Microextraction Gas Chromatography-tandem Mass Research Articles

Impact of the Interactions between Fragrances and Cosmetic Bases on the Fragrance Olfactory Performance: A Tentative to Correlate SPME-GC/MS Analysis with That of an Experienced Perfumer

“Seta e Ciliegia” and “Narguilé” fragrances were mixed to form a binary blend with chemically stable, non-volatile, odourless, simple bases of different lipophilicity widely used in skin care and hair care formulations, such as caprylic-capric triglyceride, glycerine, paraffin, dimethicone, isopropyl myristate and butylene glycol, with the objective to verify how the olfactory performance of fragrances can be influenced by skin or hair care ingredients. The semiquantitative approach applied in this study aims in providing a practical solution to appropriately combine a fragrance with cosmetic ingredients. Pure fragrance and binary blends were analysed by solid phase microextraction gas chromatography tandem mass spectrometry (SPME-GC/MS), based on the assumption that the solid phase microextraction is able to extract volatile compounds, mimicking the ability of the nose to capture similar volatile compounds. Fifty-seven and forty-four compounds were identified by SPME-GC/MS in pure fragrances “Seta e Ciliegia” and “Narguilé”, respectively. Once mixed with the bases, the analysis of the blends revealed that a qualitative modification in the chromatograms could occur according to the characteristics of the bases. In general, for both fragrances, blends with glycerin and butylene glycol, which are the most hydrophilic bases among the ones tested, were able to release most of the peaks, that were thus still present in the chromatograms. Differently, in the blends with caprylic-capric triglyceride, most of the peaks are lost. Blends with paraffine, dimethicone and isopropyl myristate showed an intermediate behaviour. These results were thus compared with the sensory evaluation made by an experienced perfumer, capable of assessing the different olfactory performances of pure fragrances and their different binary blends. The evaluation made by the perfumer fitted well with the analytical results, and in the blends where most of the peaks were revealed in the chromatogram, the perfumer found a similar olfactory profile for example with glycerin, butylene glycol, while a modification of the olfactory profile was highlighted when several peaks were not still present in the chromatogram, as it was the case with caprylic-capric triglyceride. Interestingly, when the most typical peaks of a fragrance were still observed in the blend, even if some of them were lost, the olfactory performance was not lost, as was the case of paraffin and isopropyl myristate. In the case of dimethicone, its high volatility was considered responsible for a certain decrease in the fragrance “volume”. The results achieved with this investigation can be used to hypothesize that the different compounds of a fragrance, characterized for the first time by different volatility and solubility, could be differently retained by the bases: the more lipophilic are strongly retained by the lipophilic bases with a consequently reduced volatility that limits the possibility of being appreciated by the nose and that corresponds to disappearance or a percentage reduction from the chromatogram. Therefore, in a more accurate and helpful view for a formulator, we could come to the conclusion that based on the results achieved by our investigation, the inclusion of a less lipophilic base can be more appropriate to exalt more lipophilic fragrances.

Assessment of genetic diversity and volatile content of commercially grown banana (Musa spp.) cultivars

Banana is an important fruit crop in the tropics and subtropics; however, limited information on biomarkers and signature volatiles is available for selecting commercial cultivars. Clonal fidelity is a major contributor to banana yield and aroma; however, there are no useful biomarkers available to validate clonal fidelity. In this study, we performed the molecular profiling of 20 banana cultivars consisting of diploid (AA or AB) and triploid (AAA or AAB or ABB) genomic groups. We screened 200 molecular markers, of which 34 markers (11 RAPD, 11 ISSR, and 12 SSR) yielded unequivocally scorable biomarker profiles. About 75, 69, and 24 allelic loci per marker were detected for RAPD, ISSR, and SSR markers, respectively. The statistical analysis of molecular variance (AMOVA) exhibited a high genetic difference of 77% with a significant FST value of 0.23 (p < 0.001). Interestingly, the UBC-858 and SSR CNMPF-13 markers were unique to Grand Nain and Ardhapuri cultivars, respectively, which could be used for clonal fidelity analysis. Furthermore, the analysis of banana fruit volatilome using headspace solid-phase microextraction-gas chromatography-tandem mass spectrometry (HS-SPME-GCMS) revealed a total of fifty-four volatile compounds in nine banana cultivars with 56% of the total volatile compounds belonging to the ester group as the significant contributor of aroma. The study assumes significance with informative biomarkers and signature volatiles which could be helpful in breeding and for the authentic identification of commercial banana cultivars.

Development of a solid phase microextraction gas chromatography tandem mass spectrometry methodology for the analysis of sixty personal care products in hydroalcoholic gels ˗ hand sanitizers ˗ in the context of COVID-19 pandemic

Because of the coronavirus pandemic, hydroalcoholic gels have become essential products to prevent the spread of COVID-19. This research aims to develop a simple, fast and sustainable microextraction methodology followed by gas chromatography tandem mass spectrometry (GC-MS/MS) to analyze simultaneously 60 personal care products (PCPs) including fragrances allergens, synthetic musks, preservatives and plasticizers in hand sanitizers. Micro-matrix-solid-phase dispersion (μMSPD) and solid-phase microextraction (SPME) were compared with the aim of obtaining high sensitivity and sample throughput. SPME demonstrated higher efficiency being selected as sample treatment. Different dilutions of the sample in ultrapure water were assessed to achieve high sensitivity but, at the same time, to avoid or minimize matrix effect. The most critical parameters affecting SPME (fibre coating, extraction mode and temperature) were optimized by design of experiments (DOE). The method was successfully validated in terms of linearity, precision and accuracy, obtaining recovery values between 80 and 112% for most compounds with relative standard deviation (RSD) values lower than 10%. External calibration using standards prepared in ultrapure water demonstrated suitability due to the absence of matrix effect. Finally, the simple, fast and high throughput method was applied to the analysis of real hydroalcoholic gel samples. Among the 60 target compounds, 39 of them were found, highlighting the high number of fragrance allergens, at concentrations ranging between 0.01 and 217 μg g−1. Most of the samples were not correctly labelled attending cosmetic Regulation (EU) No 1223/2009, and none of them followed the World Health Organization (WHO) recommendation for hand sanitizers formulation.

Development and optimization of a quantitative analysis of main odorants causing off flavours in cork stoppers using headspace solid-phase microextraction gas chromatography tandem mass spectrometry.

A simple and sensitive method was developed and validated to simultaneously separate and determine the 2-Methoxy-3,5-dimethylpyrazine, 2-Isopropyl-3-methoxypyrazine, guaiacol, 2-Isobutyl-3-methoxypyrazine, 2-Methylisoborneol, geosmin, 2,4,6-Trichloroanisole, 2,3,4,6-Tetrachloroanisole, 2,4,6-Tribromoanisole and Pentachloroanisole in cork stoppers via headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography tandem mass spectrometry (GC-MS/MS). The influence of the fibre coating used, the extraction times and temperatures, the sodium chloride additions and the desorption temperatures were investigated. Once done, the optimial HS-SPME conditions established were divinylbenzene/carboxenpolydimethylsiloxane/polydimethylsiloxane (DVB/CAR/PDMS) fibres, a 50°C extraction temperature, 60-min extraction time, an ionic strength of 3-g sodium chlorid and a 290°C desorption temperature. The method showed a good linearity (R2 ≥ 0.994) within the tested range (from 0.1 to 50 ng L-1 ) for all the compounds. Using TCA-d10 and MIB-d3 as internal standards the precision, expressed as repeatability and reproducibility RSD, was <10% in both. Note that the limits of quantifications (LOQs) are below the sensory threshold levels for such compounds in water and wine. Good recoveries were obtained for cork macerates (from 100.4% to 126%) and when compared with other reported methods using HS-SPME in water and cork stopper samples, the present method had more analytes with the lowest limit of detection for most of the targeted compounds, along with good precision and recovery.

Evaluation of the volatile from Lonicera macranthoides obtained with different processing methods by headspace–solid-phase microextraction–gas chromatography–tandem mass spectrometry (HS–SPME–GC–MS)

Headspace–solid-phase microextraction coupled to gas chromatography–tandem mass spectrometry (HS–SPME–GC–MS) method was used to determine the composition and content of volatiles in dried flower buds of Lonicera macranthoides obtained by five processing methods (PMs). Sixty-five compounds were identified, which included alcohols, aldehydes, ketones, hydrocarbons, acids, esters, terpenoids, and others. Alcohols were the most abundant compounds in most of the samples while acids were present in negligible amounts. Samples obtained by sun drying (PM4) and by heating in an oven with a programmed temperature cycle (PM2) were characterized by higher amounts of esters and terpenoids. PM4 resulted in larger numbers of compounds albeit in lower amounts. The principal component analysis confirmed that terpenoids and esters were the most prominent volatiles from PM2. The HS–SPME–GC–MS method can be used to rapidly ascertain the volatile content in L. macranthoides samples; the results herein provided provide a valuable source for comparing the effects of applying different processing methods.

Quantification of Seven Terpenes in Human Serum by Headspace Solid-Phase Microextraction-Gas Chromatography-Tandem Mass Spectrometry.

Terpenes are a class of volatile organic hydrocarbons commonly produced by vegetation and released into the atmosphere. These compounds are responsible for the scents of pine forests, citrus fruits, and some flowers. Human terpene exposure can come from inhalation, diet, smoking, and more recently, using e-cigarettes. Terpenes are present in tobacco smoke and are used as flavor chemicals in e-liquids. The health effects of terpenes are not widely known, though several studies have suggested that they may prove useful in future medical applications. We have developed a novel, high-throughput method of quantifying seven terpenes (α-pinene, β-pinene, β-myrcene, 3-carene, limonene, β-caryophyllene, and α-humulene) in human serum to aid human-exposure investigations. This method employs headspace sampling using solid-phase microextraction (SPME) coupled to gas chromatography-tandem mass spectrometry to detect and quantify five monoterpenes and two sesquiterpenes in the low parts-per-trillion to low parts-per-billion range. The intraday and interday variability (percent error) of the method are ≤2 and ≤11%, respectively. In addition, this method showed excellent recovery in human serum (between 80 and 120% for all analytes). The assay precision ranges between 4.0 and 11%. Limits of detection ranged between 0.032 and 0.162 μg/L. Using serum cotinine values to classify tobacco use showed that smokers have higher serum concentrations of six terpenes compared to nonusers. Terpene concentrations were 14-78% higher in smokers than nonusers. Our method can provide essential biomonitoring data to establish baseline exposure levels for terpenes in humans.

Development and optimization of a solid-phase microextraction gas chromatography–tandem mass spectrometry methodology to analyse ultraviolet filters in beach sand

A methodology based on solid-phase microextraction (SPME) followed by gas chromatography–tandem mass spectrometry (GC–MS/MS) has been developed for the simultaneous analysis of eleven multiclass ultraviolet (UV) filters in beach sand. To the best of our knowledge, this is the first time that this extraction technique is applied to the analysis of UV filters in sand samples, and in other kind of environmental solid samples. Main extraction parameters such as the fibre coating, the amount of sample, the addition of salt, the volume of water added to the sand, and the temperature were optimized. An experimental design approach was implemented in order to find out the most favourable conditions. The final conditions consisted of adding 1 mL of water to 1 g of sample followed by the headspace SPME for 20 min at 100 °C, using PDMS/DVB as fibre coating. The SPME-GC–MS/MS method was validated in terms of linearity, accuracy, limits of detection and quantification, and precision. Recovery studies were also performed at three concentration levels in real Atlantic and Mediterranean sand samples. The recoveries were generally above 85% and relative standard deviations below 11%. The limits of detection were in the pg g−1 level. The validated methodology was successfully applied to the analysis of real sand samples collected from Atlantic Ocean beaches in the Northwest coast of Spain and Portugal, Canary Islands (Spain), and from Mediterranean Sea beaches in Mallorca Island (Spain). The most frequently found UV filters were ethylhexyl salicylate (EHS), homosalate (HMS), 4-methylbenzylidene camphor (4MBC), 2-ethylhexyl methoxycinnamate (2EHMC) and octocrylene (OCR), with concentrations up to 670 ng g−1.

Rapid Analysis of 27 Volatile Sulfur Compounds in Wine by Headspace Solid-Phase Microextraction Gas Chromatography Tandem Mass Spectrometry

Volatile sulfur-containing compounds (VSCs) play an important role in wine aroma conferring at high concentrations unpleasant odors but also participating positively at low concentration. A large number of VSCs are formed at different stages of winemaking and storage. To monitor this phenomenon, a HS-SPME-GC-MS/MS method has been developed. The method is proposed in order to quantify 27 different sulfur-containing compounds. SPME extraction was performed using a carboxen-polydimethylsiloxane (CAR-PDMS) fiber, which resulted the most effective fiber coating. Time and temperature extraction conditions were optimized using response surface methodology. The selectivity and sensitivity of the method were considerably increased using triple-quadrupole in multiple reaction monitoring (MRM) mode. The number of VSCs analyzed in a single run was higher than in any other method previously reported using single-quadrupole MS or other detectors. The overall process was successfully applied to identify and quantify sulfur compounds both in white and red wines.

Development of a multi-preservative method based on solid-phase microextraction–gas chromatography–tandem mass spectrometry for cosmetic analysis

A simple methodology based on solid-phase microextraction (SPME) followed by gas chromatography–tandem mass spectrometry (GC–MS/MS) has been developed for the simultaneous analysis of different classes of preservatives including benzoates, bronidox, 2-phenoxyethanol, parabens, BHA, BHT and triclosan in cosmetic products. In situ acetylation and subsequent organic modifier addition have been successfully implemented in the SPME process as an effective extractive strategy for matrix effect compensation and chromatographic performance improvement. Main factors affecting SPME procedure such as fiber coating, sampling mode, extraction temperature and salt addition (NaCl) were evaluated by means of a 3×23–1 factorial experimental design. The optimal experimental conditions were established as follows: direct solid-phase microextraction (SPME) at 40°C and addition of NaCl (20%, w/v), using a DVB/CAR/PDMS fiber coating. Due to the complexity of the studied matrices, method performance was evaluated in a representative variety of both rinse-off and leave-on samples, demonstrating to have a broad linear range (R2>0.9964). In general, quantitative recoveries (>85% in most cases) and satisfactory precision (RSD<13% for most of compounds) were obtained, with limits of detection (LODs) well below the maximum authorized concentrations established by the European legislation. One of the most important achievements of this work was the use of external calibration with cosmetic-matched standards to accurately quantify the target analytes. The validated methodology was successfully applied to the analysis of different types of cosmetic formulations including body milks, moisturizing creams, deodorants, sunscreen, bath gel, dental cream and make-up products amongst others, demonstrating to be a reliable multi-preservative methododology for routine control.

Headspace–Solid Phase Microextraction–Gas Chromatography–Tandem Mass Spectrometry (HS-SPME-GC-MS2) Method for the Determination of Pyrazines in Perilla Seed Oils: Impact of Roasting on the Pyrazines in Perilla Seed Oils

A new headspace (HS)-solid phase microextraction (SPME)-gas chromatography-tandem quadrupole mass spectrometry (GC-MS(2)) was established for the simultaneous characterization and quantitation of pyrazines in perilla seed oils. HS-SPME conditions such as fiber choice, extraction temperature, and adsorption times were tested. The established GC-MS(2) showed low detection limit (LOD) and high specificity, recovery, and precision for analysis of pyrazines in perilla seed oils. The LODs for the pyrazines were in the range of 0.07-22.22 ng/g oil. The relative standard deviations (RSDs) for the intra- and interday repeated analyses of pyrazines were less than 9.49 and 9.76%, respectively. The mean recoveries for spiked pyrazines in perilla seed oil were in the range of 94.6-107.92%. Perilla seed oils were obtained by mechanical pressing from perilla seeds roasted to different degrees of roasting (mild, medium, medium dark, and dark roasting). Fourteen pyrazine compounds in perilla seed oils were isolated, identified, and quantitated. Among them, 2-methyl-3-propylpyrazine, tetramethylpyrazine, and 2,3-diethyl-5-methylpyrazine were the first identified in perilla seed oils. Degree of roasting influenced greatly the composition and contents of pyrazines in perilla seed oils. In light-roasted perilla seed oil, 2,5-dimethylpyrazine was the most predominant pyrazine. However, in dark-roasted perilla seed oil, 2-methylpyrazine was the most abundant pyrazine in the oil, representing 38.3% of its total pyrazine content. Dark-roasted perilla seed oil contains 16.78 times higher quantity of pyrazines than light-roasted perilla seed oil. This represents the first report on the quantity of pyrazines in perilla seed oils.

Development of a solid-phase microextraction–gas chromatography–tandem mass spectrometry method for the analysis of chlorinated toluenes in environmental waters

In the present work, a simple and fast methodology has been developed for the analysis of chlorotoluenes in water samples using solid-phase microextraction (SPME) coupled to gas chromatography–tandem mass spectrometry (GC/MS/MS). A multifactorial experimental design strategy was used for studying the influence on extraction yield of factors such as fiber coating, extraction mode, temperature, and addition of sodium chloride. Quantitative recoveries (≥84%) and satisfactory precision (relative standard deviations (RSD) ≤ 12%) have been obtained. Limits of detection (LODs) in the sub-picogram per litre level from 0.030 to 0.330 were achieved for all analyzed compounds. Linearity was studied in a wide range of concentrations and an analysis of variance with a lack-of-fit test was run to validate the calibration data. Extraction time profiles were also studied, showing that most of chlorotoluenes reached the equilibrium or were close to it. Finally, the applicability of the proposed method has been demonstrated for real samples including river and sewage water samples. Since no matrix effects were observed, quantification could readily be carried out by external calibration with ultrapure water standards.

Headspace solid-phase microextraction gas chromatography tandem mass spectrometry for the determination of brominated flame retardants in environmental solid samples

A headspace solid-phase microextraction gas chromatography coupled with tandem mass spectrometry (HSSPME-GC-MS-MS) methodology for determination of brominated flame retardants in sediment and soil samples is presented. To the best of our knowledge, this is the first time that SPME has been applied to analyze polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in environmental solid samples. Analyses were performed using 0.5-g solid samples moisturized with 2 mL water, employing a polydimethylsiloxane (PDMS) fiber coating, exposed to the headspace at 100 degrees C for 60 min. Several types of environmental solid samples were included in this study and the extraction efficiency was related to the organic matter content of the sample. Calibration was performed using real samples, and the method showed good linearity over a wide concentration range, precision, and afforded quantitative recoveries. The obtained detection limits were in the sub-ng g(-1) for all the target analytes in both samples. The proposed procedure was applied to several marine and river sediments and soils, some of which were found to contain PBDEs at concentrations in the ng g(-1) level; BDE-47, BDE-100, and BDE-99 were the major congeners detected. The proposed method constitutes a rapid and low-cost alternative for the analysis of the target brominated flame retardants in environmental solid samples, since the clean-up steps, fractionation, and preconcentration of extracts inherent to the classical multi-step solvent extraction procedures are avoided.