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Common wheat (Triticum aestivum L.) is one of the most valuable cereal crops worldwide. This study examined leaf extracts of 30 accessions of T. aestivum and its subspecies using 48 h maceration with methanol by GC-MS and GCxGC-MS. The plants were grown from seeds of the wheat genetics collection of the Wheat Genetics Sector of the Institute of Cytology and Genetics, SB RAS. The analysis revealed 263 components of epicuticular waxes, including linear and branched alkanes, aliphatic alcohols, aldehydes, ketones, ß-diketones, carboxylic acids and their derivatives, mono- and diterpenes, phytosterols, and tocopherols. Hierarchical cluster analysis and principal component analysis were used to identify and visualize the differences between the leaf extracts of different wheat cultivars. Three clusters were identified, with the leading components being (1) octacosan-1-ol, (2) esters of saturated and unsaturated alcohols, and (3) fatty acid alkylamides, which were found for the first time in plant extracts. The results highlight the importance of metabolic studies in understanding the adaptive mechanisms and increasing wheat resistance to stress factors. These are crucial for breeding new-generation cultivars with improved traits.

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Several aromatic amines (AA) are classified as human carcinogens, and tobacco smoke is one of the main sources of exposure. Once in the human body, they undergo different metabolic pathways which lead to either their excretion or ultimately to the formation of DNA and protein adducts. The aim of this study was to investigate AA in 68 urine samples (aged 29-79, 47% female), including 10 smokers (S), 28 past-smokers (PS) and 30 never-smokers (NS), and to study if there was a relation between the smoking status and the amount of the AA present. GCxGC-MS was used to analyze AA in complex urine samples due to its high peak capacity and the fact that it provides two sets of retention times and structural information, which facilitates the separation and identification of the target analytes. First, a qualitative comparison of an example set of a NS, PS and S sample was carried out, in which 38, 45 and 46 AA, respectively, could be tentatively identified. Afterwards, seven AA were successfully quantified in the samples. Of these, 4-ethylaniline (4EA, p = 0.015), 2,4,6-trimethylaniline (2,4,6TMA, p = 0.030), 2-naphthylamine (2NA, p = 0.014) and the sum of 2,4- and 2,6-dimethylaniline (DMA, p = 0.017) were found in significantly different (α = 0.05) concentrations for the S, 29 ± 14, 87 ± 49, 41 ± 26, and 105 ± 57 ng/L respectively, compared to the NS, 15 ± 6, 42 ± 30, 16 ± 6, and 48 ± 28 ng/L. And 2,4,6TMA (39 ± 26, p = 0.022), 2NA (18 ± 9, p = 0.025) and DMA (53 ± 46, p = 0.030), were also found at significantly higher concentrations in samples from S when compared to PS. However, some samples had AA concentrations outside the calibration curve and could not be taken into account, especially for 2-methylaniline (2MA). Therefore, all the samples were evaluated using a quantitative screening approach, by which the intensities of 4EA (p = 0.019), 2,4,6TMA (p = 0.048), 2NA (p = 0.016), DMA (p = 0.019) and 2MA (p = 0.006) in S were found to be significantly (α = 0.05) higher than in the NS, and 2MA (p = 0.019) and 4EA (p = 0.023) in S were found to be significantly higher than in the PS. An association between the smoking status and the amount of certain AA present could therefore be found. This information could be used to study the relation between the smoking status, the amount of AA present, and smoking related diseases like bladder cancer.

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Coppa Piacentina is an Italian protected designation of origin (PDO) dry-cured product obtained from the muscle of pork neck and ripened for at least six months. Metabolomics- and volatilomics-based strategies, combined with a chemical characterization of free amino acids were applied to identify biomarkers of long-ripened Coppa Piacentina PDO. Long ripening induced a significantly increase of total free amino acids, mainly represented by glutamic acid, involved in the umami taste perception. Untargeted metabolomics, performed using UHPLC-HRMS, allowed to identify 32 putative gamma-glutamyl-peptides, known as main contributors to the kokumi taste. Unsupervised and supervised multivariate statistics observed a clear modification of these peptides over the ripening, with gamma-glutamyl-peptides which significantly increased in long-ripened samples. A volatilomics-based strategy, conducted with GCxGC-MS, was then performed, and 93 different compounds were identified, with aldehyde and ketones deriving from the lipid auto-oxidation which increased according to ripening.

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Food supplement authentication is an important concern worldwide due to the ascending consumption related to health benefits and its lack of effective regulation in underdeveloped countries, making it a target of fraudulent activities. In this context, this study evaluated fish oil supplements by comprehensive two-dimensional gas chromatography coupled to mass spectrometry (GC×GC-MS) to obtain fingerprints, which were used to build predictive models for automated authentication of the most popular products sold in Brazil. The authentication process relied on a one-class classifier model using data-driven soft independent modeling of class analogy (DD-SIMCA). The output of the model was a binary classifier: certified IFOS fish oils and non-certified ones - regardless of the source of adulteration. The compositional analysis showed a significant variation in the samples, which validated the need for reliable statistical models. The DD-SIMCA algorithm is still incipient in GC×GC studies, but it proved to be an excellent tool for authenticity purposes, achieving a chemometric model with a sensitivity of 100%, specificity of 98.6%, and accuracy of 99.0% for fish oil authentication. Finally, orthogonalized partial least square discriminant analysis (OPLS-DA) was used to identify the features that distinguished the groups, which ascertained the results of the DD-SIMCA model that IFOS-certified oils are positively correlated to omega-3 fatty acids, including eicosapentaenoic acid (EPA, C20:5 n-3) and docosahexaenoic acid (DHA, C22:6 n-3).

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A step-by-step approach to easily adapt and use a GC-FID as an olfactometer, as well as a detailed description of acquisition and interpretation of olfactometric data by the OSME (from the Greek word for odor, ὀσµÎ®) method. A Merlot wine was used to exemplifly this strategy and its volatiles were characterized, rendering 43 volatiles in 1D-GC/MS and 142 in GCxGC/MS. GC-O showed the presence of 24 odor-active compounds and GCxGC/MS indicated aditional 14 odor-active compounds, which were found as coelutions. Six compounds (isoamyl acetate, ethyl octanoate, ethyl decanoate, 3-methylthio-1-propanol, carvone, benzyl alcohol and nonanoic acid) were described in 1D-GC-O analyses as having distinct odors by the same and by different assessors. This fact indicated the presence of coeluting bands, which were resolved by GCxGC/MS. The adapted GC-O in combination with the use of GCxGC/MS may be a tool to more accurate investigation of the odor-active compounds of wine.

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Infection from severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) can lead to severe respiratory tract damage and acute lung injury. Therefore, it is crucial to study breath-associated biofluids not only to investigate the breath's biochemical changes caused by SARS-CoV-2 infection, but also to discover potential biomarkers for the development of new diagnostic tools. In the present study, we performed an untargeted metabolomics approach using a bidimensional gas chromatography mass spectrometer (GCxGC-TOFMS) on exhaled breath condensate (EBC) from COVID-19 patients and negative healthy subjects to identify new potential biomarkers for the noninvasive diagnosis and monitoring of the COVID-19 disease. The EBC analysis was further performed in patients with acute or acute-on-chronic cardiopulmonary edema (CPE) to assess the reliability of the identified biomarkers. Our findings demonstrated that an abundance of EBC fatty acids can be used to discriminate COVID-19 patients and that they may have a protective effect, thus suggesting their potential use as a preventive strategy against the infection.

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A new approach based on online pyrolysis-comprehensive gas chromatography/mass spectrometry (Py-GCxGC/MS) is introduced for analysis of lacquer saps with potential applications to analysis of Asian lacquers. The bidimensional GCxGC separation demonstrated its benefits for characterization of the markers of lacquer saps, alkylhydrocarbons, alkylbenzenes, alkylphenols, and alkylcatechols, in a visual way not attainable in monodimensional Py-GC/MS analysis. Moreover, the potentiality offered by GCxGC allows the separation of regioisomers difficult to obtain with a monodimensional separation. Under these circumstances, urushiol (Japanese, Chinese), laccol (Vietnamese), and thitsiol (Myanmar) lacquer sap films were differentiated by their marker fingerprints with a limit of detection in the low µg range. Additionally, thermally assisted pyrolysis with tetramethylammonium hydroxyde (TMAH) clearly differentiated the alkylcatechol markers of the four lacquer samples investigated, with a net separation of stereoisomers particularly well exemplified in the case of the Myanmar lacquer sample. The proposed Py-GCxGC/MS approach greatly facilitates the analysis of Asian lacquer saps, and is very promising for sensitive detection of lacquers in archaeological artifacts.

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We explored the use of pulsed flow modulation (PFM) two-dimensional comprehensive gas chromatography (GCxGC) mass spectrometry with supersonic molecular beams (SMB) (also named Cold electron ionization (EI)) for achieving universal pesticide analysis in agricultural products. The use of GCxGC serves as an alternative to MS-MS in the needed reduction of matrix interference while enabling full-scan MS operation for universal pesticide analysis with reduced number of false negatives. Matrix interference is further reduced with Cold EI in view of the enhancement of the molecular ions. Pulsed flow modulation is a simple GCxGC modulator that does not consume cryogenic gases while providing tuneable second GCxGC column injection time for enabling the use of quadrupole-based mass spectrometry regardless its limited scanning speed. PFM-GCxGC-MS with Cold EI combines improved separation of GCxGC with Cold EI benefits of tailing-free ultra-fast ion source response time and enhanced molecular ions for the provision of increased sample identification information and reduced matrix interference. Consequently, PFM GCxGC-MS with Cold EI also improved NIST library identification probabilities of the spiked pesticides. PFM GCxGC is further characterized by largely increased second column sample and matrix capacity that as a result performs much better than thermal modulation GCxGC-MS with standard EI in the suppression of matrix interference. In a comparison with standard GC-MS, we measured with PFM GCxGC-MS with Cold EI an average total ion count matrix interference reduction factor of 32 for 12 pesticides in two matrices of baby leaves mixture and lettuce. In addition, Cold EI further increases the range of pesticides amenable for GC-MS analysis and its response is relatively uniform hence with it the need for pesticides specific calibration is reduced. Graphical abstract Pulsed flow modulation GCxGC-MS with Cold EI significantly reduces matrix interference and improves sample identification.

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We have analyzed the chemical variety obtained by Miller-Urey-type experiments using nuclear magnetic resonance (NMR) spectroscopy and coherent anti-Stokes Raman scattering (CARS) spectroscopy, gas chromatography followed by mass spectrometry (GC/MS) and two-dimensional gas chromatography followed by mass spectrometry (GCxGC/MS). In the course of a running Miller-Urey-type experiment, a hydrophobic organic layer emerged besides the hydrophilic aqueous phase and the gaseous phase that were initially present. The gas phase mainly consisted of aromatic compounds and molecules containing C≡C or C≡N triple bonds. The hydrophilic phase contained at least a few thousands of different molecules, primarily distributed in a range of 50 and 500 Da. The hydrophobic phase is characterized by carbon-rich, oil-like compounds and their amphiphilic derivatives containing oxygen with tensioactive properties. The presence of a wide range of oxidized molecules hints to the availability of oxygen radicals. We suggest that they intervene in the formation of alkylated polyethylene glycol (PEG) in the oil/water interface. CARS spectroscopy revealed distinct vibrational molecular signatures. In particular, characteristic spectral bands for cyanide compounds were observed if the broth was prepared with electric discharges in the gaseous phase. The characteristic spectral bands were absent if discharges were released onto the water surface. NMR spectroscopy on the same set of samples independently confirmed the observation. In addition, NMR spectroscopy revealed overall high chemical variability that suggests strong non-linearities due to interdependent, sequential reaction steps.

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Polar organic compounds found in industrial process waters, particularly those originating from biodegraded petroleum residues, include 'naphthenic acids' (NA). Some NA have been shown to have acute toxicity to fish and also to produce sub-lethal effects. Whilst some of these toxic effects are produced by identifiable carboxylic acids, acids such as sulphur-containing acids, which have been detected, but not yet identified, may produce others. Therefore, in the present study, the sulphur-containing acids in oil sands process water were studied. A fraction (ca 12% by weight of the total NA containing ca 1.5% weight sulphur) was obtained by elution of methylated NA through an argentation solid phase extraction column with diethyl ether. This was examined by multidimensional comprehensive gas chromatography-mass spectrometry (GCxGC-MS) in both nominal and high resolution mass accuracy modes and by GCxGC-sulphur chemiluminescence detection (GCxGC-SCD). Interpretation of the mass spectra and retention behaviour of methyl esters of several synthesised sulphur acids and the unknowns allowed delimitation of the structures, but not complete identification. Diaromatic sulphur-containing alkanoic acids were suggested. Computer modelling of the toxicities of some of the possible acids suggested they would have similar toxicities to one another and to dehydroabietic acid. However, the sulphur-rich fraction was not toxic or estrogenic to trout hepatocytes, suggesting the concentrations of sulphur acids in this sample were too low to produce any such effects in vitro. Further samples should probably be examined for these compounds.

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