Search Results (97)

Amino acids (AAs), a type of nitrogen-based organic compounds in the atmosphere, are directly and indirectly related to climate change, and as their link to allergic diseases becomes more known, the need for quantitative analysis of ultrafine dust (PM_2.5) will become increasingly necessary. When sensing water-soluble AAs using a gas chromatograph combined with a tandem mass spectrometer (GC-MS/MS), derivatization should be considered to increase the volatility and sensitivity of target analytes. In this study, two methods were used to compare and evaluate 13 AA derivatives in PM_2.5 samples: N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide with 1% tert-butyldimethylchlorosilane (MTBSTFA w/1% t-BDMCS), which is preferred for silylation, and ethyl chloroformate (ECF) with methanol (MeOH) for chloroformate derivatization. The most appropriate reaction conditions for these two derivative methods, such as temperature and time, and the analytical conditions of GC-MS/MS for the qualitative and quantitative analysis of AAs were optimized. Furthermore, the calibration curve, detection limit, and recovery of both methods for validating the quantification were determined. The two derivative methods were applied to 23 actual PM_2.5 samples to detect and quantify target AAs. The statistical significances between pairwise measurements of individual AAs detected by both methods were evaluated. This study will help in selecting and utilizing appropriate derivative methods for the quantification of individual AAs in PM_2.5 samples. Full article

Volatile organic compounds (VOCs) in urine headspace are potential biomarkers for different medical conditions, as canines can detect human diseases simply by smelling VOCs. Because dogs can detect disease-specific VOCs, gas chromatography–mass spectrometry (GC–MS) systems may be able to differentiate medical conditions with enhanced accuracy and precision, given they have unprecedented efficiency in separating, quantifying, and identifying VOCs in urine. Advancements in instrumentation have permitted the development of portable GC–MS systems that analyze VOCs at the point of care, but these are designed for environmental monitoring, emergency response, and manufacturing/processing. The purpose of this study is to repurpose the HAPSITE^® ER portable GC–MS for identifying urinary VOC biomarkers. Method development focused on optimizing sample preparation, off-column conditions, and instrumental parameters that may affect performance. Once standardized, the method was used to analyze a urine standard (n = 10) to characterize intra-day reproducibility. To characterize inter-day performance, n = 3 samples each from three volunteers (and the standard) were analyzed each day for a total of four days (n = 48 samples). Results showed the method could detect VOC signals with adequate reproducibility and distinguish VOC profiles from different volunteers with 100% accuracy. Full article

Artisanal kefir is produced by fermenting milk with kefir grains, resulting in a lightly carbonated drink with health-promoting bioactive compounds. However, sensory variability and fermentation conditions challenge its standardization, limiting commercialization in Brazil due to regulatory requirements. This study evaluated the physicochemical properties, volatile compounds, and microbiological stability of artisanal kefir produced in southern Brazil during 30 days of storage. Metabarcoding analysis, carried out by sequencing the V3/V4 regions of the 16S rRNA gene (bacteria) and the ITS region (fungi), revealed an increase in bacterial diversity, with a predominance of Enterococcus and Acetobacter, while fungal diversity decreased, with a predominance of Kazachstania. The physicochemical parameters remained stable. The concentration of volatile compounds, analyzed using a gas chromatograph coupled to a mass spectrometer, decreased, except for an increase in 2-heptanol. The aromatic profile was enriched with alcohols and ketones, possibly influenced by Enterococcus and Acetobacter. These findings show that kefir maintained microbiological stability and adequate sensory characteristics throughout the period analyzed. The study provides subsidies for the standardization of artisanal kefir and compliance with Brazilian quality standards, as well as guiding future research into durability, quality, and consumer perception. Full article

Brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA) and dibromoneopentyl glycol (DBNPG), are present in both saturated and unsaturated polyester resins (UPRs). Given their toxicity, it is imperative to assess the content of this group of chemicals to ensure product safety and environmental sustainability, considering the paucity in the literature of analytical methods to evaluate them, particularly in solid matrices as UPRs. This study aimed to develop a fully automated gas chromatographic analysis of these BFRs, utilizing a flame ionization detector (FID), with prior derivatization of TBBPA and DBNPG with acetic anhydride. A chemometric evaluation was conducted for the derivatization step to enhance the yield of the procedure. The optimized method met the desired requirements for specificity, accuracy, and sensitivity, showing limits of detection (LOD) and quantitation (LOQ), respectively, of 1.1 µg/mL and 3.3 µg/mL for DBNPG and 3.6 µg/mL and 10.8 µg/mL for TBBPA. Other conventional detectors, i.e., an Electron Capture Detector (ECD) and a Mass Spectrometer (MS), were tested. The ECD showed a higher sensitivity than the FID and MS; however, its linearity proved to be more limited, making it unsuitable for higher concentration scenarios. The MS detector yielded results comparable with those of the FID, yet the latter is a cheaper and more sensitive alternative. Full article

Citrus x limonia is an aromatic species belonging to the Rutaceae family. In the present study, the chemical composition, enantiomeric distribution, and biological activity of the essential oil isolated from leaves of Citrus x limonia were determined. The essential oil was extracted through hydrodistillation. The chemical composition of the essential oil was determined by gas chromatography (GC) coupled to a flame ionization detector (GC-FID), and a mass spectrometer detector (GC-MS) using a nonpolar column. The enantiomeric distribution was performed using two enantioselective chromatographic columns. Antimicrobial activity was determined using the broth microdilution method. The antimicrobial activity was tested against eight bacteria and two fungi. The antioxidant activity was determined through ABTS and DPPH methods. The spectrophotometric method was used to determine anticholinesterase activity. In the essential oil, forty-three compounds were identified. These compounds represent 99.13% of the total composition. Monoterpene hydrocarbons were the most representative group in number of compounds (fourteen) and in terms of relative abundance (65.67%). The main constituent is found to be limonene (25.37 ± 0.80%), β-pinene (23.29 ± 0.15%) and sabinene (8.35 ± 0.10%). Six pairs of enantiomers were identified in the essential oil from fruits of Citrus x limonia. The essential oil showed moderate antibacterial activity against Gram-positive cocci Enterococcus faecalis, and Gram-positive bacillus Lysteria monocytogenes with a MIC of 1000 μg/mL. The oil exhibited strong antifungal activity against fungi Aspergillus niger, and yeasts Candida albicans with a MIC of 250 and 500 μg/mL, respectively. The antioxidant activity of essential oil was weak in ABTS method with a SC₅₀ of 9.12 mg/mL. Additionally, the essential oil presented moderate anticholinesterase activity with an IC₅₀ of 71.02 ± 1.02 µg/mL. Full article

The course and kinetics of the reactions of sulfur mustard, nitrogen mustard and their selected analogues with sodium ethoxide were studied using a gas chromatograph coupled with a mass spectrometer. 2-chloroethyl ethyl sulfide (CEES), a monofunctional analogue of sulfur mustard (HD), bis(2-chloroethyl) ether (BCEE), an oxygen analogue of sulfur mustard, and bis(2-chloroethyl)amine, an analogue of nitrogen mustard HN-3, in which one hydrogen atom remains unsubstituted with a chloroethyl group, were used as imitators of mustards. For the study, the last mentioned compound was given the acronym HN-0. The research included checking how the form of sodium ethoxide influences the reaction rate. Two solutions were used: sodium ethoxide solution obtained by dissolving a commercially available compound in crystalline form and ethoxide solution obtained by dissolving sodium in ethanol. Additionally, the extent to which diethylenetriamine (DETA) accelerates the reactions of the studied compounds with sodium ethoxide was checked. The decontamination reactions were carried out in an anhydrous environment at a constant temperature of 25.0 °C. The rate of the mustard decontamination reaction increased significantly in systems containing DETA. Therefore, this amine can be used as a catalyst for this reaction. DETA has the most significant effect on the rate of the reaction of sodium ethoxide with CEES. The effect of the EtONa form was tested in the decontamination reaction of HD, revealing that both forms are equally effective, with only minor differences in reaction rates. Freshly synthesised sodium ethoxide reacts with HD 1.24 times faster. The study also assessed whether selected non-CWA compounds can be successfully used in studies as mustard imitators. Nitrogen mustard and bis(2-chloroethyl)amine reactions proceed according to the same mechanism—nucleophilic substitution. Bis(2-chloroethyl)amine reacts slightly faster than HN-3, both in solution with and without the addition of a catalyst. Sulfur mustard (HD) and CEES with sodium ethoxide and DETA undergo an elimination reaction, while BCEE undergoes a substitution reaction, which proceeds much slower. The observed differences disqualify BCEE as a sulfur mustard imitator. HD and CEES react with sodium ethoxide and DETA so quickly that the exact kinetic parameters under the developed experimental conditions could not be determined. Full article

The use of essential oils from certain herbal plants offers a promising alternative to synthetic insecticides for controlling the maize weevil, Sitophilus zeamais Motschulsky (Coleoptera: Dryophthoridae), a major pest that causes significant damage to stored grains. Essential oils, particularly from aromatic herbs in the Apiaceae family, are widely used in medicinal, cosmetic, and food industries and provided insecticidal properties to mitigate the environmental and health hazards associated with synthetic insecticides. This research aimed to investigate the insecticidal and repellent effects of Apium graveolens L. (celery) seed essential oil against S. zeamais. Chemical analysis of the commercially produced essential oil from A. graveolens seeds was conducted using a gas chromatograph–mass spectrometer (GC-MS), and the biological activity of the essential oil was determined by ingestion, contact, fumigation, and repellent tests. The analysis identified D-limonene (64.21%) and α-humulene (17.46%) as primary components of the oil. Toxicity assays revealed an observable contact toxicity, with higher concentrations and prolonged exposure increasing its effectiveness. The contact toxicity assays reported an LC₅₀ of 19.83 nL/adult after 72 h. Additionally, the essential oil displayed repellent effects, effectively deterring weevils at concentrations above 16 µL/L air, but its feeding deterrence was weak. The essential oil’s strong insecticidal and repellent properties, which were concentration- and time-dependent, highlighted its potential as a sustainable alternative to synthetic pesticides for integrated pest management. Full article

The expansion of atmospheric observation networks for hydrofluorocarbons (HFCs), which are closely related to climate change and contribute to global warming, significantly impacts our society and daily life. Their emissions are estimated to increase in the future, which is a major challenge. Observations of HFCs globally were performed using expensive GHG–specific equipment installed at AGAGE and other sites, but many research institutions find it difficult to install such equipment. Therefore, we successfully developed a measurement method for six components of HFCs (HFC–23, HFC–32, HFC–125, HFC–134a, HFC–143a, and HFC–152a) with high atmospheric concentrations in various parts of the world by optimizing measurement parameters such as the sample transfer volume and rate, module cooling temperatures, the injection time, the GC oven temperature program, and the monitored ions of a commercially available preconcentrator–GC–MS. Because this developed measurement method is cost–effective and simpler to operate than those of GHG–specific equipment, it is expected to provide an opportunity for many research institutes to measure HFCs. Furthermore, in addition to HFCs, we confirmed that simultaneous measurements can be performed for 97 volatile organic compounds (VOCs), including hazardous components. This research can contribute to the observation of HFCs in countries and regions where the actual status of emissions is unclear or where no or few atmospheric observations were conducted. The results of those observations can be used to formulate more detailed global warming countermeasures. Full article

Mass spectrometry (MS) is the only instrumental analytical technology that utilizes unique properties of matter, that is, its mass (m) and electrical charge (z). In the magnetic and/or electric fields of mass spectrometers, electrically charged native or chemically modified (millions) endogenous and (thousands) exogenous substances, the analytes, are separated according to their characteristic mass-to-charge ratio (m/z) values. Mass spectrometers coupled to gas chromatographs (GC) or liquid chromatographs (LC), the so-called hyphenated techniques, i.e., GC-MS and LC-MS, respectively, enable reliable determination of the concentration of analytes in complex biological samples such as plasma, serum, and urine. A particular technology is represented by inductively coupled plasma-mass spectrometry (ICP-MS), which is mainly used for the analysis of metal ions. The highest analytical accuracy is reached by using mass spectrometers with high mass resolution (HR) or by tandem mass spectrometers, as it can be realized with quadrupole-type instruments, such as GC-MS/MS and LC-MS/MS, in combination with stable-isotope labeled analytes that serve as internal standards, like a standard weight in scales. GC-MS belongs to the oldest and most advanced instrumental analytical technology. From the very beginning, GC-MS found broad application in basic and applied research sciences. GC-MS has played important roles in discovering biochemical pathways, exploring underlying mechanisms of disease, and establishing new evidence-based pharmacological therapy. In this article, we make an inventory of the use of instrumental mass spectrometry in the life sciences and attempt to provide a perspective study on the future of analytical mass spectrometry in clinical science, mainly focusing on GC-MS and LC-MS. We used information freely available in the scientific database PubMed (retrieved in August–November 2024). Specific search terms such as GC-MS (103,000 articles), LC-MS (113,000 articles), and ICP-MS (14,000 articles) were used in the Title/Abstract in the “PubMed Advanced Search Builder” including filters such as search period (1970–2024). In total, around 103,000 articles on GC-MS, 113,000 articles on LC-MS (113,000), and 14,000 articles on ICP-MS were found. In the period 1995–2023, the yearly publication rate accounted for 3042 for GC-MS articles and 3908 for LC-MS articles (LC-MS/GC-MS ratio, 1.3:1). Our study reveals that GC-MS/MS, LC-MS/MS, and their high-resolution variants are indispensable instrumentations in clinical science including clinical pharmacology, internal and forensic medicine, and doping control. Long-tradition manufacturers of analytical instruments continue to provide increasingly customer-friendly GC-MS and LC-MS apparatus, enabling fulfillment of current requirements and needs in the life sciences. Quantitative GC-MS and GC-MS/MS methods are expected to be used worldwide hand in hand with LC-MS/MS, with ICP-MS closing the gap left for metal ions. The significance of analytical chemistry in clinical science in academia and industry is essential. Full article

This study deals with the separation and detection methods for 12 synthetic musk compounds (SMCs), which are some of the emerging contaminants in fish samples, are widely present in environmental media, and can be considered serious risks due to their harmful effects. For the separation of co-extracted substances and the target SMCs in fish samples after ultrasonic extraction, four solid-phase extraction (SPE) sorbents were investigated. The recoveries of SMCs from 10 mL of eluent, as optimized by the elution profile, were within the acceptable range of 80–120% in all SPE types, and it was found that nitro musk and polycyclic musk compounds were separated more clearly in Florisil SPE than others (Aminopropyl, Alumina-N, PSA). Furthermore, the results of measuring the matrix effects by each SPE through the spiking experiments showed that Florisil SPE was superior. The comparison of a gas chromatograph-single quadrupole mass spectrometer (GC-SQ/MS) with selected ion monitoring (SIM) mode and GC-triple quadrupole mass spectrometer (GC-QqQ-MS/MS) with multiple reaction monitoring (MRM) modes regarding the detection method of SMCs showed that the method detection limits (MDLs) of SMCs were on average ten times lower when GC-QqQ-MS/MS with MRM mode was used. The differences between the two methods can provide essential information for selecting an analytical method in related research fields that require appropriate detection levels, such as risk assessment or pollution control. Full article

One of the still-debated topics regarding the olfactory function concerns the presence or absence of sex-related differences in individuals. In this study, we checked for a relationship between the olfactory function of females and males and their ability to perceive single molecules, and researched how this can influence the intensity with which the complex odor formed by a set of single molecules is perceived. First, females and males were classified as normosmic or hyposmic based on the TDI olfactory score obtained using the Sniffin’ Sticks test. Subsequently, the headspace of roasted coffee beans, as a complex olfactory stimulus, was broken down into single molecules by means of a chromatographic column; these were simultaneously conveyed to a mass spectrometer (for their subsequent classification) and to the human nose, which acts as a chemical sensor by means of an olfactometer port. The results obtained with this gas chromatography–olfactometry approach show both qualitative and quantitative differences between females and males, with females performing better than males. In addition, the odor intensity reported by females when sniffing pen #10, containing coffee aroma, is significantly higher than that reported by males. In conclusion, these data highlight that the human ability to perceive both single compounds and complex odors is strongly conditioned, not only by the olfactory function of individuals, but also by their sex. Full article

The interactions between plants and rhizosphere microbes mediated by plant root exudates are increasingly being investigated. The root-derived metabolites of medicinal plants are relatively diverse and have unique characteristics. However, whether medicinal plants influence their rhizosphere microbial community remains unknown. How medicinal plant species drive rhizosphere microbial community changes should be clarified. In this study involving high-throughput sequencing of rhizosphere microbes and an analysis of root exudates using a gas chromatograph coupled with a time-of-flight mass spectrometer, we revealed that the root exudate metabolites and microorganisms differed among the rhizosphere soils of five medicinal plants. Moreover, the results of a correlation analysis indicated that bacterial and fungal profiles in the rhizosphere soils of the five medicinal plants were extremely significantly or significantly affected by 10 root-associated metabolites. Furthermore, among the 10 root exudate metabolites, two (carvone and zymosterol) had opposite effects on rhizosphere bacteria and fungi. Our study findings suggest that plant-derived exudates modulate changes to rhizosphere microbial communities. Full article

Background: Fatty acids are essential for human health. Currently, there is a search for alternative sources of fatty acids that could supplement such sources as staple crops or fishes. Turions of aquatic plants accumulate a variety of substances such as starch, free sugars, amino acids, reserve proteins and lipids. Our aim is to see if turions can be a valuable source of fatty acids. Methods: Overwintering shoots and turions of aquatic carnivorous plants were collected. The plant material was extracted with hexane. The oils were analyzed using a gas chromatograph with mass spectrometer. Results: The dominant compound in all samples was linolenic acid. The oil content was different in turions and shoots. The oil content of the shoots was higher than that of the turions, but the proportion of fatty acids in the oils from the shoots was low in contrast to the oils from the turions. The turions of Utricularia species were shown to be composed of about 50% fatty acids. Conclusions: The turions of Utricularia species can be used to obtain oil with unsaturated fatty acids. In addition, the high fatty acid content of turions may explain their ability to survive at low temperatures. Full article

In this work, a novel, silicon-based micro-electromechanical valve that includes a submicrometric orifice and can operate at pressure gradients of 1 bar was used to enhance sampling for gas chromatograph mass spectrometers. The valve is based on a membrane-in-membrane design and operates with thermomechanical actuation. It includes a pin to enable self-cleaning. Prototypes were fabricated and preliminary testing was performed. Full article

The correlation between a gas sensor pattern and its corresponding odor impression on human noses remains a scientific challenge for the development of technical odor detection systems. Small, inexpensive gas sensors, for example, those based on a metal oxide semiconductor (MOS), offer a versatile platform for the development of application-specific sensor systems for odor detection or monitoring. The training of MOS sensors for odor detection remains a challenging task that has been addressed by recent advances. We hereby present a comprehensive method and instrumentation for the characterization and validation of MOS sensors using a gas chromatograph with a mass spectrometer and odor detection port. Full article