The Effect of Ethnicity on Human Axillary Odorant Production.

Previous findings from our laboratory highlighted marked ethnic differences in volatile organic compounds (VOCs) from cerumen among individuals of Caucasian, East Asian, and African-American descent, based, in part, on genetic differences in a gene that codes for a transport protein, which is a member of the ATP-binding cassette transporter, sub-family C, member 11 (ABCC11). In the current work, we hypothesized that axillary odorants produced by East Asians would differ markedly from those obtained from individuals of European or African descent based on the pattern of ethnic diversity that exists in ABCC11. Using gas chromatography/mass spectrometry (GC/MS) we examined differences in axillary odorant VOCs among 30 individuals of African-American, Caucasian, and East Asian descent with respect to their ABCC11 genotype. While no qualitative differences in the type of axillary odorants were observed across ethnic groups, we found that characteristic axillary odorants varied quantitatively with respect to ethnic origin. We propose that ABCC11 is not solely responsible for predicting the relative amounts of volatiles found in axillary secretions and that other biochemical pathways must be involved.

Food odors trigger Drosophila males to deposit a pheromone that guides aggregation and female oviposition decisions.

Animals use olfactory cues for navigating complex environments. Food odors in particular provide crucial information regarding potential foraging sites. Many behaviors occur at food sites, yet how food odors regulate such behaviors at these sites is unclear. Using Drosophila melanogaster as an animal model, we found that males deposit the pheromone 9-tricosene upon stimulation with the food-odor apple cider vinegar. This pheromone acts as a potent aggregation pheromone and as an oviposition guidance cue for females. We use genetic, molecular, electrophysiological, and behavioral approaches to show that 9-tricosene activates antennal basiconic Or7a receptors, a receptor activated by many alcohols and aldehydes such as the green leaf volatile E2-hexenal. We demonstrate that loss of Or7a positive neurons or the Or7a receptor abolishes aggregation behavior and oviposition site-selection towards 9-tricosene and E2-hexenal. 9-Tricosene thus functions via Or7a to link food-odor perception with aggregation and egg-laying decisions.

Mn(V)(O) versus Cr(V)(O) Porphyrinoid Complexes: Structural Characterization and Implications for Basicity Controlling H-Atom Abstraction.

Isomorphous crystals of Mn(V)(O) and Cr(V)(O) corrolazines were characterized by single crystal X-ray diffraction. Reactivity studies with H atom donors and separated PCET reagents show a dramatic difference in H atom abstracting abilities for these two complexes. The implied large difference in driving force is opposite the trend in redox potentials, indicating that basicity is a key factor in determining the striking difference in reactivity for two metal-oxo species in identical ligand environments.

Ethnic/racial and genetic influences on cerumen odorant profiles.

This report describes the volatile organic compounds (VOCs) associated with human cerumen (earwax) and the effects of ethnicity/race and variation on the ATP-binding cassette, sub-family C, member 11 gene (ABCC11). A single nucleotide polymorphism (SNP) in ABCC11 affects the cerumen VOC profiles of individuals from African, Caucasian, and Asian descent. Employing gas chromatography/mass spectrometry (GC/MS) we have identified the nature and relative abundance of cerumen VOCs from 32 male donors. Our results show that cerumen contains a complex mixture of VOCs and that the amounts of these compounds vary across individuals as well as across ethnic/racial groups. In six of the seven compounds whose detected concentrations were found to be statistically different across groups, individuals of African descent (AfD) > Caucasian descent (CaD) > Asians descent (AsD). Our findings also reveal that ABCC11 genotype alone does not predict the type and relative levels of volatiles found in human cerumen, and suggest that other biochemical pathways must be involved. Examination of the composition and diversity of external auditory canal microbiota in a small subset of our subject population revealed that the ear microbiota may not be directly correlated with either ethnic group membership or ABCC11 genotype.

Dramatic influence of an anionic donor on the oxygen-atom transfer reactivity of a Mn(V) -oxo complex.

Addition of an anionic donor to an Mn(V) (O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [Mn(V) (O)(TBP8 Cz)(CN)](-) was generated from addition of Bu4 N(+) CN(-) to the 5-coordinate Mn(V) (O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives MnO=1.53 Å, MnCN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN(-) complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e(-) -reduced Mn(III) (CN)(-) complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives ΔH(≠) =14 kcal mol(-1) , ΔS(≠) =-10 cal mol(-1) K(-1) . Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate Mn(V) (O) complexes.

Identification of volatile organic compounds in human cerumen.

We report here the initial examination of volatile organic compounds (VOCs) emanating from human earwax (cerumen). Recent studies link a single nucleotide polymorphism (SNP) in the adenosine triphosphate (ATP) binding cassette, sub-family C, member 11 gene (ABCC11) to the production of different types of axillary odorants and cerumen. ABCC11 encodes an ATP-driven efflux pump protein that plays an important function in ceruminous apocrine glands of the auditory canal and the secretion of axillary odor precursors. The type of cerumen and underarm odor produced by East Asians differ markedly from that produced by non-Asians. In this initial report we find that both groups emit many of the same VOCs but differ significantly in the amounts produced. The principal odorants are volatile organic C2-to-C6 acids. The physical appearance of cerumen from the two groups also matches previously reported ethnic differences, viz., cerumen from East Asians appears dry and white while that from non-Asians is typically wet and yellowish-brown.

Photochemical oxidation of a manganese(III) complex with oxygen and toluene derivatives to form a manganese(V)-oxo complex.

Visible light photoirradiation of an oxygen-saturated benzonitrile solution of a manganese(III) corrolazine complex [(TBP8Cz)Mn(III)] (1): [TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)] in the presence of toluene derivatives resulted in formation of the manganese(V)-oxo complex [(TBP8Cz)Mn(V)(O)]. The photochemical oxidation of (TBP8Cz)Mn(III) with O2 and hexamethylbenzene (HMB) led to the isosbestic conversion of 1 to (TBP8Cz)Mn(V)(O), accompanied by the selective oxidation of HMB to pentamethylbenzyl alcohol (87%). The formation rate of (TBP8Cz)Mn(V)(O) increased with methyl group substitution, from toluene, p-xylene, mesitylene, durene, pentamethylbenzene, up to hexamethylbenzene. Deuterium kinetic isotope effects (KIEs) were observed for toluene (KIE = 5.4) and mesitylene (KIE = 5.3). Femtosecond laser flash photolysis of (TBP8Cz)Mn(III) revealed the formation of a tripquintet excited state, which was rapidly converted to a tripseptet excited state. The tripseptet excited state was shown to be the key, activated state that reacts with O2 via a diffusion-limited rate constant. The data allow for a mechanism to be proposed in which the tripseptet excited state reacts with O2 to give the putative (TBP8Cz)Mn(IV)(O2(•-)), which then abstracts a hydrogen atom from the toluene derivatives in the rate-determining step. The mechanism of hydrogen abstraction is discussed by comparison of the reactivity with the hydrogen abstraction from the same toluene derivatives by cumylperoxyl radical. Taken together, the data suggest a new catalytic method is accessible for the selective oxidation of C-H bonds with O2 and light, and the first evidence for catalytic oxidation of C-H bonds was obtained with 10-methyl-9,10-dihydroacridine as a substrate.