Gas Chromatography-tandem Mass Spectrometry Research Articles

Doping Control Analysis of Perfluorocarbons in Equine Plasma by Headspace Gas Chromatography-Tandem Mass Spectrometry.

In order to control the potential misuse of perfluorocarbons as an oxygen carrier in equine sports, a simple and sensitive method for detecting perfluorocarbons in equine plasma by gas chromatography/tandem mass spectrometry using negative chemical ionization with methane as reagent gas has been developed and fully validated. The method covers seven perfluorocarbons, which are the active components in blood substitute products, and shows good sensitivity and robustness. Limits of detection as low as 0.01 ng/mL could be achieved by the method. To the best of our knowledge, this is the first report of a detection method for the screening of perfluorocarbons in equine biological samples.

Postmortem distribution of ropivacaine and its metabolite in human body fluids and solid tissues by GC-MS/MS using standard addition method.

An analytical method was developed for determining ropivacaine and its main metabolite, 3-hydroxyropivacaine in biomedical samples using gas chromatography-tandem mass spectrometry (GC-MS/MS). Then, this established method was applied to investigate the distribution of ropivacaine and its metabolite in human fluids and solid tissues obtained from an authentic case ropivacaine involved. The fluid sample was added acetonitrile, and solid tissue was homogenized using a freezer mill and then added into acetonitrile. Then, an internal standard solution was added to the mixtures. The mixture was centrifuged at 12,000 × g for 5min, and the upper layer of acetonitrile was transferred to magnesium sulfate and octadecyl silica (C18) gel for cleaning up the sample. After centrifugation, the upper layer was then evaporated to dryness with nitrogen, and dissolved with methanol, then injected into the GC-MS/MS system. The coefficients of determination (r2) of constructed calibration curves were all greater than 0.999. The limits of detection for ropivacaine and 3-hydroxyropivacaine in target samples were 15ng/mL and 10ng/mL, respectively. The recovery rates of ropivacaine and 3-hydroxyropivacaine ranged from 97.6% to 103% and from 96.5% to 104%, respectively. The inter-day precision values of ropivacaine and 3-hydroxyropivacaine were not greater than 6.25% and 7.98%, respectively, and the inter-day trueness values were not greater than 6.90% and 8.33%, respectively; the intra-day precision and trueness values of ropivacaine and 3-hydroxyropivacaine were not greater than 3.20%, 6.78%, 7.84% and 8.99%, respectively. GC-MS/MS method for simultaneous detection and quantification of ropivacaine and 3-hydroxyropivacaine in biological samples was successfully developed. The method could also be applied to samples obtained from an authentic case; their distribution among tested fluids and solid tissues were also measured. This is the first report on the distribution of ropivacaine and its major metabolite 3-hydroxyropivacaine in a human case.

Investigation of the Thermokinetic and Thermodynamic Parameters of Biodiesel and Associated Oil from Palm Kernel Oil During Thermal Degradation

ABSTRACT This study investigates the kinetic and thermodynamic parameters of the thermal degradation of biodiesel produced from low-grade palm kernel oil. In this work, biodiesel was produced through a two-step transesterification from a palm kernel oil having a free fatty acid content of 5.7%. The first step uses 25% methanol (wt% of palm kernel oil) and 1% sulfuric acid (wt% of palm kernel oil) to reduce the free fatty acids content to 0.3% within 30 min reaction time. In the second step, a methanol-to-oil molar ratio of 6:1 and 0.6% (wt% of palm kernel oil) of KOH yielded a palm kernel oil conversion of 96.96% after 30 min reaction time. The palm kernel biodiesel was analyzed using Fourier Transform Infrared spectroscopy, gas Chromatography tandem mass spectrometry, nuclear magnetic resonance spectroscopy (1H and13C), and thermogravimetric analysis. The thermal stability of palm kernel biodiesel was assessed through the kinetic and thermodynamic parameters of biodiesel thermal decomposition using isoconversional techniques. The Flynn-Wall-Ozawa, Kissinger-Akariha-Sunose, and Starink models were used to evaluate the kinetic parameters, while the Coats and Redfern technique was used to forecast the most probable mechanism of the palm kernel biodiesel thermal degradation. The average activation energies of 108.60 kJ mol−1, 107.75 kJ mol−1 and 95.77 kJ mol−1 using the Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, and Starink methods, respectively. FWO method best described palm kernel oil and biodiesel decomposition, with the highest R2 values of 0.94 for the oil and 0.93 for biodiesel The results obtained from the thermodynamic study (ΔH = 218.48 kJ.mol−1, ΔG = 200.05 kJ.mol−1 and ΔS = 27.10 J.mol−1.K−1) revealed that the biodiesel thermal degradation was an endothermic, non-spontaneous process governed by a three-dimensional diffusion reaction mechanism.

A capsule phase microextraction protocol combined with GC–MS/MS for the determination of polychlorinated biphenyls in water samples

Due to the adverse effects of polychlorinated biphenyls (PCBs) on human health and ecosystems, their careful monitoring is necessary. In this work, capsule phase microextraction (CPME) combined with gas chromatography-tandem mass spectrometry (GC–MS/MS) was used to extract and determine eight PCBs in water samples. As an extraction device for the CPME procedure, two permeable microporous polypropylene tubes were employed. They contained sol–gel carbowax 20 M (sol–gel CW 20 M) sorbent and a cylindrical magnet. The adsorption and desorption conditions (i.e., type of capsule, sample volume, extraction time, stirring rate, ionic strength, type and volume of eluent, and desorption time) of the microextraction procedure were studied. Under optimum conditions, the extraction was achieved within 20 min using 20 mL of sample at a stirring rate of 100 rpm, while the elution was performed by immersing the CPME device in 500 μL of acetone for 5 min. Accordingly, the analytical method was validated in terms of linearity, sensitivity, selectivity, enhancement factor, accuracy, and precision, and its greenness and applicability were evaluated. The obtained limits of quantification were 0.01–0.05 μg L−1. The relative recoveries were 91.4 and 110.6 % for intra-day and 88.0–111.2 % for inter-day study, while the relative standard deviation values were better than 10.9 %. Finally, the developed method was used for the analysis of real water samples, proving good fitness for the purpose.

Rice sheath blight disease control by native endophytic Bacillus subtilis from Kuttanad, a Globally Important Agricultural Heritage System

ABSTRACT Kuttanad in India is known as ‘the rice bowl of Kerala’ and renowned for its unique rice cultivation system that is below sea level. However, rice production in this wetland ecosystem is seriously threatened by sheath blight disease caused by the fungus Rhizoctonia solani, which has resulted in a significant decline in grain quality and a 50% loss in yield. In the present study, we isolated two endophytic Bacillus subtilis strains, NIIST B616 and NIIST B627, from the roots of rice plants growing in the Kuttanad region and tested their efficacy in controlling sheath blight disease. We found that rice plants inoculated with a combination of both Bacillus strains and R. solani had a 64.71% lower disease incidence and a 31.02% higher harvest index than plants treated with R. solani alone. An analysis of defence-related enzymes and chemicals revealed that treatment with both isolates together greatly enhanced levels of l-phenylalanine ammonia-lyase (PAL; 2.8 fold), peroxidase (POX; 7.4 fold), polyphenol oxidase (PPO; 4.5 fold), and total phenol (8.5 fold) compared with plants treated solely with R. solani, indicating that these isolates significantly increased plant defence responses through induced systemic resistance (ISR), and this finding was validated through a split-root experiment. More detailed analysis using gas chromatography–tandem mass spectrometry (GC-MS/MS) and liquid chromatography–tandem mass spectrometry (LC-MS/MS) techniques revealed that cyclo-(Pro-Leu) and cyclo-(Pro-Phe) were the major components responsible for the antifungal properties of the two isolates and their capacity to trigger ISR in plants. Thus, the Bacillus strains and their metabolites may be deemed viable alternatives for controlling the prevalence of sheath blight disease in rice plants and augmenting rice production at unique locations such as Kuttanad.

Extraction of pesticides from soil using direct-immersion SPME LC-Tips followed by GC–MS/MS: Evaluation and proof-of-concept

A new method was evaluated and developed for the analysis of pesticides in sandy-loam soil by direct-immersion solid phase microextraction (DI-SPME) followed by gas chromatography tandem-mass spectrometry (GC–MS/MS) determination. Ten pesticides were selected based on a literature survey of the compounds reported to be present in EU soils. The extraction was performed using SPME LC-Tips, a new SPME configuration with the coated fibers attached to a disposable and easy-to-handle micropipette tip, which was immersed into a soil slurry made by the addition of an aqueous solution to the soil sample. Ten experimental parameters were evaluated with a Plackett-Burman design, after which the extraction time and percentage of organic solvent in the aqueous extraction were optimized separately. The two fiber chemistries available (PDMS/DVB and C18) were evaluated in parallel for the entire work. In the final method, slurry samples were made by adding an aqueous solution (6 % methanol v/v) to 2 g of soil. The fiber was conditioned and then inserted, for extraction, into the samples, stirred by a magnetic bar. Afterwards, the analytes were desorbed onto 100 µL of methanol. After the addition of analyte protectants (ethylglycerol, gulonolactone, and sorbitol) the extract was injected into the GC–MS/MS system. Isotopically labelled penconazole was used as internal standard. A calibration was performed by extracting spiked soil with analyte concentrations of 0.1–50 µg/kg. Coefficients of determination of the linear calibration were between 0.94–0.98 for the PDMS/DVB and 0.92–0.99 for the C18. Limits of detection range between 0.01–10 µg/kg for the PDMS/DVB and 0.1–10 µg/kg for the C18. Overall, the C18 analytically outperformed the PDMS/DVB but required a longer extraction time (120 min vs 75 min for the PDMS/DVB). This method allows automation and generates low residual toxic waste, having the potential to be introduced as a greener and simpler alternative to currently used sample preparation methodologies.

A vortex-assisted MSPD method for the extraction of Polycyclic Aromatic Hydrocarbons from shrimp with determination by GC-MS/MS

Polycyclic Aromatic Hydrocarbons (PAHs) are organic compounds with two or more condensed aromatic rings, formed from incomplete organic matter combustion. PAHs pose potential health risks due to their carcinogenic and mutagenic properties, accumulating in edible tissues of aquatic organisms, such as shrimp, which is extensively produced in the southern region of Rio Grande do Sul state (Brazil) and it is the most consumed seafood globally. Therefore, this study aimed to optimize and validate an analytical method for extracting 16 priority PAHs from shrimp samples using Vortex-Assisted Matrix Solid-Phase Dispersion (VA-MSPD) with determination by Gas Chromatography Tandem Mass Spectrometry (GC-MS/MS). The optimized method, which uses a reused solid support, was validated according to INMETRO and SANTE guidelines. PAHs demonstrated adequate linearity with correlation coefficients > 0.99. The matrix effect was assessed, and 12 out of the 16 PAHs showed a matrix effect of less than ±20%. The method's quantification limits ranged from 6.67 to 33.35 ng g-1. Accuracy and precision showed recovery values ranging from 55 to 115% with relative standard deviation (RSD) lower than 17% for all PAHs. In the applicability, 11 PAHs were detected, such as benzo[a]pyrene and benzo[b]fluoranthene, and the ∑PAHs ranged from 25.14 to 79.52 ng g-1, confirming the environmental contamination in the region and the need for monitoring these contaminants in shrimp destined for human consumption.

Genetic predisposition to impaired beta-cell function modifies the association between serum pyrethroid levels and the risk of type 2 diabetes: A gene-environment interaction study

Previous studies suggested that pyrethroid exposure was associated with elevated type 2 diabetes (T2D) risk, while it remains uncertain whether genetic predisposition modifies this association. A nested case-control study within the prospective Dongfeng-Tongji cohort comprised 1832 T2D cases, age- (±5 years) and sex-matched controls with qualified genotyping data. Serum pyrethroids were measured by gas chromatography-tandem mass spectrometry. Overall diabetes-related genetic risk score (GRS) or pathway-specific GRS, including unweighted GRSs (uGRS) and weighted GRSs (wGRS), was developed by genetic variants identified in Asian populations. Higher overall diabetes-related GRS and GRS specific to the pathway of impaired beta cell function (Beta-cell GRS) were associated with a higher incident T2D risk. Beta-cell uGRS significantly modified the association of serum permethrin (Pinteraction=0.04) and deltamethrin (Pinteraction=0.01) with T2D. Specifically, for each doubling increase in serum deltamethrin, the odds ratios (ORs) (95 % confidence intervals [CIs]) for T2D were 1.23 (0.98–1.56) and 0.91 (0.77–1.07) in the highest and lowest Beta-cell uGRS group, as well as 1.23 (1.02–1.47) and 0.95 (0.78–1.15) for Beta-cell wGRS group, respectively. When considering jointly, those with the highest deltamethrin levels and highest Beta-cell GRS had a substantially higher T2D risk, compared with the reference group (OR for uGRS: 3.79 [95 % CI: 2.03–7.07], Pinteraction=0.03 and 3.23 [95 % CI: 1.78–5.87], Pinteraction=0.05 for wGRS). Our findings suggested that genetic susceptibility to impaired beta-cell function should be considered for T2D prevention targeting pyrethroid exposure, particularly deltamethrin.

Development of a unified method for the determination of legacy and metabolites of current pesticides in serum for exposure assessment.

The use of pesticides is often regarded as a fundamental aspect of conventional agriculture. However, these compounds have gained recognition as some of the oldest and most widely employed xenobiotic contaminants, necessitating effective strategies for human biomonitoring. In this context, a method was developed for the determination of 16 legacy organochlorine pesticides, 6 metabolites of current pesticides (2,4-D, malathion, parathion, fipronil, pyraclostrobin, cypermethrin, permethrin, cyfluthrin), and 1 triazine herbicide (atrazine) in serum. Samples were prepared with water, formic acid, acetonitrile, and ultrasound irradiation, followed by solid-phase extraction with Oasis Prime HLB. Subsequently, metabolites from current pesticides underwent derivatization using MTBSTFA with 1% TBDMSCl for analysis via gas chromatography-tandem mass spectrometry (GC-MS/MS), employing an SLB-5MS fused silica capillary column. Analytical curves were generated with limits of quantification from 0.3 to 4.0ng.mL-1. Accuracy ranged from 69 to 124%, and the coefficient of variation from 2 to 28%. Moreover, determining 1-(4-chlorophenyl)-1H-pyrazol-3-ol was suggested as a biomarker for pyraclostrobin biomonitoring. This analytical approach facilitated the determination of both legacy and metabolites of current pesticides in the same serum sample, presenting an interesting and cost-effective option for large cohorts, and multi-omics studies that evaluate time-dependent biomarkers in blood samples, thereby enabling biomonitoring within the same matrix. Furthermore, a proof-of-concept involving 10 volunteers demonstrated exposure to 9 pesticides at mean concentrations measured in ngmL-1, consistent with findings from various biomonitoring initiatives.

Computational exploration of bioactive compounds from Albizia procera: Molecular docking, dynamics, and pharmacokinetics for AchE and BchE inhibition in Alzheimer's disease treatment

Current treatments for Alzheimer's disease (AD) are inadequate and primarily target inhibition of butyrylcholinesterase (BchE) and acetylcholinesterase (AChE) enzymes. This study focused on identifying potential anti-AD compounds from the leaf extract of Albizia procera using gas chromatography-tandem mass spectrometry (GC-MS) analysis and computational approaches. Ethanol seed extract analysis revealed 10 phytoconstituents, which were evaluated for their binding affinities using Autodock Vina and Desmond software against AD-related targets (PDB IDs: 4PQE, 2WJO, and 2POA). Five compounds, along with the control drug, showed significant docking energies. Subsequent in silico ADMET analysis assessed parameters such as intestinal absorption, blood-brain barrier permeability, gastrointestinal absorption, carcinogenicity, and acute oral toxicity. The results extract showed notable affinity for BchE and acetylcholinesterase targets. Molecular dynamics (MD) simulations supported the involvement of hydrogen bonding with ASP207 and GLY75 residues in binding these ligands, demonstrating that disrupting these forces causes destabilization. A ligand plot study also presented a two-dimensional plot of these interactions. The docking results indicate that 7-Oxabicyclo [4.1.0] heptan-2-one could be a promising agent for the treatment of AD because of its higher stability with respect to the two best ligands among all compounds tested. Therefore, from this study, it can be concluded that the compounds present in the leaf extract of A. procera have potential as targets linked to AD and may be helpful for the development of new drugs. Therefore, these data draw a focus on non-synthetic compounds during drug discovery and could possibly provide approaches for exploring existing therapies for AD.

In-depth phytochemical profiling of Roscoea purpurea (Kakoli): Comparative UHPLC-MS/QToF and GC-MS/MS analysis of supercritical CO2 fluid - and conventional solvent - based extractive processes

The remarkable biodiversity of medicinal plants worldwide highlights their significance in traditional and alternative medicine. Astavarga, a group of eight medicinal herbs from the Himalayan region of India, including Roscoea purpurea (commonly known as Kakoli), is esteemed in Ayurveda for its health-promoting and rejuvenating properties. In this comprehensive study, we aimed to develop and optimise robust UHPLC-MS/QToF (Ultra-high-performance liquid chromatography-mass spectrometry coupled with quadrupole time of flight) and GC-MS/MS (Gas chromatography-tandem mass spectrometry) methods to identify the phytochemicals in R. purpurea root hydromethanolic extract and essential oil. We also conducted a comparative assessment of supercritical fluid extraction and conventional solvent extraction methods for the first time in R. purpurea root, highlighting their relevance to the medicinal field. Using the UHPLC/MS-QToF method, we identified a total of fifty-six phytometabolites, while sixteen volatile constituents were discerned within the essential oil of R. purpurea by GC-MS/MS method. Among the volatile constituents, β-eudesmol (40.84 %), guaiac acetate (10.55 %), and γ-eudesmol (10.31 %) were emerged as the principal components. Our findings were further compared with the volatile constituents extracted via supercritical fluid extraction and conventional solvent extraction methods. Notably, our research unveiled the presence of a carotenoid metabolite, 15-methyl retinol, for the first time. Furthermore, our fatty acid analysis of the supercritical fluid extract revealed elevated levels of unsaturated fatty acids, particularly oleic and linoleic acids. The methods were validated in terms of system specificity also. The discovery of these well-recognised therapeutically active components in R. purpurea significantly enhances its potential, highlighting its unique profile among medicinal plants in the Himalayan region and its suitability for traditional Ayurveda.

Aged Brain Metabolomics Study by Metabolic Profiling Analysis of Amino Acids, Organic Acids, and Fatty Acids in Cortex, Cerebellum, Hypothalamus, and Hippocampus of Rats.

Aging is a progressive process characterized by weakness in brain function. Although metabolomics studies on the brain related with aging have been conducted, it is not yet fully understood. A systematic metabolomics study was performed to search for biomarkers and monitor altered metabolism in various brain tissues of the cortex, cerebellum, hypothalamus, and hippocampus of young (8 months old) and old rats (22 months old). Simultaneous profiling analysis of amino acids (AAs), organic acids (OAs), and fatty acids (FAs) in the brain tissues of young and old rats were performed by gas chromatography-tandem mass spectrometry. Under optimal conditions, AA, OA, and FA profiling methods showed good linearity (r ≥0.995) with limit of detection of ≤30 and 73.2 ng and limit of quantification of ≤90.1 and 219.5 ng, respectively. Repeatability varied from 0.4 to 10.4 and 0.8 to 14.8% relative standard deviation and accuracy varied from -11.3 to 10.3 and -12.8 to 14.1% relative error, respectively. In the profiling analysis, total 32, 43, 45, and 30 metabolites were determined in cortex, cerebellum, hypothalamus, and hippocampus, respectively. In statistical analysis, eight AAs (alanine, valine, leucine, isoleucine, threonine, serine, proline, and phenylalanine) in the cortex and four metabolites (alanine, phenylalanine, 3-hydoxypropionic acid, and eicosadienoic acid) in the cerebellum were significantly evaluated (Q-value <0.05, variable importance in projection scores ≥1.0). In all brain tissues, the score plots of orthogonal partial least square discriminant analysis were clearly separated between the young and old groups. Metabolomics results indicate that mechanistic targets of rapamycin complex 1, branched chain-amino acid, and energy metabolism are related to inflammation and mitochondrial dysfunction in the brain during aging. Thus, these results may explain the characteristic metabolism of brain aging.

Determination of 8 N-nitrosamines in the workplace air by GC-MS/MS method

Objective: To establish a method for the determination of eight N-nitrosamines (N-nitrosodimethylamine, N-nitrosodimethylamine, N-nitrosomethylmethylamine, N-nitrosodibutylamine, N-nitrosopropylamine, N-nitrosomorpholine, N-nitrosodianiline and N-nitrosopiperidine) in the air of workplace by gas chromatography-tandem mass spectrometry (GC-MS/MS) . Methods: From January to August 2023, eight N-nitrosamines in the air of workplace were collected by ThermoSorb/N column, eluted with 4 ml methanol-dichloromethane (1∶1 volume ratio), separated by VF-624 ms capillary column, detected by multiple reaction monitoring mode and quantified by external standard method. The detection limit and precision of the method were also analyzed. Results: The linear range of the method for the determination of eight N-nitrosamines was 1.0-20.0 μg/L, the correlation coefficient was 0.9993-0.9999, the detection limit was 0.051-0.132 μg/L, and the minimum quantitative concentration was 0.030-0.078 μg/m(3) (calculated by collecting 22.5 L of air sample and eluting with 4.0 ml stripping liquid). The within-run precisions were 2.05%-6.89% and the between-run precisions were 2.41%-8.26%. The desorption rates were 67.20%-102.60%. The sample can be kept at least 7 days at 4 ℃. Conclusion: GC-MS/MS method for the determination of eight N-nitrosamines in workplace air has high sensitivity and good precision, and can accurately determine the content of eight N-nitrosamines in workplace air.

A rapid and validated GC-MS/MS method for simultaneous quantification of serum Myo- and D-chiro-inositol isomers

BackgroundMyo-inositol (MI) and D-chiro-inositol (DCI) are two paramount isomers of inositol, both vital in glucose and steroid metabolism. Deficits in MI, DCI or MI/DCI ratio are expressly concerned with several pathological process, whereas MI and DCI lack practical measurement for human specimen. MethodsTo quantify MI and DCI in serum samples simultaneously, a gas chromatography tandem mass spectrometry (GC-MS/MS) method was established. The process flow was optimized in ion source, derivative agent volume and reaction time. The performance characteristics were verified by commercial standards and clinical serums. ResultsThis method was confirmed to be sensitive (LOD ≤ 30 ng/mL of MI, ≤3 ng/mL of DCI) and reproducible (RSD < 6 % for repeated analyses). Quantitative determinations performed good linearity within the measurement range of 0.500–10.00 and 0.005–0.500 μg/mL for MI and DCI respectively (R2 > 0.999). The recoveries of MI and DCI were 97.11–99.35 % and 107.82–113.09 %, respectively. This method was successfully applied to 114 clinical specimens. No significant matrix effect was observed in serum samples under current conditions.

Associations of prenatal and concurrent exposure to phenols mixture with anthropometric measures and blood pressure during childhood: A time-varying mixture approach

BackgroundEnvironmental phenols were recognized as endocrine disrupting chemicals (EDCs). However, their impact on childhood anthropometric measures and blood pressure (BP) is still inconclusive. Limited studies have simultaneously considered prenatal and childhood exposures in analyzing mixtures of phenols. ObjectiveWe investigated the relationships between combined prenatal and childhood exposures (two periodic exposures) to phenol mixtures and anthropometric measure and BP, to further identify the vulnerable periods of phenol exposure and to explore the important individual contribution of each phenol. MethodsWe analyzed 434 mother-child dyads from the Sheyang Mini Birth Cohort Study (SMBCS). The urinary concentrations of 11 phenolic compounds were measured using gas chromatography tandem mass spectrometry. Generalized linear regression models (GLMs) and hierarchical Bayesian Kernel Machine Regression (hBKMR) were used to examine the effects of individual phenolic compounds at each period and of two periodic exposures. ResultsIn the single-chemical analysis, prenatal or childhood exposure to specific phenols, especially Benzopheone-3 (BP3), 4-tert-Octylphenol (4-tOP), and Benzyl paraben (BePB) were associated with BMI z-scores (BAZ), Waist-to-height ratio (WHtR), and BP. In the hBKMR models, two periodic exposures to phenol mixtures had a U-shaped association with WHtR, primarily driven by childhood BePB exposure. Moreover, among the phenol mixtures analysis, childhood 4-tOP exposure was identified as the primary contributor to the positive association with diastolic BP. Concurrent exposure to phenol mixtures resulted in greater susceptibility. ConclusionsWe found that prenatal and childhood exposure to phenol mixtures might influence childhood obesity and elevate blood pressure levels. Concurrent exposure to 4-tOP may be the primary driver of the positive associations with BP.

Analysis of nitrogen-containing rocket fuel transformation products in loamy soil by thermal desorption gas chromatography-tandem mass spectrometry.

Unsymmetrical dimethylhydrazine (UDMH) based rocket fuel, when released into the soil, undergoes oxidative transformations to form a variety of toxic nitrogen-containing products (TPs). Loamy soils containing aluminosilicates (clay) are capable of strong binding and retention of UDMH TPs due to a combination of polar sorption and cation-exchange properties, posing challenges for their extraction and quantification. To overcome this problem, the present study proposes direct thermal desorption (TD) of analytes from loam facilitated by the addition of modifiers competing with UDMH TPs for sorption centers and ensuring their conversion into molecular form. Among tested additives, the mixture of potassium chloride and hydroxide demonstrated the best performance and provided recoveries of the most UDMH TPs exceeding 70% under optimized TD conditions (200°C, 30min). The online combination of TD with gas chromatography-tandem mass spectrometry allowed for the development of a method for the determination of 15 UDMH TPs in loamy soils with limits of detection in the range of 0.2-15µg/kg. The use of matrix-matched calibration and deuterated internal standards ensured high accuracy (80%-100%) and precision (relative standard deviation<18%) of the analysis. The developed method was validated and successfully tested in the analyses of real loamy soil samples polluted with rocket fuel.

Monoclonal antibody based colloidal gold immunochromatographic assay for the visual and rapid screening of profenofos

Profenofos (PFF) is a commonly used organophosphorus insecticide that requires strict monitoring due to its potential environmental, ecological, and human health risks originating from residues in soil and water systems, as well as accumulation in crops. In this study, a novel monoclonal antibody (mAb) specific to PFF was prepared for the first time and the recognition mechanism was investigated through molecular simulation. Subsequently, a mAb-based colloidal gold immunochromatographic assay (GICA) was developed for the rapid screening of PFF in fruit and vegetable samples. The mAb exhibited an IC50 value of 12.9 ng/mL, and limit of detection (LOD) of 4.6 ng/mL, respectively in indirect competitive immunosorbent enzyme-linked immunosorbent assay (ic-ELISA). After optimization, the developed GICA exhibited a visual limit of detection (vLOD) of 20 ng/mL and a quantitative of detection (qLOD) of 5.2 ng/mL, with a linear range from 10.0 to 83.8 ng/mL. Good correlation was observed between the results of GICA and standard Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS) in matrix and recovery test. The developed GICA can be used for rapid sample detection within 15 min, which is an excellent tool for screening PFF in foods and environmental samples.

France-Wide Monitoring of 1,4-Dioxane in Raw and Treated Water: Occurrence and Exposure Via Drinking Water Consumption

In recent years, 1,4-dioxane has emerged as a pollutant of increasing concern following widespread detection in the aquatic environment of several countries. This persistent contaminant with specific physical and chemical properties can be rapidly dispersed and transported to river banks, groundwater and drinking water. Given the limited data on its occurrence in France, it was considered necessary to assess the potential exposure of the French population to this compound in drinking water. An analytical method based on solid-phase extraction (SPE) combined with gas chromatography tandem mass spectrometry (GC–MS/MS) was developed and validated during this study with a limit of quantification (LOQ) of 0.15 µg/L. Recoveries in natural water matrices ranged from 113 to 117% with a relative bias not exceeding 17%. This method was used for a nationwide campaign at almost 300 sites, evenly distributed over 101 French départements (administrative units), including some that were overseas. Of the 587 samples analysed, only 8% had a concentration that was greater than or equal to the LOQ. 1,4-Dioxane was detected mainly (63%) in raw and treated water from sites associated with historical industrial practices related to the use of chlorinated solvents. Concentrations of 1,4-dioxane ranging from 0.19 to 2.85 µg/L were observed in the raw water and from 0.18 to 2.46 µg/L in the treated water. Drinking water treatment plants using ozonation, granular activated carbon and chlorination have limited effectiveness in the removal of 1,4-dioxane. The results of this study are the first step towards bridging the knowledge gap in the occurrence of 1,4-dioxane in France.

A new strategy for volatile organics detection – Molecularly imprinted polymers-enabled headspace extracting and electrochemical sensing

The widely accepted method for detecting trace odor compounds such as 2-methylisoborneol (2-MIB) requires high-cost solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry (SPME-GC/MS). As for now, cases that directly used SPME-GC/MS in the field are unseen, and most detection activities are still carried out in rigorous laboratory conditions. However, lengthy logistics and storage issues can compromise sample conditions, underscoring the significance of on-site detection methods. Here, we reported molecularly imprinted polymers-enabled headspace extracting and electrochemical sensing (MHEES) with the core feature of using the same piece of MIP for both headspace extracting and electrochemical sensing, allowing rapid on-site detection of trace 2-MIB in natural water bodies with a total cost of less than $2.10 per test. MHEES demonstrated exceptional sensitivity during extensively repeated laboratory experiments, achieving a detection limit of 3.7 ng∙L−1 and a standard deviation of 4.58 %. The practicality of MHEES was confirmed by conducting two rounds of on-site analyses on different reservoirs with fluctuating seasonal concentrations of 2-MIB. The developing flow of MHEES, from molecules docking to on-site application, was rigorous and could be cross-referenced to related research. The proposed MHEES design can potentially revolutionize the field of analytical chemistry by providing a versatile and affordable platform for on-site volatile compounds detection. It can readily adapt to various organic compounds and effectively address real-world challenges such as monitoring emerging pollutants, tracing disease biomarkers in body fluids, inspecting food safety, identifying chemical reaction intermediates, and supporting healthcare applications.

Impact of Bacillus subtilis on Chinese yellow rice wine (Huangjiu) fermentation: Method variations and flavor analysis

This investigation explores the impact of various fermentation techniques and the inoculation of Bacillus subtilis spores on the physicochemical properties and principal flavor profiles of Huangjiu. Employing sensory analysis, headspace solid-phase microextraction, gas chromatography-tandem mass spectrometry (HS-SPME-GC–MS), and orthogonal partial least squares discriminant analysis (OPLS-DA), we observed that these variables significantly alter the physicochemical attributes of Huangjiu. Our analysis, integrating volatile organic compounds (VOCs) with odor activity values (OAV), revealed that while B. subtilis inoculation modifies the concentrations of key flavor compounds, it does not affect their types. Notably, the inoculation enhances the concentrations of 13 primary flavor compounds, thereby enriching floral and fruity notes while reducing higher alcohol levels. These findings contribute valuable insights into the flavor formation mechanisms of Huangjiu and guide the optimization of fermentation processes.