Donald Wiesler

Individual and gender fingerprints in human body odour

Individuals are thought to have their own distinctive scent, analogous to a signature or fingerprint. To test this idea, we collected axillary sweat, urine and saliva from 197 adults from a village in the Austrian Alps, taking five sweat samples per subject over 10 weeks using a novel skin sampling device. We analysed samples using stir bar sorptive extraction in connection with thermal desorption gas chromatograph–mass spectrometry (GC–MS), and then we statistically analysed the chromatographic profiles using pattern recognition techniques. We found more volatile compounds in axillary sweat than in urine or saliva, and among these we found 373 peaks that were consistent over time (detected in four out of five samples per individual). Among these candidate compounds, we found individually distinct and reproducible GC–MS fingerprints, a reproducible difference between the sexes, and we identified the chemical structures of 44 individual and 12 gender-specific volatile compounds. These individual compounds provide candidates for major histocompatibility complex and other genetically determined odours. This is the first study on human axillary odour to sample a large number of subjects, and our findings are relevant to understanding the chemical nature of human odour, and efforts to design electronic sensors (e-nose) for biometric fingerprinting and disease diagnoses.

Positive identification of the puberty-accelerating pheromone of the house mouse: the volatile ligands associating with the major urinary protein

Five structurally diverse small ligands, all binding to the major urinary protein (MUP) of the male house mouse, show individually puberty-accelerating pheromonal activity in the recipient females. A recombinant MUP (identical structurally to the natural protein) has shown no biological activity. While four of these ligands were previously implicated in oestrus synchronization (Whitten effect), the same chemosignals now appear responsible for both sexual maturation and cycling in adult females.

Urinary volatile constituents of the house mouse, Mus musculus, and their endocrine dependency

Mouse urine contains a great number of volatile constituents that may be used in chemical communication. Some of these volatiles, identified in this study by combined gas chromatography-mass spectrometry and gas chromatography-Fourier-transform infrared spectroscopy, appear unique to the mouse. Certain urinary volatiles exhibit strong dependence on the sex and endocrine status of the animals, as shown through castration, treatment with an antiandrogen, and hormone supplementation.

A unique urinary constituent, 6-hydroxy-6-methyl-3-heptanone, is a pheromone that accelerates puberty in female mice.

BACKGROUND Olfactorily mediated puberty acceleration in female mice (measured by an increase in uterine weight) has been observed since the 1960s without the active chemosignal being structurally identified. There are many controversies in the literature as to whether this male-originated pheromone is a volatile substance. We investigated the chemical nature of the urinary fractions that are responsible for the characteristic uterine weight increases. RESULTS The active pheromone was identified as 5,5-dimethyl-2-ethyltetrahydrofuran-2-ol and/or its open-chain tautomer (6-hydroxy-6-methyl-3-heptanone). A series of cyclic vinyl ethers were isolated from chromatographically active fractions of the urine. Because these compounds did not accelerate puberty, we postulated that these ethers were degradation products of a lactol (5,5-dimethyl-2-ethyltetrahydrofuran-2-ol). The lactol was then detected directly in the mouse urine extract using a silylation agent. Synthetic 6-hydroxy-6-methyl-3-heptanone had strong biological activity, whereas its close structural analogs did not. CONCLUSIONS The male house mouse excretes into its urine a large quantity of a volatile substance that has a unique lactol/hydroxyketone structure. This substance is capable of binding to the less volatile urinary constituents, such as proteins or peptides, and is active in puberty-acceleration bioassays. The controversies regarding the volatility of the puberty-accelerating pheromones can now be explained by considering a complex of volatile lactol/hydroxyketone and urinary proteins.

Compositional studies of coal tar by capillary gas chromatographymass spectrometry

Abstract High-temperature coal-tar samples were fractionated by a liquid-liquid partition scheme to provide aromatic, aliphatic, basic, acidic and ‘neutral polar’ fractions which were subsequently analysed by an optimum methodology for each compound class. Combined glass-capillary gas chromatography/mass spectrometry was used for the analysis. The results verifty some earlier identifications and also report constituents identified for the first time. Crude-tar samples derived from coals of different geographical origin were found to be similar in their major constituents.

Seasonal Variation in Volatile Compound Profiles of Preen Gland Secretions of the Dark-eyed Junco (Junco hyemalis)

Quantitative stir bar sorptive extraction methodology, followed by gas chromatography-mass spectrometry (GC-MS) and element-specific atomic emission detection (AED) were utilized to analyze seasonal changes in volatile components of preen oil secretions in Junco hyemalis. Juncos were held in long days to simulate breeding conditions, or short days to simulate nonbreeding conditions. Linear alcohols (C10–C18) were the major volatile compounds found in preen oil, and in both sexes their levels were higher when birds were housed on long as opposed to short days. Methylketones were found at lower levels, but were enhanced in both sexes during long days. Levels of 2-tridecanone, 2-tetradecanone, and 2-pentadecanone were also greater on long days, but only in males. Among carboxylic acids (C12, C14, and C16), linear but not branched acids showed some differences between the breeding and nonbreeding conditions, although the individual variation for acidic compounds was large. Qualitatively, more sulfur-containing compounds were found in males than females during the breeding season. Functionally, the large increase in linear alcohols in male and female preen oil during the breeding season may be an indication of altered lipid biosynthesis, which might signal reproductive readiness. Linear alcohols might also facilitate junco odor blending with plant volatiles in the habitat to distract mammalian predators. Some of the volatile compounds from preen oil, including linear alcohols, were also found on the wing feather surface, along with additional compounds that could have been of either metabolic or environmental origin.

Puberty-affecting synthetic analogs of urinary chemosignals in the house mouse, Mus domesticus

Endocrinologically- and socially-dependent volatile constituents of female mouse urine, identified in a previous study, were tested for their capability to accelerate puberty and extend the estrous period in young females. Several volatile ketones advanced puberty by approximately three days and extended the period of vaginal cornification in 55-75% of exposed females. High High concentrations of these substances were capable of overriding the known puberty-delaying chemosignals. Volatile cyclic enol ethers were also effective in extending estrus, but not puberty acceleration.

Identification of a testosterone-dependent unique volatile constituent of male mouse urine: 7-exo-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]-3-octene

Investigations regarding the chemical composition of the volatiles in male mouse urine have recently enabled the structural elucidation of a hitherto unreported urinary component, 7-exo-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]-3-octene. This compounds uniqueness to mouse urine and its dependence on testosterone levels in the male suggest its probable role as a mouse pheromone or pheromone adjuvant.

Fractionation and capillary gas chromatographic—mass spectrometric characterization of the neutral components in marijuana and tobacco smoke condensates

Abstract Polar and non-polar “neutral” constituents of the smoke condensates of Mexican marijuana and standard tobacco were resolved by capillary gas chromatography and structurally characterized through mass spectrometry. Comparisons of the two materials reveal substantial qualitative and quantitative differences. The cannabinoid-like substances partition into both the non-polar and polar fraction. In total, over 130 “neutral” smoke components have been characterized.

Chemical scent constituents in urine of wolf (Canis lupus) and their dependence on reproductive hormones

The volatile components of castrated male and ovariectomized female wolf urine were investigated and correlated with the administration of testosterone or estradiol and progesterone. The results indicate that testosterone induces in the castrated male the formation of some compounds typically associated with the intact male, while reducing the levels of some compounds associated with castrated male and female. The production of some of the “male” compounds was also induced in the ovariectomized female, although at lower levels. Changes in hormone levels during treatment of females are reflected in the composition of the urinary volatiles. Consequently, many of these compounds could be used to communicate gender as well as reproductive status.