, 13-; 11, 15-; 13, 17-; 9, 21-; 11, 19-; and 13, 21-); with a carbon number range of C₃₁–C₄₃ were identified. The relative abundances of these hydrocarbons were low, comprising approximately 0.0125% of total biomass. The amides were a homologous series (C₁₆–C₂₂ in chain length), with the major amide being stearoyl amide. In addition to the amides, free fatty acids (C_16:1, C_16:0, C_18:2, C_18:1, and C_18:0 in chain length) and three straight chain aldehydes (C₁₅, C₁₆, and C_17:1 in chain length) also occurred as cuticular components. These findings are discussed in terms of the chemical and physiological ecology of this species.