Whether olfaction recognizes odorants by their shape, their molecular vibrations, or both remains an open and controversial question. A convenient way to address it is to test for odor character differences between deuterated and undeuterated odorant isotopomers, since these have identical ground-state conformations but different vibrational modes. In a previous paper (Franco et al. (2011) Proc Natl Acad Sci USA 108:9, 3797-802) we showed that fruit flies can recognize the presence of deuterium in odorants by a vibrational mechanism. Here we address the question of whether humans too can distinguish deuterated and undeuterated odorants. A previous report (Keller and Vosshall (2004) Nat Neurosci 7:4, 337-8) indicated that naive subjects are incapable of distinguishing acetophenone and d-8 acetophenone. Here we confirm and extend those results to trained subjects and gas-chromatography [GC]-pure odorants. However, we also show that subjects easily distinguish deuterated and undeuterated musk odorants purified to GC-pure standard. These results are consistent with a vibrational component in human olfaction.
Patchouli is used as an incense material and essential oil. The characteristic odor of patchouli leaves results from the drying process used in their production; however, there have to date been no reports on the changes in the odor of patchouli leaves during the drying process. We investigated the aroma profile of dried patchouli leaves using the hexane extracts of fresh and dried patchouli leaves. We focused on the presence or absence of the constituents of the fresh and dried extracts, and the differences in the content of the common constituents. Fourteen constituents were identified as characteristic of dried patchouli extract odor by gas chromatography-olfactometry analysis. The structures of seven of the 14 constituents were determined by gas chromatography-mass spectrometry (α-patchoulene, seychellene, humulene, α-bulnesene, isoaromadendrene epoxide, caryophyllene oxide, and patchouli alcohol). The aroma profile of the essential oil obtained from the dried patchouli leaves was clearly different from that of dried patchouli. The aroma profile of the essential oil was investigated by a similar method. We identified 12 compounds as important odor constituents. The structures of nine of the 12 constituents were determined by gas chromatographymass spectrometry (cis-thujopsene, caryophyllene, α-guaiene, α-patchoulene, seychellene, α-bulnesene, isoaromadendrene epoxide, patchouli alcohol, and corymbolone). Comparing the odors and constituents demonstrated that the aroma profile of patchouli depends on the manufacturing process.
- Journal of exposure science & environmental epidemiology
- Published over 5 years ago
Several phthalates, particularly diethyl phthalate (DEP) and di-n-butyl phthalate, can be used in personal care products (PCPs) to fix fragrance and hold color. We investigated associations between women’s reported use of PCPs within the 24 h before urine collection and concentrations of several urinary phthalate metabolites. Between 2002 and 2005, 337 women provided spot urine samples and answered questions regarding their use of 13 PCPs at a follow-up visit 3-36 months after pregnancy. We examined associations between urinary concentrations of several phthalate metabolites and use of PCPs using linear regression. Use of individual PCPs ranged from 7% (nail polish) to 91% (deodorant). After adjusting for age, education, and urinary creatinine, women reporting use of perfume had 2.92 times higher (95% CI: 2.20-3.89) concentration of monoethyl phthalate (MEP; the primary metabolite of DEP) than other women. Other PCPs that were significantly associated with MEP concentrations included: hair spray, nail polish, and deodorant. MEP concentrations increased with the number of PCPs used. PCP use was widespread in this group of recently pregnant women. Women’s use of PCPs, particularly of perfumes and fragranced products, was positively associated with urinary concentration of multiple phthalate metabolites.Journal of Exposure Science and Environmental Epidemiology advance online publication, 21 November 2012; doi:10.1038/jes.2012.105.
Female hawkmoths, Manduca sexta, use olfactory cues to locate nectar sources and oviposition sites. We investigated if the behavioral significance of odorants is represented already in the antennal lobe, the first olfactory neuropil of the insect’s brain. Using in vivo calcium imaging, we first established a functional map of the dorsal surface of the antennal lobe by stimulating the moths with 80 ecologically relevant and chemically diverse monomolecular odorants. We were able to address 23 olfactory glomeruli, functional subunits of the antennal lobe, in each individual female. Next, we studied the relevance of the same odorants with two-choice experiments (odorant versus solvent) in a wind tunnel. Depending on odorant identity, naive moths made attempts to feed or to oviposit at the scented targets. A correlation of wind tunnel results with glomerular activation patterns revealed that feeding and oviposition behaviors are encoded in the moth’s antennal lobe by the activation of distinct groups of glomeruli.
The volatile oil parts of frankincense (Boswellia carterii Birdw.) were extracted with supercritical carbon dioxide under constant pressure (15, 20, or 25 MPa) and fixed temperature (40, 50, or 60°C), given time (60, 90, or 120 min) aiming at the acquisition of enriched fractions containing octyl acetate, compounds of pharmaceutical interest. A mathematical model was created by Box-Behnken design, a popular template for response surface methodology, for the extraction process. The response value was characterized by synthetical score, which comprised yields accounting for 20% and content of octyl acetate for 80%. The content of octyl acetate was determined by GC. The supercritical fluid extraction showed higher selectivity than conventional steam distillation. Supercritical fluid-CO(2) for extracting frankincense under optimum condition was of great validity, which was also successfully verified by the pharmacological experiments.
Different compositions of monoterpenes are utilized for their pleasant scent in cosmetics and perfumes. However, the most commonly used fragrance terpenes easily oxidize upon contact with air, forming strongly skin-sensitizing hydroperoxides. Due to their thermolability and low UV absorbance, detection methods for hydroperoxides are scarce. For the first time, a simple and sensitive method using liquid chromatography/electrospray ionization-tandem mass spectrometry was developed to quantitatively determine hydroperoxides from the common fragrance compounds linalool, linalyl acetate, and limonene. The method was applied to autoxidized petitgrain oil and sweet orange oil. A separation was accomplished using a C(3) column. The method limit of detection for the investigated hydroperoxides in the essential oils was below 0.3 μg/mL, corresponding to 0.3 ppm. For prevention purposes and according to EU regulations, concentrations in cosmetics exceeding 100 ppm in “rinse-off” and 10 ppm in “stay-on” products of linalool and limonene must be labeled. However, the products may still contain allergens, such as hydroperoxides, formed by oxidative degradation of their parent terpenes. The sensitivity and selectivity of the presented LC/MS/MS method enables detection of hydroperoxides from the fragrance terpenes linalool, linalyl acetate, and limonene. However, for routine measurements, the method requires further validation.
Frankincense has been known, traded and used throughout the ages for its exceptional aroma properties, and is still commonly used in both secular and religious settings to convey a pleasant odor. Surprisingly, the odoriferous principle(s) underlying its unique odor profile have never been published. In this study, resin samples of Boswellia sacra Flueck. from both Somalia and Oman were investigated by aroma extract dilution analysis. In a comprehensive, odor-activity guided approach both chemo-analytical and human-sensory parameters were used to identify odor active constituents of the volatile fraction of B. sacra. Among the key odorants found were α-pinene, β-myrcene, linalool, p-cresol and two unidentified sesquiterpenoids. Overall, a total of 23 odorants were detected and analyzed by gas chromatography-olfactometry and heart-cut two-dimensional gas chromatography-mass spectrometry/olfactometry. The majority of the identified odorant compounds were oxygenated monoterpenes, along with some relevant mono- and sesquiterpenes and only one diterpenoid substance. Several of these compounds were reported here for the first time as odorous constituents in B. sacra. Identifying bioactive compounds might support a better understanding with regard to the potential benefits of frankincense, for example in aromatherapy or ecclesial settings.
Phlorotannins are one of the most important bioactive polyphenols; however, their purification using chromatographic methods has not been explored. Here, we studied purification of phlorotannins from the crude phlorotannin extract (CPhE) of the brown seaweed Ecklonia cava using macroporous adsorption resins. For purification of phlorotannins, four resins (HP-20, SP-850, XAD-7HP, and XAD-2) were screened. Among them, HP-20 resin showed the highest adsorption and desorption capacities. In static adsorption tests, the adsorption capacity of HP-20 increased with increasing temperature (25-45°C). Optimal conditions for the dynamic experiments can be summarized as follows: total phlorotannin content (TPhC) in loading solution: 1.5mg PGE/mL, processing volume: 4 BV, flow rate: 1 mL/min, temperature: 45°C, desorption solvent: 40% ethanol solution. After purification, TPhC (452 mg PGE/g) and arsenic (180 μg/g) of CPhE increased and decreased to 905 mg PGE/g and 48 μg/g, respectively. Recovery rate of phlorotannins from CPhE was 92%.
Oil and xanthorrhizol extraction from Curcuma xanthorrhiza Roxb. rhizome by supercritical carbon dioxide was optimized using Taguchi method. The factors considered were pressure, temperature, carbon dioxide flowrate and time at levels ranging between 10-25 MPa, 35-60 °C, 10-25 g/min and 60-240 min respectively. The highest oil yield (8.0 %) was achieved at factor combination of 15 MPa, 50 °C, 20 g/min and 180 min whereas the highest xanthorrhizol content (128.3 mg/g oil) in Curcuma xanthorrhiza oil was achieved at a factor combination of 25 MPa, 50 °C, 15 g/min and 60 min. Soxhlet extraction with n-hexane and percolation with ethanol gave oil yield of 5.88 %, 11.73 % and xanthorrhizol content of 42.6 mg/g oil, 75.5 mg/g oil, respectively. The experimental oil yield and xanthorrhizol content at optimum conditions agreed favourably with values predicted by computational process. The xanthorrizol content extracted using supercritical carbon dioxide was higher than extracted using Soxhlet extraction and percolation process.
Black pepper (Piper nigrum L.), the King of Spices is the most popular spice globally and its active ingredient, piperine, is reportedly known for its therapeutic potency. In this work, enzyme-assisted supercritical carbon dioxide (SC-CO2) extraction of black pepper oleoresin was investigated using α-amylase (from Bacillus licheniformis) for enhanced yield of piperine-rich extract possessing good combination of phytochemical properties. Optimization of the extraction parameters (without enzyme), mainly temperature and pressure, was conducted in both batch and continuous modes and the optimized conditions that provided the maximum yield of piperine was in the batch mode, with a sample size of 20 g of black pepper powder (particle diameter 0.42 ± 0.02 mm) at 60°C and 300 bar at 2 L/min of CO2 flow. Studies on activity of α-amylase were conducted under these optimized conditions in both batch and continuous modes, with varying amounts of lyophilized enzyme (2 mg, 5 mg and 10 mg) and time of exposure of the enzyme to SC-CO2 (2.25 h and 4.25 h). The specific activity of the enzyme increased by 2.13 times when treated in the continuous mode than in the batch mode (1.25 times increase). The structural changes of the treated enzymes were studied by (1)H NMR analyses. In case of α-amylase assisted extractions of black pepper, both batch and continuous modes significantly increased the yields and phytochemical properties of piperine-rich extracts; with higher increase in batch mode than in continuous.