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Measurement of gas-liquid partition coefficient and headspace concentration profiles of perfume materials by solid-phase microextraction and capillary gas chromatography-mass spectrometry

An empirical model describing the relationship between the partition coefficients (K) of perfume materials in the solid-phase microextraction (SPME) fiber stationary phase and the Linearly Temperature Programmed Retention Index (LTPRI) is obtained. This is established using a mixture of eleven selected fragrance materials spiked in mineral oil at different concentration levels to simulate liquid laundry detergent matrices. Headspace concentrations of the materials are measured using both static headspace and SPME-gas chromatography analysis. The empirical model is tested by measuring the K values for fourteen perfume materials experimentally. Three of the calculated K values are within 2-19% of the measured K value, and the other eleven calculated K values are within 22-59%. This range of deviation is understandable because a diverse mixture was used to cover most chemical functionalities in order to make the model generally applicable. Better prediction accuracy is expected when a model is established using a specific category of compounds, such as hydrocarbons or aromatics. The use of this method to estimate distribution constants of fragrance materials in liquid matrices is demonstrated. The headspace SPME using the established relationship between the gas-liquid partition coefficient and the LTPRI is applied to measure the headspace concentration of fragrances. It is demonstrated that this approach can be used to monitor the headspace perfume profiles over consumer laundry and cleaning products. This method can provide high sample throughput, reproducibility, simplicity, and accuracy for many applications for screening major fragrance materials over consumer products. The approach demonstrated here can be used to translate headspace SPME results into true static headspace concentration profiles. This translation is critical for obtaining the gas-phase composition by correcting for the inherent differential partitioning of analytes into the fiber stationary phase.

Journal Article↗

The sensitization potential of some perfume ingredients tested using a modified draize procedure.

A modified Draize procedure was used to test 23 natural and 46 synthetic perfume ingredients for their potential to induce allergic contact dermatitis in guinea pigs. Fifty-three ingredients did not induce sensitization. Two synthetic ingredients showed a strong sensitization potential and 14 ingredients, 7 natural and 7 synthetic, showed a weak sensitization potential. The findings indicate that there is little risk of sensitization in man to most of these perfume ingredients.

Animals↗

Comprehensive two-dimensional gas chromatography in combination with rapid scanning quadrupole mass spectrometry in perfume analysis.

Single column gas chromatography (GC) in combination with a flame ionization detector (FID) and/or a mass spectrometer is routinely employed in the determination of perfume profiles. The latter are to be considered medium to highly complex matrices and, as such, can only be partially separated even on long capillaries. Inevitably, several monodimensional peaks are the result of two or more overlapping components, often hindering reliable identification and quantitation. The present investigation is based on the use of a comprehensive GC (GC x GC) method, in vacuum outlet conditions, for the near to complete resolution of a complex perfume sample. A rapid scanning quadrupole mass spectrometry (qMS) system, employed for the assignment of GC x GC peaks, supplied high quality mass spectra. The validity of the three-dimensional (3D) GC x GC-qMS application was measured and compared to that of GC-qMS analysis on the same matrix. Peak identification, in all applications, was achieved through MS spectra library matching and the interactive use of linear retention indices (LRI).

Gas Chromatography-Mass Spectrometry↗

Fungistatic activity of some perfumes against otomycotic pathogens.

The sporostatic effect of five otomycotic pathogens, i.e. Aspergillus niger, A. flavus, Absidia corymbifera, Penicillium nigricans and Candida albicans to nine different perfumes was determined on the basis of their spore germination. These organisms were isolated from patients suffering from fungal infection of the external auditory canal. Volatile vapours emanating from musk, phulwari, jasmine, nagchampa and bela caused approximately 100% inhibition in spore germination of all the test fungi. Volatiles emanating from chandan, khas and hina showed no inhibition for the test pathogens, displaying their resistant character to these perfumes.

Antifungal Agents↗

Contact sensitivity to flavourings and perfumes in atopic dermatitis.

16 children with atopic dermatitis and 4 nonatopics were skin tested with flavourings and perfumes. Immediate reactions to balsam of Peru and fragrance-mix were found in 9 atopics, and none among nonatopics. An irritant is more probable than an immunologic mechanism. Allergen solutions should probably be assayed at a lower concentration in atopic patients. This study points to a possible aggravating factor from perfumes and flavourings ingested, inhaled, or used as cosmetics.

Child↗

Patch testing with fragrances: results of a multicenter study of the European Environmental and Contact Dermatitis Research Group with 48 frequently used constituents of perfumes.

The objective of this study was to determine the frequency of reactivity to a series of commonly used fragrances in dermatological patients. A total of 48 fragrances (FF) were chosen, based on the publication of Fenn in 1989 in which the top 25 constituents of 3 types (1. perfumes, 2. household products, 3. soaps) of 400 commercial products on the US market had been determined. In a pilot study on a total of 1069 patients in 11 centres, the appropriate test concentration and vehicle were examined. For most fragrances, 1% and 5% were chosen, and petrolatum proved to be the best vehicle in comparison to isopropyl myristate and diethyl phthalate. In the main study, a set of 5 to 10 fragrances at 2 concentrations was patch tested in each centre on a minimum of 100 consecutive patients seen in the patch test clinic. These patients were also patch tested to a standard series with the 8% fragrance mix (FM) and its 8 constituents. In patients with a positive reaction to any of the 48 FF, a careful history with regard to past or present reactions to perfumed products was taken. A total of 1323 patients were tested in 11 centres. The 8% FM was positive in 89 patients (8.3% of 1072 patients). Allergic reactions to the constituents were most frequent to oak moss (24), isoeugenol (20), eugenol (13), cinnamic aldehyde (10) and geraniol (8). Reactions read as allergic on day 3/4 were observed only 10X to 7 materials of the new series (Iso E Super (2), Lyral (3), Cyclacet (1), DMBCA (1), Vertofix (1), citronellol (1) and amyl salicylate (1)). The remaining 41 fragrances were negative. 28 irritant or doubtful reactions on day 3/4 were observed to a total of 19 FF materials (more than 1 reaction: 5% citronellol (2), 1% amyl salicylate (2), 1% isononyl acetate (3), 0.1% musk xylol (2), 1% citral (2), and 1% ionone beta (2)). Clinical relevance of positive reactions to any of the FF series was not proved in a single case. This included the 4 reactions in patients who were negative to the 8% FM. In conclusion, the top 25 fragrances commonly found in various products caused few reactions in dermatological patients and these few appeared to be clinically irrelevant, with the possible exception of Lyral. However, this data should be interpreted in the light of the relatively small number of patients tested (only 100 in most centres).

Acrolein↗

Identification of coumarin as the sensitizer in a patient sensitive to her own perfume but negative to the fragrance mix.

The aim of this study was to identify the chemicals responsible for the sensitivity of a 44-year-old woman to her own perfume, but showing negative patch test results to the fragrance mix. For this purpose, the perfume concentrate from the eau de toilette was chemically fractionated. Each fraction obtained was afterwards tested on the patient using a ROAT and/or a patch test. Only 1 fraction gave a positive ROAT result. This fraction was analyzed and found to contain coumarin and ethyl vanillin. Coumarin, one of the most widely used fragrance compounds that is not present in the fragrance mix, was confirmed as being the sensitizer.

Adult↗

A report of acute ethanol poisoning in a child: mouthwash versus cologne, perfume and after-shave.

The ingestion of ethanol-containing products, such as cologne, perfume and after-shave, in children under six years of age is common, but serious poisoning is rarely reported. Thus, it has been recently suggested that children ingesting up to 3.5 ounces of these products may be safely observed at home as long as they remain asymptomatic. While it may be assumed that products with a significantly lower alcohol content represent a much smaller poisoning hazard, mouthwashes are a relatively frequent cause of serious poisoning in children. In the following case report, 75 milliliters of mouthwash caused hypoglycemia, coma and manifestations of tonic seizure activity. Because of the palatable nature of mouthwash, wine and liquor, it appears that children are more apt to drink large quantities, consuming dangerous amounts of ethanol. The apparent safety of cologne, perfume, and after-shave may be due to a lack of palatability as well as the irritant nature of high concentrations of ethanol. This case suggests that consumer items such as mouthwash should be packaged in child-resistant containers.

Alcoholic Intoxication↗

A perfume odour-sensing system using an array of piezoelectric crystal sensors with plasticized PVC coatings.

Using PVC polymer as membrane matrix and di-n-octylphenyl phosphate (DOPP) as plasticizer, a piezoelectric crystal sensor (PCS) array with 12 adsorptive materials selected from 68 compounds by cluster analysis has been constructed as a perfume odour-sensing system. The frequency shift data obtained from the sensor array responding to four commercial perfume odours are first autoscaled and then treated by principal component analysis. The experimental results show that the plasticized PVC membrane PCS array provides improved performance of pattern recognition compared with the single adsorptive coating PCS array. The frequency shift response characteristics of these sensors have been investigated experimentally. The proposed sensor array has also been applied to the classification of commercial spirituous liquor, wine and soft drink samples, as well as aliphatic alcohol homologues and isomers.

Journal Article↗

Ti-direct, powerful, stereoselective aldol-type additions of esters and thioesters to carbonyl compounds: application to the synthesis and evaluation of lactone analogs of jasmone perfumes.

An efficient TiCl(4)-Et(3)N or Bu(3)N-promoted aldol-type addition of phenyl and thiophenyl esters or thioaryl esters with aldehydes and ketones was performed (total 46 examples). The present method is advantageous from atom-economical and cost-effective viewpoints; good to excellent yields, moderate to good syn-selectivity, substrate variations, reagent availability, and simple procedures. Utilizing the present reaction as the key step, an efficient short synthesis of three lactone [2(5H)-furanone] analogs of jasmine perfumes was performed. Among them, the lactone analog of cis-jasmone had a unique perfume property (tabac).

Journal Article↗

Perfume dermatitis. a study of 20 patients.

Patch tests to several screening sets of fragrance materials were performed on 20 perfume-sensitive patients. The most common allergens were found to be a jasmin synthetic (18 of 20 patients), cinnamic alcohol (15 of 20 patients), and hydroxycitronella (9 of 20 patients). More than half of the patients were also contact sensitive to other ingredients of cosmetics and over-the-counter and prescription preparations.

Aged↗

Do perfume additives termed human pheromones warrant being termed pheromones?

Two studies of the effects of perfume additives, termed human pheromones by the authors, have conveyed the message that these substances can promote an increase in human sociosexual behaviour [Physiol. Behav. 75 (2003) R1; Arch. Sex. Behav. 27 (1998) R2]. The present paper presents an extended analysis of this data. It is shown that in neither study is there a statistically significant increase in any of the sociosexual behaviours for the experimental groups. In the control groups of both studies, there are, however, moderate but statistically significant decreases in the corresponding behaviour. Most notably, there is no support in data for the claim that the substances increase the attractiveness of the wearers of the substances to the other sex. It is concluded that more research using matched homogenous groups of participants is needed.

Adult↗

Allergic contact dermatitis to the perfume in Mycolog cream.

Mycolog contact allergy is due primarily to its ethylenediamine and fragrance components. In the evaluation of Mycolog-sensitive patients, the major constituents, including the perfume at 5% or 10% in petrolatum, should be tested.

Dermatitis, Atopic↗

Patch testing with perfume ingredients.

From the large number of substances used in perfumes it is difficult and tedious to identify the allergen in a specific case of dermatitis. Many substances are both irritants and sensitizers. Based on personal experience, a list has been prepared of potential sensitizers, their concentrations and diluents suitable for patch testing.

Dermatitis, Contact↗

Perfume allergy due to oak moss and other lichens.

During a period of 2 1/2 years, 7 of 2000 patients routinely tested at our laboratory revealed contact allergy to oak moss in perfumes. All reacted to a mixture of different lichens and to some specific lichen compounds. The sensitivity was probably induced by cosmetics containing lichen substances. The following 3 compounds caused reactions in all patients tested: atranorin, evernic and usnic acids. 3 patients were photosensitive, but stronger reactions were elicited by prolonged contact during occlusion of the patches and complete protection against light, rather than by irradiation alone. The data suggest that the sensitizing capacity of the lichen compounds is primarily of a contact rather than of a photocontact nature.

Adult↗

Phototoxicity, photoallergy, and contact sensitization of nitro musk perfume raw materials.

The potential of 4 related nitro musk substances (musk tibetene, musk ketone, musk xylol, and musk moskene) to cause photoallergy, phototoxicity, and/or contact sensitivity was compared to that of musk ambrette, a known photoallergen. Musk ambrette caused a high incidence of photoallergy as indicated by the severity of the skin grades as compared to a control group. Musk tibetene and musk moskene were negative for phototoxicity, photoallergenicity and contact sensitivity under the test conditions. Musk xylol was shown to be a weak contact sensitizer. Musk ketone gave challenge responses suggestive of a weak phototoxin and a weak contact sensitizer. The latter was not affected by light exposure. These data suggest that except for musk ambrette, the nitro musks as a group do not have the potential to produce photoallergy. Some members of this type of perfume raw material could be classified as weak sensitizers (musk xylol, musk ketone) or weakly phototoxic (musk ketone). These latter biological qualities have not been expressed clinically.

Animals↗

Experimental techniques and laboratory apparatus in ancient Greece: drug and perfume preparation.

Ancient greek laboratory experts - phycisians, drogists or perfumers - may be accredited with the evolution of rather sophisticated techniques for the isolat-ion of plant ingredients and the preparation of medicines and fragnances. Mainly based on literary sources, from linear B tablets to Galen or the alchemic corpus, the present paper presents these procedures and describes the apparatus use.

Equipment and Supplies↗