Multidimensional Gas Chromatography-mass Spectrometry Research Articles

Development of an analytical method for the determination of sterol compounds in boars’ saliva

“Boar taint” compounds influence the sexual behavioral responses of sows and stimulate their reproduction. This paper reports a fast, easier, and a non-invasive analytical method for the analysis of three “boar taint” compounds in boar’ saliva samples: androstenone, androsten-3α-ol, and androsten-3β-ol. This method was developed and validated based on solid-phase extraction (SPE) and multidimensional gas chromatography-mass spectrometry (MDGC-MS). All the compounds were detected without derivatization. This method affords good reproducibility (4%–8%), accuracy (80%–105%), precision (5.5%–9.1%), linearity (R2 = 0.98–0.99), and lower limits of quantitation (LLOQ) (0.1–0.2 μg/L). Although the presence of these compounds in saliva has been known for a long time, no simple and easy analytical method has been developed.

Changes of Androstenone Concentrations in Saliva of Boars with Age.

Simple SummaryPork is one of the most consumed meats worldwide. In many countries, pork is produced only from gilts or barrows because of the presence of boar taint in boar’s meat. Boar taint is an unpleasant odour, which is present in the meat and fat of boars. This odour is related to the increasing age and body weight of boars. The absence of boar taint in the final product can be achieved by castration of boars. Regarding the welfare of the animals, it would be appropriate to find a non-invasive, reliable, and working method for the determination of boar taint during the fattening of boars. Androstenone, which is one of the main compounds responsible for boar taint, can be determined from saliva. This method appears to be a hopeful way to predict individuals with a high level of this compound. Based on the current knowledge, the early slaughter of boars could be a suitable and functional step to avoid boar taint in the meat or fat, respectively. This is a pilot study that is focused on the non-invasive determination of boar taint on live animals. In the future, this method could be simplified and adjusted for use in farm conditions.With the increasing age of boars, the possibility of androstenone (5α-androst-16-en-3-one (AND), 5α-androst-16-en-3α-ol (α-AND), and 5α-androst-16-en-3β-ol (β-AND)) occurrence increases as well. The aim of this study was to evaluate concentrations of androstenone compounds in the saliva of boars concerning the age of animals. In total, 72 boars were evaluated (24 boars per replication). The effect of age (three different ages—152, 163, and 172 days) was observed, and (Landrace × Large White) × Pietrain genotypes were used. Chemical analysis of saliva samples was conducted by multidimensional gas chromatography/mass spectrometry (MDGC/MS). Salivary α-AND increased with age (p < 0.05), and positive correlations were found between age and submaxillary salivary gland weight (p < 0.05), age, and salivary AND concentration (p < 0.05), body weight and submaxillary salivary gland weight (p < 0.05), submaxillary salivary gland weight and salivary β-AND concentration (p < 0.05), as well as submaxillary salivary gland weight and total salivary 5α-androstenone (AND total) concentration (p < 0.001). Nowadays, animal welfare is becoming a more and more discussed topic, and pig breeding is not an exception. Specifically, the castration ban is a current issue, so it is very important to know as much as possible about compounds responsible for boar taint. Androstenone’s appearance in boars’ saliva could be one of the most important precursors for future early detection of boar taint.

Determination of Volatiles in Rosa Rugosa by Knitting Aromatic Polymer – Polydopamine (KAP@PDA) Solid-Phase Microextraction (SPME) and Multidimensional Gas Chromatography – Mass Spectrometry (MDGC-MS)

The volatile compounds in Rosa rugosa ‘Zi Zhi’, R. rugosa ‘Feng Hua’, and R. cv ‘Crimson Glory’ from three regions were determined by two-dimensional gas chromatography with quadrupole time-of-flight mass spectrometry coupled with knitting aromatic polymer – polydopamine (KAP@PDA) solid-phase microextraction. 82 compounds were identified by peak matching and retention indices, and R. cv ‘Crimson Glory’ contained the most volatile components. D-Limonene (up to 5131 μg kg−1), benzyl alcohol (up to 16,510 μg kg−1), benzeneacetaldehyde (up to 13,820 μg kg−1), phenylethyl alcohol (up to 49,020 μg kg−1) and citronellol (up to 7129 μg kg−1) were the major constituents in all R. rugosa species. In addition, benzaldehyde was highly abundant in R. cv ‘Crimson Glory’ (up to 23,130 μg kg−1). The primary volatile components responsible for the differences among the three R. rugosa cultivars and regions were distinguished by orthogonal partial least-squares discriminant analysis. The results suggested that phenylethyl alcohol contributed the most in distinguishing aroma quality for R. rugosa cultivars and those from different regions.

Detection of Sub-Aroma Threshold Concentrations of Wine Methoxypyrazines by Multidimensional GCMS

Complex matrices, such as wine, provide a challenge in the quantification of compounds. There exists a high likelihood of co-elution in these matrices, thereby artificially increasing the observed concentration. This can often lead to confusing data where compounds are above aroma detection thresholds, but are not detected by olfactory analysis. Additionally, the lack of sensitivity in assays can lead to the non-detection of sub-aroma threshold concentrations and contrasting data when olfactory analysis detects these aromas. To eliminate these pitfalls and gain a better understanding of the role that methoxypyrazines impart green character to wine, a quantitative method using headspace solid-phase microextraction coupled to heart-cutting multidimensional gas chromatography mass spectrometry was developed. The method can quantitate the three common methoxypyrazines found in wine at the picogram per liter level while resolving co-eluting compounds. The proposed method was validated using model wine and wine solutions and was ultimately used for the comparative analysis of white, rosé, and red wines.

Advanced mono- and multi-dimensional gas chromatography-mass spectrometry techniques for oxygen-containing compound characterization in biomass and biofuel samples.

A wide variety of biomass, from triglycerides to lignocellulosic-based feedstock, are among promising candidates to possibly fulfill requirements as a substitute for crude oils as primary sources of chemical energy feedstock. During the feedstock processing carried out to increase the H:C ratio of the products, heteroatom-containing compounds can promote corrosion, thus limiting and/or deactivating catalytic processes needed to transform the biomass into fuel. The use of advanced gas chromatography techniques, in particular multi-dimensional gas chromatography, both heart-cutting and comprehensive coupled to mass spectrometry, has been widely exploited in the field of petroleomics over the past 30 years and has also been successfully applied to the characterization of volatile and semi-volatile compounds during the processing of biomass feedstock. This review intends to describe advanced gas chromatography-mass spectrometry-based techniques, mainly focusing in the period 2011-early 2020. Particular emphasis has been devoted to the multi-dimensional gas chromatography-mass spectrometry techniques, for the isolation and characterization of the oxygen-containing compounds in biomass feedstock. Within this context, the most recent advances to sample preparation, derivatization, as well as gas chromatography instrumentation, mass spectrometry ionization, identification, and data handling in the biomass industry, are described.

Multidimensional gas chromatographic‒Mass spectrometric method for separation and identification of triacylglycerols in olive oil.

A 'heart-cut' multidimensional gas chromatography‒mass spectrometry (H/C MDGC‒MS) method for separation and identification of triacylglycerols (TAGs) in extra virgin olive oil was developed. A GC configuration, comprising a non-polar first dimension (1D) column (15 m length) and a mid-polarity second dimension (2D) column (9 m length), was employed. Standard TAGs were used to test and demonstrate the H/C MDGC method, for identification of TAG components and to validate the method. Various chromatographic conditions such as column flow and temperature program were evaluated. The 1D separation resulted in overlap of some standard TAG peaks. These overlapped 1D regions of the standard TAGs were H/C to 2D for further separation and resulted in clearly distinguished individual TAG component peaks. The 1D separation of olive oil TAGs displayed three major peaks and four minor peaks. The application of the H/C MDGC method to olive oil TAGs resulted in the separation of each sampled 1D region into two or more TAG peaks. TAG components in olive oil resolved on the 2D column were identified based on characteristic mass fragment ions such as [M-RCO2]+, [RCO+128]+, [RCO+74]+ and RCO+ and comparison of their mass spectra with that of the standard TAGs. Sixteen olive oil TAGs were identified by MS after 2D separation. The repeatability of the H/C method was evaluated in terms of retention time shift and area response in the 2D and found to be <0.02% and <8% RSD respectively.

Biosignature Analysis of Mars Soil Analogs from the Atacama Desert: Challenges and Implications for Future Missions to Mars.

The detection of biosignatures on Mars is of outstanding interest in the current field of astrobiology and drives various fields of research, ranging from new sample collection strategies to the development of more sensitive detection techniques. Detailed analysis of the organic content in Mars analog materials collected from extreme environments on Earth improves the current understanding of biosignature preservation and detection under conditions similar to those of Mars. In this article, we examined the biological fingerprint of several locations in the Atacama Desert (Chile), which include different wet and dry, and intermediate to high elevation salt flats (also named salars). Liquid chromatography and multidimensional gas chromatography mass spectrometry measurement techniques were used for the detection and analysis of amino acids extracted from the salt crusts and sediments by using sophisticated extraction procedures. Illumina 16S amplicon sequencing was used for the identification of microbial communities associated with the different sample locations. Although amino acid load and organic carbon and nitrogen quantities were generally low, it was found that most of the samples harbored complex and versatile microbial communities, which were dominated by (extremely) halophilic microorganisms (most notably by species of the Archaeal family Halobacteriaceae). The dominance of salts (i.e., halites and sulfates) in the investigated samples leaves its mark on the composition of the microbial communities but does not appear to hinder the potential of life to flourish since it can clearly adapt to the higher concentrations. Although the Atacama Desert is one of the driest and harshest environments on Earth, it is shown that there are still sub-locations where life is able to maintain a foothold, and, as such, salt flats could be considered as interesting targets for future life exploration missions on Mars.

Signatures of Biologically Driven Hemicellulose Modification Quantified by Analytical Pyrolysis Coupled with Multidimensional Gas Chromatography Mass Spectrometry

Biomass storage conditions are a major source of feedstock quality variability that impact downstream preprocessing, feeding, handling, and conversion into biofuels, chemicals and products. Microbi...

Review of recent developments in GC-MS approaches to metabolomics-based research.

Metabolomics aims to identify the changes in endogenous metabolites of biological systems in response to intrinsic and extrinsic factors. This is accomplished through untargeted, semi-targeted and targeted based approaches. Untargeted and semi-targeted methods are typically applied in hypothesis-generating investigations (aimed at measuring as many metabolites as possible), while targeted approaches analyze a relatively smaller subset of biochemically important and relevant metabolites. Regardless of approach, it is well recognized amongst the metabolomics community that gas chromatography-mass spectrometry (GC-MS) is one of the most efficient, reproducible and well used analytical platforms for metabolomics research. This is due to the robust, reproducible and selective nature of the technique, as well as the large number of well-established libraries of both commercial and 'in house' metabolite databases available. This review provides an overview of developments in GC-MS based metabolomics applications, with a focus on sample preparation and preservation techniques. A number of chemical derivatization (in-time, in-liner, offline and microwave assisted) techniques are also discussed. Electron impact ionization and a summary of alternate mass analyzers are highlighted, along with a number of recently reported new GC columns suited for metabolomics. Lastly, multidimensional GC-MS and its application in environmental and biomedical research is presented, along with the importance of bioinformatics. The purpose of this review is to both highlight and provide an update on GC-MS analytical techniques that are common in metabolomics studies. Specific emphasis is given to the key steps within the GC-MS workflow that those new to this field need to be aware of and the common pitfalls that should be looked out for when starting in this area.

New method based on Solid Phase Microextraction and Multidimensional gas chromatography-mass spectrometry to determine pesticides in strawberry jam

Although, the use of pesticides is necessary in agriculture to prevent crops destruction and to avoid the attack to leaves and stems of the plants, which cause quality defects of fruits and yield reduction, the control of pesticide is important in order to guarantee human safety. In the present study, a new method based on the use of solid-phase microextraction (SPME) followed by multidimensional gas chromatography-mass spectrometry (MDGC-MS) analysis was developed to detect pesticides in strawberry jam. Commercial and home-made jams as well as spiked non-spiked samples were included in the study. The method was validated by analysing commercial jam samples spiked with a pesticide mixture (ie, standard Mix 101). As a result, Relative Standard Deviation estimated from five replicates, was always below 16%. Limit detection values varied from 0.11 to 0.42 ng/kg on the first dimension and from 0.013 to 0.093 ng/kg on the second dimension. These levels are considerably lower than the Maximum Residue Levels established for strawberry pesticides by EU Regulations. Also, the matrix effect of the strawberry jam on the effectiveness of the SPME extraction was evaluated. The data presented demonstrate that the method proposed is capable of detecting reliably very low concentrations of pesticides in strawberry jams between 0.013 and 0.093 ng/kg. Additional advantages of the method are its repeatability, rapidity, simplicity, selectivity and environmental friendly nature.

Complementary Use of Multi-dimensional Gas Chromatography and Proton Transfer Reaction Mass Spectrometry for Identification of Rapeseed Oil Quality Indicators

The change of concentration of various volatiles generated during frying may be an indicator of oil quality. Chemical compounds such as aldehydes, ketones, alcohols and carboxyl acids are the products of oxidation during thermal degradation of edible oils. Shown in this work is a complementary use of GC×GC-TOFMS and PTR-MS for the detection and determination of quality indicators of rapeseed oil. The former technique was used for the identification of potential markers and the latter for their quantitative determination. As a result of the GC×GC analysis, it was determined that 2-pentanone, heptane, octane, 1-heptanol and nonanal can be considered indicators of thermal degradation of rapeseed oil. Using PTR-MS, it was possible to monitor the concentration of these volatile indicators in real time. Based on the results of the analysis and of the reference method, it was concluded that 1-heptanol is best suited for the role of a quality indicator of thermal degradation of rapeseed oil.

Free Monoterpene Isomer Profiles of Vitis Vinifera L. cv. White Wines.

Monoterpene compounds contribute floral and fruity characters to wine and are desired by grape growers and winemakers for many white wines. However, monoterpene isomers, especially monoterpene enantiomers, have been little explored. It is possible to identify and quantitate 17 monoterpene isomers in 148 varietal wines from eight grape varieties; Chardonnay, Gewürztraminer, Muscat, Pinot gris, Riesling, Sauvignon blanc, Torrontes, and Viognier in two vintages by Headspace solidphase microextraction multidimensional gas chromatography mass spectrometry (HS-SPME-MDGC-MS). Results obtained from general linear models and discriminant analysis showed significant differences for the isomer profiles and enantiomer fractions among the eight grape varieties and four wine styles. The high R2 values from the fitted line show low variation in enantiomeric differences based on variety. These results provide an overview of the monoterpene isomers of wide varietal wines, and support that isomer profiles and enantiomer fractions could differentiate our wines by varietal and wine style.

Relationship between the terpene enantiomeric distribution and the growth cycle of lemon fruit and comparison of two extraction methods

Lemon essential oil is one of the most widely used natural flavours in the food and beverage industries. Knowledge of the enantiomeric ratio in flavours has gained relevance because they may indicate differences in their organoleptic characteristics or their authenticity. The study was carried out during the growth of the lemon fruit to evaluate the possible variations of the enantiomeric ratio of four characteristic terpenes: α-pinene, β-pinene, linalool and limonene. Two extraction methods were applied to extract the terpenes: simultaneous distillation–extraction at reduced pressure (V-SDE) and solid-phase microextraction; the results were equivalent whatever the method applied. In both cases, the target compounds were obtained from the lemon peel. Enantiomeric profiles were obtained by enantioselective multi-dimensional gas chromatography–mass spectrometry (enantio-MDGC-MS). Consistent enantiomeric ratios of α-pinene, β-pinene and limonene were observed; however, the enantiomeric ratio of linalool varied significantly according to the growth stage of the lemons in a spontaneous and natural way.

Determination of ppq-levels of alkylmethoxypyrazines in wine by stirbar sorptive extraction combined with multidimensional gas chromatography-mass spectrometry

Alkylmethoxypyrazines are powerful odorants in many food products. A new method for analysing 3-isopropyl-2-methoxypyrazine, 3-s-butyl-2-methoxypyrazine and 3-isobutyl-2-methoxypyrazine has been developed and applied to wine. The analytes were extracted from 5 mL of wine using stirbar sorptive extraction followed by thermal desorption and multidimensional gas chromatography-mass spectrometry analysis in a single oven. The extraction conditions were optimized in order to obtain a high recovery of the 3-alkyl-2-methoxypyrazines (MP). The detection limits of the method in all cases were under 0.08 ng/L, well below the olfactory thresholds of these compounds in wine. The reproducibility of the method was adequate (below 10%), the linearity satisfactory and the recoveries in all cases close to 100%. The method has been applied to the analysis of 111 Spanish and French wine samples. The levels found suggest that MP have a low direct impact on the aroma properties of wines from the regions around the Pyrenean massif.

Multidimensional Gas Chromatography–Mass Spectrometry Method for Fingerprinting Polycyclic Aromatic Hydrocarbons and Their Alkyl-Homologs in Crude Oil

ABSTRACTThe composition of polycyclic aromatic hydrocarbons in crude oil is usually too complex to use standard capillary gas chromatography to separate all of the components. In this study, a multidimensional gas chromatography–mass spectrometry (GC-MS) technique was used to analyze polycyclic aromatic hydrocarbon fractions of crude oil collected from the Dongying oil field in the Bohai Sea. A DB-17MS column (30 m × 0.25 mm × 0.25 µm) was used as a prefractionating column and only selected heart-cuts were transferred to the second chromatographic dimension (HP-5MS, 15 m × 0.25 mm × 0.25 µm) by a pressure-adjusted continual flow-type switching device for quantification of the polycyclic aromatic hydrocarbons. The chromatographic elements and parameters, such as detector selection and column combinations, were optimized. Naphthalene, phenanthrene, fluorene, dibenzothiophene, chrysene, and their C1–C4 alkyl homologs were identified. The profile of the polycyclic aromatic hydrocarbons obtained using the multidimensional GC-MS method was compared with the results obtained by traditional one-dimensional GC-MS.

Quantification ethyl carbamate in wines using reaction-assisted-extraction with 9-xanthydrol and detection by heart-cutting multidimensional gas chromatography-mass spectrometry

9-Xanthydrol was introduced as an assisted-extraction-reagent to quantify ethyl carbamate (EC) in wines by heart-cutting multidimensional gas chromatography coupled with mass spectrometry (MDGC-MS). 9-Xanthydrol could help to increase the extraction efficiency, because it could react with ethyl carbamate to form the low-polar product, which facilitated the transfer of ethyl carbamate into organic phase. Then the reaction product was decomposed in high temperature, so ethyl carbamate could be obtained again in injector port. Heart-cutting multidimensional gas chromatography coupled with mass spectrometry was used not only for avoiding 9-xanthydrol interference but also for getting a larger volume injector, higher sensitivity and lower limit of detection. The method was optimized and validated in terms of sample volume, sodium chloride, the acid concentration, the 9-xanthydrol concentration and the reaction time. Good linear relationship (R2 = 0.9998) over the concentration range of 2.00 μg L−1 - 200.00 μg L−1 was obtained. The limit of detection (LOD, 0.02 μg L−1) and quantification (LOQ, 0.10 μg L−1) were lower than previously reported. The RSDs of precision (repeatability and reproducibility) were lower than 8.15%, and the recovery (96.17–99.25%) and accuracy (99.21–110.93%) were validated as well. This methodology was applied to the quantification of ethyl carbamate in several different fermented wines with values ranging from 13.05 to 155.20 μg L−1.

Exploring the analysis and differentiation of plastic explosives by comprehensive multidimensional gas chromatography-mass spectrometry (GC × GC–MS) with a statistical approach

Plastic explosives (PE) are a relatively insensitive form of explosives that are composed of several different types of chemicals. Differentiation of such a complex mixture is of interest to law enforcement agencies. In this work, we explored the possibility of utilizing a mass spectrometric method with statistical processing for PE analysis. Comprehensive two-dimensional gas chromatography coupled with a time-of-flight mass spectrometer (GC×GC–MS) was implemented for the analysis of PE extracts. The resulting chromatographic peaks were aligned using mass spectra and retention time data. The aligned peaks were then subjected to statistical analysis using scores generated via principal component analysis (PCA), followed by a k nearest neighbor classification with Euclidean distance. Using appropriate data treatment steps, a 0% error rate and a 0% unidentified rate in the classification of PE to production lots was achieved in cross validation classification of training samples and classification of test samples. This demonstrates accurate classification of PE samples into production lots using these data treatment steps.

Determination of Volatile Flavour Profiles of Citrus spp. Fruits by SDE-GC-MS and Enantiomeric Composition of Chiral Compounds by MDGC-MS.

Citrus fruits are known to have characteristic enantiomeric key compounds biosynthesised by highly stereoselective enzymatic mechanisms. In the past, evaluation of the enantiomeric ratios of chiral compounds in fruits has been applied as an effective indicator of adulteration by the addition of synthetic compounds or natural components of different botanical origin. To analyse the volatile flavour compounds of Citrus junos Sieb. ex Tanaka (yuzu), Citrus limon BURM. f. (lemon) and Citrus aurantifolia Christm. Swingle (lime), and determine the enantiomeric ratios of their chiral compounds for discrimination and authentication of extracted oils. Volatile flavour compounds of the fruits of the three Citrus species were extracted by simultaneous distillation extraction and analysed by gas chromatography-mass spectrometry. The enantiomeric composition (ee%) of chiral camphene, sabinene, limonene and β-phellandrene was analysed by heart-cutting multidimensional gas chromatography-mass spectrometry. Sixty-seven (C. junos), 77 (C. limon) and 110 (C. aurantifolia) volatile compounds were identified with limonene, γ-terpinene and linalool as the major compounds. Stereochemical analysis (ee%) revealed 1S,4R-(-) camphene (94.74, 98.67, 98.82), R-(+)-limonene (90.53, 92.97, 99.85) and S-(+)-β-phellandrene (98.69, 97.15, 92.13) in oil samples from all three species; R-(+)-sabinene (88.08) in C. junos; and S-(-)-sabinene (81.99, 79.74) in C. limon and C. aurantifolia, respectively. The enantiomeric composition and excess ratios of the chiral compounds could be used as reliable indicators of genuineness and quality assurance of the oils derived from the Citrus fruit species. Copyright © 2017 John Wiley & Sons, Ltd.

Quantitative analysis of trace-level benzene, toluene, ethylbenzene, and xylene in cellulose acetate tow using headspace heart-cutting multidimensional gas chromatography with mass spectrometry.

This study describes a method for the quantification of trace-level benzene, toluene, ethylbenzene, and xylene in cellulose acetate tow by heart-cutting multidimensional gas chromatography with mass spectrometry in selected ion monitoring mode. As the major volatile component in cellulose acetate tow samples, acetone would be overloaded when attempting to perform a high-resolution separation to analyze trace benzene, toluene, ethylbenzene, and xylene. With heart-cutting technology, a larger volume injection was achieved and acetone was easily cut off by employing a capillary column with inner diameter of 0.32 mm in the primary gas chromatography. Only benzene, toluene, ethylbenzene, and xylene were directed to the secondary column to result in an effective separation. The matrix interference was minimized and the peak shapes were greatly improved. Finally, quantitative analysis of benzene, toluene, ethylbenzene, and xylene was performed using an isotopically labeled internal standard. The headspace multidimensional gas chromatography mass spectrometry system was proved to be a powerful tool for analyzing trace volatile organic compounds in complex samples.

Enantiodifferentiation of 1,2-propanediol in various wines as phenylboronate ester with multidimensional gas chromatography-mass spectrometry.

Native concentrations and enantiomeric distribution of 1,2-propanediol in various wines were studied in order to evaluate its merits as a potential marker for aroma adulteration in wine. Heart-cut multidimensional gas chromatography coupled to mass spectrometry was applied to analyze 1,2-propanediol after salting-out of the polar phase, derivatization with phenyl boronic acid, and extraction with cyclohexane. The enantiomeric separation of the derivative was achieved with heptakis-(6-O-tert. butyl dimethylsilyl-2,3-di-O-acetyl)-β-cyclodextrin as the chiral selector. In all authentic wines studied, 1,2-propanediol showed a high enantiomeric ratio in favor of the (R)-enantiomer, proving its potential as a marker for the adulteration with flavor extracts based on industrial 1,2-propandiol as solvent. Usually, concentrations varied between 15 and 100mg/L. Higher values (up to 170mg/L) were found in wines made with high amounts of dry berries. However, despite the higher concentrations of 1,2-propanediol in such wines, no apparent influence on the enantiomeric distribution could be detected. Graphical Abstract Detection of fraudulent aromatization of wines by enantiodifferentiation of 1,2-propanediol as its phenylboronate ester.