Development of In-Needle SPME Devices for Microextraction Applied to the Quantification of Pesticides in Agricultural Water.

The chemical industry explosion in the 20th century has led to increased environmental pollution, affecting fauna, flora, and waterways. These substances alter water's taste, color, and smell, making it unfit for consumption or toxic. Agricultural water networks face threats from pollution before and after treatment. Some chemical contaminants, like pesticides, are embedded in natural biogeochemical cycles. In this study, we developed a simple and low-cost procedure for the fabrication of needles coated with polydimethylsiloxane (PDMS) as an efficient sorbent for the microextraction of organic pollutant traces from water. The prepared needles were used as an alternative for commercial solid-phase micro-extraction (SPME) devices in analytical chemistry. The PDMS polymeric phase was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The PDMS-coated needles were used for extraction of thirteen pesticides by direct-immersion solid-phase microextraction (DI-SPME) from contaminated waters, followed by determination with gas chromatography-mass spectrometry (GC-MS). The developed analytical method showed limits of detection (LODs) between 0.3 and 2.5 ng mL-1 and RSDs in the range of 0.8-12.2%. The homemade needles were applied for the extraction of pesticides in surface and ground aqueous samples collected from an agricultural area. Several target pesticides were identified and quantified in the investigated water samples.

[The study of the features of the determination and nature of the localization of 2-amino-4.6-dinitrophenol in the body of warm-blooded animals in case of lethal poisoning]. / Izuchenie osobennostei opredeleniya i kharaktera lokalizatsii 2-amino-4,6-dinitrofenola v organizme teplokrovnykh pri letal'nykh otravleniyakh.

The aim of the work is to study the nature of the distribution of 2-A-4.6-DNP in the organisms of warm-blooded animals with intragastric administration of a toxicant. The study was carried out using the methods of TLC, UV-Visible spectroscopy, and GC-MS using derivatives of 2-A-4.6-DNP. Male Wistar rats at the age of 4 months were considered as a model of the body of a warm-blooded animal. An oily suspension of 2-A-4.6-DNF was administered intragastrically in an amount of three times the LD50. Extraction of the target substance from the biomaterial was carried out by double infusion (30 minutes each) with a mixture of acetone-acetonitrile (1:1), the amount of the mixture exceeded the weight of the biomaterial by 2 times. Extractions were purified by TLC method using «Sorbfil¼ plates and acetone-chloroform (7: 3) mobile phase. Preliminary identification was carried out at the same time using a standard substance. Confirmatory identification was carried out by the absorption of dimethylformamide eluates in «SF-2000¼, as well as by the retention time and mass spectra of the major compound of the corresponding chromatographic peaks after GC-MS analysis. The quantitative content was determined spectrophotometrically, in DMF, by optical density at the analytical wavelength (490 nm). 2-Amino-4.6-dinitrophenol was found unchanged in the blood and in all the studied hollow and parenchymal organs of poisoned rats. The largest amount of 2-amino-4.6-dinitrophenol (mg/100 g) was found in the stomach walls (199.39±25.43) and stomach contents (143.14±22.63), a significant amount of the substance was found in the heart (33.49±3.66), skeletal muscles (30.70±2.64), as well as in the spleen (24.30±1.96).

A dilute-and-inject liquid-gas chromatography-mass spectrometry method for the analysis of sixteen polycyclic aromatic hydrocarbons in extra-virgin olive oil.

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) represent a diverse group of organic compounds characterized by the fusion of two or more benzene rings arranged in various structural forms. Due to their harmful effects on human health, it is essential to implement monitoring systems and preventive measures to regulate human exposure. Given the affinity of PAHs for lipids, extensive research has been focused on their presence in vegetable oils. This study aimed to develop an on-line liquid-gas chromatography (LC-GC) method (using tandem mass spectrometry) with minimized solvent consumption for the determination of 16 PAHs in extra-virgin olive oil (EVOO). RESULTS: A side-by-side comparison of the selected-ion-monitoring and the pseudo multiple-reaction-monitoring (p-MRM) acquisition modes was performed, in terms of specificity and detectability. The results obtained using the p-MRM mode were superior, and for this reason it was selected. The method was linear over the concentration range 1-200 µg kg-1 (except in five cases, over 2-200 and 5-200 µg kg-1 ranges). Accuracy (at the 2 µg kg-1 and 20 µg kg-1 concentration levels) was in the 86.9-109.3 % range, with an RSD <10 %. Intra-day and inter-day precision (at 2 µg kg-1 and 20 µg kg-1 concentration levels) were in the 1.2-9.7 % and 3.2-10.8 % ranges, respectively. For all the PAHs, a negative matrix effect was observed. Three out of sixteen PAHs were detected in three EVOOs (among ten samples), albeit at the low ppb level. Limits of quantification were satisfactory in relation to EU legislation on the presence of PAHs in vegetable oils. SIGNIFICANCE: A dilute-and-inject LC-GC-tandem mass spectrometry method is herein proposed fulfilling EU legislation requirements; sample preparation was very simple, inasmuch that it involved only a dilution step, thus avoiding extraction, clean-up, and thus a high consumption of organic solvents. In fact, considering both oil dilution and the LC mobile phase, less than 8 mL of solvents were used.

Gas Chromatography-Mass Spectrometry Metabolites and Transcriptome Profiling Reveal Molecular Mechanisms and Differences in Terpene Biosynthesis in Two Torrya grandis Cultivars during Postharvest Ripening.

Terpene aroma compounds are key quality attributes of postharvest Torreya grandis nuts, contributing to their commercial value. However, terpene biosynthesis and regulatory networks in different T. grandis cvs. are still poorly understood. Here, chief cvs. 'Xi Fei' and 'Xiangya Fei' were investigated for their differences in terpene biosynthesis and gene expression levels during postharvest ripening using headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) and transcriptomic datasets. A total of 28 and 22 aroma compounds were identified in 'Xi Fei' and 'Xiangya Fei', respectively. Interestingly, differences in aroma composition between the two cvs. were mostly attributed to D-limonene and α-pinene levels as key determinants in Torreya nuts' flavor. Further, transcriptome profiling, correlation analysis, and RT-qPCR annotated two novel genes, TgTPS1 in 'Xi Fei' and TgTPS2 in 'Xiangya Fei', involved in terpene biosynthesis. In addition, six transcription factors (TFs) with comparable expression patterns to TgTPS1 and four TFs to TgTPS2 were identified via correlation analysis of a volatile and transcriptome dataset to be involved in terpene biosynthesis. Our study provides novel insight into terpene biosynthesis and its regulation at the molecular level in T. grandis nut and presents a valuable reference for metabolic engineering and aroma improvement in this less explored nut.

Gas Chromatography-Mass Spectrometry Metabolite Analysis Combined with Transcriptomics Reveals Genes Involved in Wax Biosynthesis in Allium fistulosum L.

Cuticular waxes are essential for protecting plants from various environmental stresses. Allium fistulosum serves as an excellent model for investigating the regulatory mechanisms underlying cuticular wax synthesis with notable epidermal wax characteristics. A combination of gas chromatography-mass spectrometry (GC-MS) metabolite analysis and transcriptomics was used to investigate variations in metabolites and gene expression patterns between the wild type (WT) and glossy mutant type (gl2) of A. fistulosum. The WT surface had a large number of acicular and lamellar waxy crystals, whereas the leaf surface of gl2 was essentially devoid of waxy crystals. And the results revealed a significant decrease in the content of 16-hentriacontanone, the principal component of cuticular wax, in the gl2 mutant. Transcriptomic analysis revealed 3084 differentially expressed genes (DEGs) between WT and gl2. Moreover, we identified 12 genes related to fatty acid or wax synthesis. Among these, 10 DEGs were associated with positive regulation of wax synthesis, whereas 2 genes exhibited negative regulatory functions. Furthermore, two of these genes were identified as key regulators through weighted gene co-expression network analysis. Notably, the promoter region of AfisC5G01838 (AfCER1-LIKE1) exhibited a 258-bp insertion upstream of the coding region in gl2 and decreased the transcription of the AfCER1-LIKE1 gene. This study provided insights into the molecular mechanisms governing cuticular wax synthesis in A. fistulosum, laying the foundation for future breeding strategies.

Development and performance of an analytical method for polychlorinated naphthalenes and other persistent organic pollutants in dried blood spots.

BACKGROUND: Dried blood spots (DBSs) collected and archived in newborn screening programs (NSP) represent a potentially valuable resource for assessing exposure to a range of organic and inorganic chemicals in newborns. This study develops and optimizes a method to measure polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs) in DBS using the isotope dilution technique, ultrasonic-assisted liquid-liquid extraction, simple cleanup, triple quadrupole GC-MS/MS analysis, and background correction. RESULTS: We minimize the number of extraction repetitions and the volume of solvent, which helps increase throughput while minimizing the potential for contamination. We obtained high recovery and precision for most compounds, and method detection limits (MDLs) were sufficiently low to detect the more prevalent compounds based on representative sample of the US population. MDLs averaged 0.020 ng/mL (recovery: 107 %, precision: 4 %) for PCNs, 0.021 ng/mL (recovery: 97 %, precision: 4 %) for PCBs, 0.021 ng/mL (recovery: 117 %, precision: 2 %) for OCPs, and 0.021 ng/mL (recovery: 96 %, precision: 3 %) for PBDEs. SIGNIFICANCE AND NOVELTY: To our knowledge, this is the first study presenting an analytical method and for PCNs in DBS, and one of the few studies providing an assessment of method performance for persistent organic pollutants in DBS. The optimized method can be applied to a wide range of applications, including exposure assessment, environmental epidemiology, forensics, environmental surveillance, and ecological monitoring.

Lipidomics profile and volatile compounds of squids (Illex argentinus, Ommastrephes Bartram and Dosidicus gigas) in the Argentine, North Pacific Ocean, Equator and Peru by UPLC-triple TOF-MS and HS-SPME-GC-O-MS.

Comprehensive lipid and volatile compound analyses were performed with squids collected from four varied geographical locations to discriminate the regional characteristics. A total of 1442 lipid molecules and 110 volatiles were detected in the squid muscle samples. There were significant differences in the lipid profiles between Argentine squid (Illex argentinus, AGT), North Pacific Ocean squid (Ommastrephes Bartram, NPO), Equatorial squid (Dosidicus gigas, EQ), and Peruvian squid (Dosidicus gigas, PR) muscle. Phosphatidylcholines (14.64%), triacylglycerols (12.42%), and ceramides (10.97%) were the main lipid components. The contents of polyunsaturated fatty acid in phospholipids and in glycerolipids were 30.35-52.05% and 18.11-25.15%, respectively. The volatiles in squids exhibited significant regional variation; 1-pentanol and 1-octanol, 2-ethyl-1-hexanol and terpinen-4-ol, 2,7-ethyl-1-hexanol, 3-methy-1-butanol and 2-propyl-1-pentanol were identified as characteristic flavor compounds in AGT, NPO, EQ, and PR, respectively. Sphingomyelin, phosphatidylserine, phosphatidylethanolamine, and ceramide were strongly correlated with volatiles in squid muscle. Our study is a reference for the lipid nutritional value and flavor compounds of squids.

Assessing the performance of various sorbents in micro-solid phase extraction cartridges for pesticide residue analysis in feed.

Newly designed micro-solid phase extraction cartridges are now available, reflecting the increasing shift towards laboratory automation, especially in the clean-up step for the analysis of pesticide residues in food and feed. In the present study, the introduction of different sorbents on the newly designed PAL µSPE CTC cartridges was investigated for the removal of matrix interferents and the recovery of pesticides. Eight cartridges containing different sorbent combinations and different amounts were used including EMR-lipid (not activated), Z-sep, chitin, C18, PSA, and GCB. The evaluation of co-extractive removal for each cartridge showed that the optimal choice for removing fatty acids was the cartridges containing PSA and Z-sep as clean-up sorbents. However, the presence of C18 and EMR-lipid was still required for the removal of sterols and tocopherols. Two grams of sample, fish feed (FF) and rapeseed cake (RSC) were extracted using QuEChERS citrate buffer, followed by a freeze-out step. The recoveries and repeatability of QuEChERS using µ-SPE clean-up were evaluated for 216 pesticide residues (112 compounds analyzed by GC-MS/MS and 143 compounds by LC-MS/MS, from which 39 compounds were analyzed using both techniques). The best results, with recovery between 70 and 120% and RSD <20%, were achieved when FF samples were cleaned-up with 15 mg EMR-lipid and 20 mg MgSO4. This was achieved for 94% of GC-amenable compounds and 86% of LC-amenable compounds. In the case of RSC, the best results were seen when samples were cleaned-up with the cartridge containing only 20 mg Z-sep and 20 mg MgSO4. This was achieved for 88% of GC-amenable compounds and 90% of LC-amenable compounds. Although these cartridges yielded optimal results in terms of recovery, their use could require more instrument maintenance, especially for GC-MS/MS, due to the lower removal of co-extractives.

Continuous rotary kiln pyrolysis of cassava plant shoot system and wide speciation of oxygenated and nitrogen-containing compounds in bio-oil by HESI and APPI-Orbitrap MS.

This work proposes the pyrolysis of the cassava plant shoot system biomass and a comprehensive chemical characterization of the resulting bio-oil. The highest yields of liquid products were obtained at 600 °C, with 12.6 % bio-oil (organic fraction), which presented the lowest total acid number of 65.7 mg KOH g-1. The bio-oil produced at 500 °C exhibited the highest total phenolic content of approximately 41 % GAE, confirmed by GC/MS analysis (33.8 % of the total area). FT-Orbitrap MS analysis found hundreds of oxygenated constituents in the bio-oils, belonging to the O2-7 classes, as well as nitrogen compounds from the Ny and OxNy classes. Higher pyrolysis temperatures resulted in more oxygenated phenolics (O4-7) undergoing secondary degradation and deoxygenation reactions, generating O2-3 compounds. Additional classes affected were O3-5N2-3, while O1-2N1 presented more stable compounds. These findings show that cassava bio-oils are promising sources of renewable chemicals.

Evaluation of polypropylene microporous membranes as extraction devices for determination of carcinogenic aromatic amines in smoker urine by GC-MS/MS.

Exposure to tobacco smoke is highly correlated to the incidence of different types of cancer due to various carcinogenic compounds present in such smoke. Aromatic amines, such as 1-naphthylamine (1-NA) and 2-naphthylamine (2-NA), are produced in tobacco burning and are linked to bladder cancer. Miniaturized solid phase extraction techniques, such as microporous membrane solid phase extraction (MMSPE), have shown potential for the extraction of aromatic compounds. In this study, a bioanalytical method for the determination of 1-NA and 2-NA in human urine was developed using polypropylene microporous membranes as a sorptive phase for MMSPE. Urine samples were hydrolyzed with HCl for 1 h at 80 °C, after which pH was adjusted to 10. Ultrasound-assisted MMSPE procedure was optimized by factorial design as follows. To each sample, 750 µL of methanol was added, and ultrasound-assisted MMSPE was conducted for 1 h with four devices containing seven 2 mm polypropylene membrane segments. After extraction, the segments were transferred to 400 µL of hexane, and desorption was conducted for 30 min. Extracts were submitted to a simple and fast microwave-assisted derivatization procedure, by the addition of 10 µL of PFPA and heating at 480 W for 3 min, followed by clean-up with phosphate buffer pH 8.0 and GC-MS/MS analysis. Adequate linearity was obtained for both analytes in a range from 25 to 500 µg L-1, while the multiple reaction monitoring approach provided satisfactory selectivity and specificity. Intra-day (n = 6) and inter-day (n = 5) precision and accuracy were satisfactory, below 15 % and between 85 and 115 %, respectively. Recovery rates found were 91.9 and 58.4 % for 1-NA and 2-NA, respectively, with adequate precision. 1-NA was found in first-hand smokers' urine samples in a concentration range from 20.98 to 89.09 µg in 24 h, while it could be detected in second-hand smoker's urine samples, and 2-NA detected in all first and second-hand smokers' urine samples. The proposed method expands the applicability of low cost MMSPE devices to aromatic amines and biological fluids.

An in-situ versatile screening method for identifying SVOC sources in indoor environments.

Indoor semivolatile organic compounds (SVOCs) pose a substantial threat to human health. However, identifying the sources of these emissions has been challenging owing to the scarcity of convenient and practical on-site methodologies. Herein, a novel method for source screening was proposed using aluminum silicate sampling strips to adsorb SVOCs from the surface air of indoor materials. The adsorbed SVOC levels indicate the emission intensity of these materials into indoor environments. Additionally, compact sampling strips can be readily fixed to any vertical surface using a static sticker, facilitating the characterization of various materials in practical settings. Laboratory-simulated experiments demonstrated the capability of the proposed method to differentiate between source and non-source materials within a 10-cm distance in the same space. In practical scenarios, the primary emission sources identified via this method exhibited a consistent correlation with the contents of the corresponding materials obtained from the traditional solvent-extraction method. As the adsorbed SVOCs were directly transferred to a GC-MS through thermal desorption instead of the solvent-extraction procedure, the proposed method demonstrated several-fold improvements in analytical sensitivity and efficiency. Using this versatile screening technique, some emerging and important SVOC species were identified within specific indoor materials. Eliminating these sources has been demonstrated as an effective approach to mitigate SVOC pollution. Overall, the proposed method offers a powerful tool for managing indoor pollutants and safeguarding human health.

AntDAS-GCMS: A New Comprehensive Data Analysis Platform for GC-MS-Based Untargeted Metabolomics with the Advantage of Addressing the Time Shift Problem.

Over the years, a number of state-of-the-art data analysis tools have been developed to provide a comprehensive analysis of data collected from gas chromatography-mass spectrometry (GC-MS). Unfortunately, the time shift problem remains unsolved in these tools. Here, we developed a novel comprehensive data analysis strategy for GC-MS-based untargeted metabolomics (AntDAS-GCMS) to perform total ion chromatogram peak detection, peak resolution, time shift correction, component registration, statistical analysis, and compound identification. Time shift correction was specifically optimized in this work. The information on mass spectra and elution profiles of compounds was used to search for inherent landmarks within analyzed samples to resolve the time shift problem across samples efficiently and accurately. The performance of our AntDAS-GCMS was comprehensively investigated by using four complex GC-MS data sets with various types of time shift problems. Meanwhile, AntDAS-GCMS was compared with advanced GC-MS data analysis tools and classic time shift correction methods. Results indicated that AntDAS-GCMS could achieve the best performance compared to the other methods.

Comprehensive investigation on the dynamic changes of volatile metabolites in fresh scent green tea during processing by GC-E-Nose, GC-MS, and GC × GC-TOFMS.

Processing technology plays a crucial role in the formation of tea aroma. The dynamic variations in volatile metabolites across different processing stages of fresh scent green tea (FSGT) were meticulously tracked utilizing advanced analytical techniques such as GC-E-Nose, GC-MS, and GC × GC-TOFMS. A total of 244 volatile metabolites were identified by GC-MS and GC × GC-TOFMS, among which 37 volatile compounds were concurrently detected by both methods. Spreading and fixation stages were deemed as pivotal processes for shaping the volatile profiles in FSGT. Notably, linalool, heptanal, 2-pentylfuran, nonanal, ß-myrcene, hexanal, 2-heptanone, pentanal, 1-octen-3-ol, and 1-octanol were highlighted as primary contributors to the aroma profiles of FSGT by combining odor activity value assessment. Furthermore, lipid degradation and glycoside hydrolysis were the main pathways for aroma formation of FSGT. The results not only elucidate the intricate variations in volatile metabolites but also offer valuable insights into enhancing the processing techniques for improved aroma quality of green tea.

A new HS-SPME-GC-MS analytical method to identify and quantify compounds responsible for changes in the volatile profile in five types of meat products during aerobic storage at 4 °C.

Nowadays, it is important to monitor the freshness of meat during storage to protect consumers' health. Volatile organic compounds (VOCs) are responsible for odour and taste of food, and they give an indication about meat quality and freshness. This study had the aim to seek and select potential new markers of meat spoilage through a semi-quantitative analysis in five types of meat (beef, raw and baked ham, pork sausage and chicken) and then to develop a new quantitative analytical method to detect and quantify potential markers on five types of meat simultaneously. Firstly, a new headspace-solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) method was developed to evaluate the volatile profile of five types of meat, preserved at 4 °C for 5 days. Among the 40 compounds identified, 15 were chosen and selected as potential shelf-life markers on the basis of their presence in most of meat samples or/and for their constant increasing/decreasing trend within the sample. Afterwards, a quantitative HS-SPME-GC-MS analytical method was developed to confirm which VOCs can be considered markers of shelf-life for these meat products, stored at 4 °C for 12 days. Some of the compounds analyzed attracted attention as they can be considered markers of shelf-life for at least 4 types of meat: 1-butanol, 3-methylbutanol, 1-hexanol, 2-nonanone, nonanal, 1-octen-3-ol and linalool. In conclusion, in this study a new quantitative HS-SPME-GC-MS analytical method to quantity 15 VOCs in five types of meat was developed and it was demonstrated that some of the compounds quantified can be considered markers of shelf-life for some of the meat products analyzed.

Revisiting gas-chromatography/mass-spectrometry molar response factors for quantitative analysis (FID or TIC) of glycosidic linkages in polysaccharides produced by oral bacterial biofilms.

Methylation analysis was performed on methylated alditol acetate standards and Streptococcus mutans extracellular polymeric substances (EPS) produced from wild-type and Gtf knockout strains (∆GtfB, ∆GtfB, and ∆GtfD). The methylated alditol acetate standards were representative of glycosidic linkages found in S. mutans EPS and were used to calibrate the GC-MS system for an FID detector and MS (TIC) and produce molar response factor, a necessary step in quantitative analysis. FID response factors were consistent with literature values (Sweet et al., 1975) and found to be the superior option for quantitative results, although the TIC response factors now give researchers without access to an FID detector a needed option for molar response factor correction. The GC-MS analysis is then used to deliver the ratio of the linkage types within a biofilm.

Online sequential analysis of volatile and semivolatile organic compounds in water matrices by double robotic sample preparations and dual-channel mono and comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry system.

The monitoring of organic compounds in aquatic matrices poses challenges due to its complexity and time-intensive nature. To address these challenges, we introduce a novel approach utilizing a dual-channel mono (1D) and comprehensive two-dimensional (2D) gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS) system, integrated with a robotic pretreatment platform, for online monitoring of both volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) in water matrices. Employing the robotic platform, we establish a suite of online liquid-liquid extraction (LLE) pretreatment processes for water samples, marking the first instance of such procedures. Leveraging the automatic headspace (HS) module, dual robotic preparations of HS and LLE are sequentially executed to extract VOCs and SVOCs from water matrices. The GC × GC-TOFMS system is distinguished by its dual-channel analytical column configuration, facilitating sequential analysis of VOCs in GC-TOFMS mode and SVOCs in GC × GC-TOFMS mode. Quantitative detection of 55 target VOCs and 104 SVOCs is achieved in a water sample using the instrument system. Our method demonstrates excellent correlation coefficients ranging from 0.990 to 1.000, method detection limits ranging from 0.08 to 4.78 µg L-1, relative standard deviations below 19.3 %, and recovery rates ranging from 50.0 % to 124.0 %. To validate the online monitoring capabilities of our system, we assess target SVOCs at three different concentration levels over a 3-day period. Most compounds exhibit recovery rates ranging from 70.0 % to 130.0 %. Furthermore, we apply our method to analyze a real water sample, successfully identifying over 100 target and nontarget VOCs/SVOCs, including alcohols, aldehydes, ketones, acids, esters, and phenols. These results highlight the efficacy of the proposed analysis system, capable of conducting two distinct analyses in automatic sequence, thereby enhancing the efficiency and accuracy of organic compound analysis in water matrices.

An exploratory metabolomic study reveals the Dipsacus asper-Achyranthes bidentate herb pair against osteoarthritis by modulating imbalance in polyunsaturated fatty acids and energy metabolism.

Osteoarthritis (OA) is a degenerative joint disease primarily affecting the cartilage. The therapeutic potential of the Dipsacus asper-Achyranthes bidentate herb pair for OA has been acknowledged, yet its precise mechanism remains elusive. In this study, we conducted a comprehensive analysis of metabolomic changes and therapeutic outcomes in osteoarthritic rats, employing a gas chromatography-mass spectrometry-based metabolomics approach in conjunction with histopathological and biochemical assessments. The rats were divided into six groups: control, model, positive control, Dipsacus asper treated, Achyranthes bidentata treated, and herb pair treated groups. Compared to the model group, significant reductions in levels of tumor necrosis factor-α (TNF-α), interleukin-1ß (IL-1ß), interleukin-6 (IL-6), and iNOS were observed in the treated groups. Multivariate statistical analyses were employed to investigate metabolite profile changes in serum samples and identify potential biomarkers, revealing 45 differential biomarkers, with eighteen validated using standard substances. These analytes exhibited excellent linearity across a wide concentration range (R2>0.9990), with intra- and inter-day precision RSD values below 4.69% and 4.83%, respectively. Recoveries of the eighteen analytes ranged from 93.97% to 106.59%, with RSD values under 5.72%, underscoring the method's reliability. Treatment with the herbal pair effectively restored levels of unsaturated fatty acids such as linoleic acid and arachidonic acid, along with glucogenic amino acids. Additionally, levels of phosphoric acid and citric acid were reversed, indicating restoration of energy metabolism. Collectively, these findings highlight the utility of metabolomic analysis in evaluating therapeutic efficacy and elucidating the underlying molecular mechanisms of herb pairs in OA treatment.

Exploration of the Lipid Profile of Edible Oleaginous Microgreens by Mass Spectrometry-Based Lipidomics.

The spreading awareness of the health benefits associated with the consumption of plant-based foods is fueling the market of innovative vegetable products, including microgreens, recognized as a promising source of bioactive compounds. To evaluate the potential of oleaginous plant microgreens as a source of bioactive fatty acids, gas chromatography-mass spectrometry was exploited to characterize the total fatty acid content of five microgreens, namely, chia, flax, soy, sunflower, and rapeseed (canola). Chia and flax microgreens appeared as interesting sources of α-linolenic acid (ALA), with total concentrations of 2.6 and 2.9 g/100 g of dried weight (DW), respectively. Based on these amounts, approximately 15% of the ALA daily intake recommended by the European Food Safety Authority can be provided by 100 g of the corresponding fresh products. Flow injection analysis with high-resolution Fourier transform single and tandem mass spectrometry enabled a semi-quantitative profiling of triacylglycerols (TGs) and sterol esters (SEs) in the examined microgreen crops, confirming their role as additional sources of fatty acids like ALA and linoleic acid (LA), along with glycerophospholipids. The highest amounts of TGs and SEs were observed in rapeseed and sunflower microgreens (ca. 50 and 4-5 µmol/g of DW, respectively), followed by flax (ca. 20 and 3 µmol/g DW). TG 54:9, 54:8, and 54:7 prevailed in the case of flax and chia, whereas TG 54:3, 54:4, and 54:5 were the most abundant TGs in the case of rapeseed. ß-Sitosteryl linoleate and linolenate were generally prevailing in the SE profiles, although campesteryl oleate, linoleate, and linolenate exhibited a comparable amount in the case of rapeseed microgreens.

Interference of the gas chromatography- mass spectrometry instrumental background on the determination of trace cyclic volatile methylsiloxanes and exclusion of it by delayed injection.

Cyclic volatile methylsiloxanes (cVMS) have been widely found in various types of environmental media and attracted increasing attention as new pollutants. However, there is still a great challenge in the accurate quantification of trace cVMS, due to their volatility, and the high background originating from GC/MS accessories and surroundings. In this work, the main sources of the high background were investigated in detail for octamethylcyclotetrasiloxane (D4), decmethylcyclopentasiloxane (D5) and dodecmethylcyclohexosiloxane (D6). Several effective measures were employed to minimize these backgrounds, including the delayed injection method to minimize the interference from the injection septum. Then, a GC-MS method was developed for the accurate determination of D4, D5 and D6, with a linear range of 2 - 200 µg/L. The coefficient of determination was 0.9982-0.9986, the limit of detection (LOD) was 0.40-0.52 µg/L, and the quantitative range was 1.88-190 µg/L. Good reproducibility and recovery were obtained, indicating the reliability of the established analytical method.

GC/MS-based untargeted metabolomics reveals the differential metabolites for discriminating vintage of Chenxiang-type baijiu.

The "outstanding and unique aged aroma" of Chinese Chenxiang-type baijiu (CXB)-Daoguang 25 (DG25) mainly originates from a "extraordinary storage technology" of Mujiuhai (a wooden container), so it is mysterious and interesting. In this study, an untargeted GC/MS-based metabolomics was used to reveals the volatile differential metabolites for discriminating six different vintages of DG25 combing with chemometrics. A total of 100 volatile metabolites (including unknowns) were extracted and identified, including esters (41%), alcohols (10%) and acids (7%) so on. Finally, 33 differential metabolites were identified as aging-markers. Among them, 25 aging-markers showed a downtrend, including 17 esters such as ethyl acetate, ethyl hexanoate and ethyl palmitate so on. Moreover, it was interesting and to further study that furans showed a significant downtrend. Statistically speaking, ethyl benzoate played an important role in discriminating vintage of 1Y and 3Y, and the other 24 differential metabolites with downtrend discriminating the unstored (0Y-aged) DG25. Eight differential metabolites, such as ethyl octanoate, benzaldehyde, 3-methylbutanol and 1,1-diethoxyaccetal so on increased during aging of DG25, and they played a statistical role in discriminating the 5Y-, 10Y- and 20Y-aged DG25. This study provides a theoretical basis way for the formation mechanism of aging aroma for CXB.