Gas Chromatography-high Resolution Mass Spectrometry Research Articles

Prevalence of Psychoactive Substance Use During Pregnancy in Argentine Women: A Pilot Study Testing Maternal Hair

Background: The use of psychoactive substances (PSs) during pregnancy is a major public health concern because of their increasing prevalence worldwide. This study examined the understudied issue of gestational PS consumption in a cohort of Argentine delivering mothers. Methods: A cross-sectional pilot study involving 51 women receiving delivery care was conducted at the Santa Rosa Hospital in La Pampa, Argentina. Information on maternal sociodemographic characteristics, pregnancy history, and drug use was obtained through standardized interviews. Maternal hair samples were analyzed for alcohol, tobacco, licit, illicit, and prescription substance biomarkers using ultra-high-performance liquid chromatography high-resolution mass spectrometry and gas chromatography mass spectrometry. Results: During pregnancy, 49.0% of participants reported alcohol consumption, 25.5% reported tobacco use, and 23.5% reported cannabis use. Hair samples from 56.9% of the women were positive for illicit PSs, with the most frequent being cocaine (41.2%) and cannabis (15.7%). Among the women, 47.1% consumed alcohol during pregnancy. Of the 24 women with hair ethyl glucuronide ≥5 pg/mg, 33.3% drank until the end of gestation and 58.3% started a social drinking habit in the second half. The analysis also detected prescription substances (anticonvulsants, antidepressants, methadone, opioids, antihistamines, antiemetics, and analgesics), caffeine (70.6%), lidocaine, and levamisole, some of which were cocaine or opioid adulterants. Conclusions: This is the first study to objectively assess the consumption of licit and illicit PSs during pregnancy in Argentina. In contrast to most nearby countries, cocaine was the most detected illicit PS in this cohort of Argentine delivering women. This finding highlights the importance of regular monitoring of local trends in PS use during pregnancy.

Qualitative transformations of street-seized ecstasy over a decade: A case study in Rio de Janeiro (Brazil).

The illegal drug market is constantly evolving, with new drugs being created and existing ones being modified. Adulterants are often added to the mix, and the primary substance may be secretly replaced by a new one. Once-known tablets can now be vastly different from what they are sold as, all due to the pursuit of profit and evasion of current drug regulations. These alterations in drug composition pose a threat to society, as their effects are still not well understood. Therefore, it is crucial for police intelligence and public health development to obtain the chemical profiles of illicit drugs. This study presents the chemical fingerprinting of ecstasy tablets seized in the state of Rio de Janeiro (Brazil) between 2012 and 2021. The tablet samples were weighed, extracted, diluted with methanol, and acidified before analysis using gas chromatography high-resolution mass spectrometry and attenuated total reflection Fourier transform infrared spectroscopy. The major constituents found were MDMA and clobenzorex, with fewer occurrences of MDA, MDEA, and 2C-B. The results also indicate that the occurrence of mega-events in the study location impacted the chemical fingerprints of ecstasy. A total of 27 combinations of cutting agents, including caffeine, ephedrine, and anesthetics, were identified. Samples composed of clobenzorex were observed throughout the evaluated period in areas near highways, suggesting that this product is mainly used by truck drivers. These findings can help police intelligence units anticipate the behavior of the illicit market during major events, identify traffic routes, and support public health initiatives.

Chemical impurity profiling: Linkage of starting materials and an intermediate synthesis product of a carbamate chemical warfare agent

Establishing links between starting materials and products is highly valuable in the investigation of the use of toxic chemicals for illicit purposes. In this study, impurity profiling was performed on starting materials and their synthesis product, 2-([dimethylamino]methyl)pyridin-3-yl dimethylcarbamate, an intermediate compound in the production route for the carbamate class of Chemical Warfare Agents. The aim was to link the five commercial starting materials to the correct synthesis products. Initially, the intermediate compound was synthesized using different batches of the two starting materials (2 plus 3 batches), producing six unique combinations. All synthesis batches and the different starting materials were analysed by gas chromatography-high resolution mass spectrometry (GC-HRMS). Chemometrics analyses were conducted with principal component analysis and orthogonal projections to latent structures discriminant analysis to extract chemical impurity profiles and to build supervised classification models.Additionally, 12 test set samples, produced using the same starting materials by two different chemists in another laboratory, were analysed by GC-HRMS. A classification model able to distinguish all supplier combinations was successfully created and used to link the test set samples to their corresponding starting material.Furthermore, a new set of synthesis samples was extracted with a work-up procedure before analysis to investigate the effect of higher sample purity on the classification model. The results show that linking the synthesis products to their starting materials was successful for one of the starting materials, despite the purification procedure.

Exposure to Polybrominated Diphenyl Ethers and Risk of All-Cause and Cause-Specific Mortality

Polybrominated diphenyl ethers (PBDEs) are an important group of persistent organic pollutants with endocrine-disrupting properties. However, prospective cohort studies regarding the association of PBDE exposure with long-term health outcomes, particularly mortality, are lacking. To examine the association of environmental exposure to PBDEs with risk of all-cause and cause-specific mortality. This nationally representative cohort study used data from the National Health and Nutrition Examination Survey 2003 to 2004 and linked mortality information through December 31, 2019. Adults aged 20 years or older with available data on PBDE measurements and mortality were included. Statistical analysis was performed from February 2022 to April 2023. PBDE analytes in serum samples were measured using solid phase extraction and isotope dilution gas chromatography high-resolution mass spectrometry. All-cause mortality, cancer mortality, and cardiovascular mortality. This study included 1100 participants (mean [SE] age, 42.9 [0.6] years; proportion [SE] female, 51.8% [1.6%]; proportion [SE] Hispanic, 12.9% [2.7%]; proportion [SE] non-Hispanic Black, 10.5% [1.6%]; proportion [SE] non-Hispanic White, 70.8% [3.7%]; proportion [SE] other race and ethnicity, 5.8% [1.1%]). During 16 162 person-years of follow-up (median [IQR] follow-up, 15.8 [15.2-16.3] years; maximum follow-up, 17 years), 199 deaths occurred. Participants with higher serum PBDE levels were at higher risk for death. After adjustment for age, sex, and race and ethnicity, lifestyle and socioeconomic factors, and body mass index, participants with the highest tertile of serum PBDE levels had an approximately 300% increased risk of cancer mortality (HR, 4.09 [95% CI, 1.71-9.79]) compared with those with the lowest tertile of serum PBDE levels. No significant association of PBDE exposure with all-cause mortality (HR, 1.43 [95% CI, 0.98-2.07]) or cardiovascular mortality (HR, 0.92 [95% CI, 0.41-2.08]) was observed. In this nationally representative cohort study, PBDE exposure was significantly associated with an increased risk of cancer mortality. Further studies are needed to replicate the findings and determine the underlying mechanisms.

Structural elucidation of derivatives of polyfunctional metabolites after methyl chloroformate derivatization by high-resolution mass spectrometry gas chromatography. Application to microbiota metabolites

Metabolomics has become an essential discipline in the study of microbiome, emerging gas chromatography coupled to mass spectrometry as the most mature, robust, and reproducible analytical technique. Silylation is the most widely used chemical derivatization strategy, although it has some limitations. In this regard, alkylation by alkyl chloroformate offers some advantages, such as a rapid reaction, milder conditions, better reproducibility, and the generation of more stable derivatives. However, commercial spectral libraries do not include many of the alkyl derivatives, mainly for polyfunctional metabolites, which can form multiple derivatives. That introduces a huge bias in untargeted metabolomics leading to common errors such as duplicates, unknowns, misidentifications, wrong assignations, and incomplete results from which non-reliable findings and conclusions will be retrieved. For this reason, the purpose of this study is to overcome these shortcomings and to expand the knowledge of metabolites in general and especially those closely related to the gut microbiota through the thorough study of the reactivity of the different functional groups in real matrix derivatized by methyl chloroformate, a common representative alkylation reagent. To this end, a systematic workflow has been developed based on exhaustive structural elucidation, along with computational simulation, and taking advantage of the high sensitivity and high-resolution gas chromatography-mass spectrometry. Several empirical rules have been established according to chemically different entities (free fatty acids, amino acids, polyols, sugars, amines, and polyfunctional groups, etc.) to predict the number of derivatives formed from a single metabolite, as well as their elution order and structure. In this work, some methyl chloroformate derivatives not previously reported as well as the mechanisms to explain them are given. Extremely important is the interconversion of E- and Z- geometric isomers of unsaturated dicarboxylic acids (case of fumaric-maleic and case of citraconic-mesaconic acids), or the formation of cycled derivatives for amino acids, as well as common metabolites, as in the case of serine and cysteine, and many others.

Comprehensive two-dimensional gas chromatography-high resolution mass spectrometry for the detailed qualitative analysis of old vine Chenin blanc wine volatiles and comparison with young vine Chenin blanc wines

Old vine Chenin blanc (OVC) wines are produced from grapes harvested from vines older than 35 years, verified as Certified Heritage Vineyards in South Africa. This emerging premium wine style is of interest due to the purported unique sensory properties of these wines, including their complex aroma. There is however limited information available on the volatile constituents of these wines, which are primarily responsible for perceived aroma. The wine volatilome is exceedingly complex, and requires advanced analytical approaches to investigate. The present contribution reports the evaluation of comprehensive two-dimensional gas chromatography (GC × GC) as a powerful separation technique to gain qualitative insight into the volatile composition of OVC wines. Extraction of volatile compounds was performed using headspace solid-phase microextraction (HS-SPME), while the GC × GC separation was hyphenated to high speed high resolution time-of-flight MS (HR-TOF-MS) for compound identification. A representative set of eight Chenin blanc wines produced from young vines (YVC) was also analysed to investigate the potential use of GC × GCHR-MS data to differentiate these two wine styles based on differences in their volatile composition. The results confirm the utility of GC × GCHR-MS for the detailed qualitative analysis of wine volatiles, with a total of 277 compounds identified in the studied wines. 53 compounds were uniquely identified in the OVC samples, and 52 in YVC wines. Successful differentiation of the young- and old-vine wines was achieved based on tile-based Fisher (F) ratios and principal component analysis (PCA), although this differentiation could not be clearly linked to winemaking practices (wood maturation) or viticultural origin.

N-dealkylation of amines during water disinfection – Revealing a new direction in the formation of disinfection by-products

Among numerous disinfection by-products (DBP) forming during aqueous chlorination nitrogen containing species are of special concern due to their toxicological properties. Nevertheless, corresponding reaction products of these natural and anthropogenic compounds are not sufficiently studied so far. An interesting reaction involves dealkylation of the substituted amine moiety. Here we present the results of the comparative study of one-electron oxidation and aqueous chlorination of several aliphatic and aromatic amines. The reaction products were reliably identified with gas chromatography – high resolution mass spectrometry (GC-HRMS), high pressure liquid chromatography – electrospray ionization high resolution mass spectrometry HPLC-ESI/HRMS), and electrochemistry - electrospray ionization high resolution mass spectrometry (EC-ESI/HRMS). Certain similarities dealing with the formation of the corresponding aldehydes and substitution of alkyl groups at the nitrogen atom for hydrogen were shown for the studied processes. The mechanism of the substituted amines’ aqueous chlorination involving one-electron oxidation is proposed and confirmed by the array of the observed reaction products. Alternative reactions taking place in conditions of aqueous chlorination, i.e. aromatic electrophilic substitution, may successfully compete with dealkylation and produce major products.

Immunotoxic, genotoxic, and endocrine disrupting impacts of polyamide microplastic particles and chemicals

Due to their exceptional properties and cost effectiveness, polyamides or nylons have emerged as widely used materials, revolutionizing diverse industries, including industrial 3D printing or additive manufacturing (AM). Powder-based AM technologies employ tonnes of polyamide microplastics to produce complex components every year. However, the lack of comprehensive toxicity assessment of particulate polyamides and polyamide-associated chemicals, especially in the light of the global microplastics crisis, calls for urgent action. This study investigated the physicochemical properties of polyamide-12 microplastics used in AM, and assessed a number of toxicity endpoints focusing on inflammation, immunometabolism, genotoxicity, aryl hydrocarbon receptor (AhR) activation, endocrine disruption, and cell morphology. Specifically, microplastics examination by means of field emission scanning electron microscopy revealed that work flow reuse of material created a fraction of smaller particles with an average size of 1–5 µm, a size range readily available for uptake by human cells. Moreover, chemical analysis by means of gas chromatography high-resolution mass spectrometry detected several polyamide-associated chemicals including starting material, plasticizer, thermal stabilizer/antioxidant, and migrating slip additive. Even if polyamide particles and chemicals did not induce an acute inflammatory response, repeated and prolonged exposure of human primary macrophages disclosed a steady increase in the levels of proinflammatory chemokine Interleukin-8 (IL-8/CXCL-8). Moreover, targeted metabolomics disclosed that polyamide particles modulated the kynurenine pathway and some of its key metabolites. The p53-responsive luciferase reporter gene assay showed that particles per se were able to activate p53, being indicative of a genotoxic stress. Polyamide-associated chemicals triggered moderate activation of AhR and elicited anti-androgenic activity. Finally, a high-throughput and non-targeted morphological profiling by Cell Painting assay outlined major sites of bioactivity of polyamide-associated chemicals and indicated putative mechanisms of toxicity in the cells. These findings reveal that the increasing use of polyamide microplastics may pose a potential health risk for the exposed individuals, and it merits more attention.

Mass Spectrometric Identification of Metabolites after Magnetic-Pulse Treatment of Infected Pyrus communis L. Microplants

The major goal of this study is to create a venue for further work on the effect of pulsed magnetic fields on plant metabolism. It deals with metabolite synthesis in the aforementioned conditions in microplants of Pyrus communis L. So far, there have been glimpses into the governing factors of plant biochemistry in vivo, and low-frequency pulsed magnestatic fields have been shown to induce additional electric currents in plant tissues, thus perturbing the value of cell membrane potential and causing the biosynthesis of new metabolites. In this study, sixty-seven metabolites synthesized in microplants within 3–72 h after treatment were identified and annotated. In total, thirty-one metabolites were produced. Magnetic-pulse treatment caused an 8.75-fold increase in the concentration of chlorogenic acid (RT = 8.33 ± 0.0197 min) in tissues and the perturbation of phenolic composition. Aucubin, which has antiviral and antistress biological activity, was identified as well. This study sheds light on the effect of magnetic fields on the biochemistry of low-molecular-weight metabolites of pear plants in vitro, thus providing in-depth metabolite analysis under optimized synthetic conditions. This study utilized high-resolution gas chromatography-mass spectrometry, metabolomics methods, stochastic dynamics mass spectrometry, quantum chemistry, and chemometrics, respectively. Stochastic dynamics uses the relationships between measurands and molecular structures of silylated carbohydrates, showing virtually identical mass spectra and comparable chemometrics parameters.

Evidence of transboundary movement of chemicals from Mexico to the U.S. in Tijuana River Estuary sediments

The Tijuana River Estuary (TRE) has been a public health hazard and point of contention between the United States and Mexico for decades, with sources of pollution on both sides of the border. The goal of our study is to determine the presence and dynamics of chemical contamination in the TRE. We sampled sediment from four TRE locations in the U.S. during stable dry conditions and immediately after a wet weather period. Organic chemicals were initially screened with non-targeted analysis using gas chromatography high-resolution mass spectrometry (GC/HRMS) that tentatively identified 6978 chemicals in the NIST 20 database. These tentative identifications were filtered using the USEPA CompTox database to guide quantitative targeted analysis at detection limits below 1 ng/g dry weight sediment. Quantitative targeted analysis of 152 organic pollutants and 18 inorganic elements via GC/HRMS revealed generally higher concentrations of contaminants in dry weather sediments compared to wet weather sediments. The highest concentrations of all chemical classes were detected at the site closest to the U.S.-Mexico border, followed by an urban area near Imperial Beach, California, U.S. All sites exhibited a mixture of petrogenic and pyrogenic polycyclic aromatic hydrocarbons (PAHs). Current-use pesticides were dominated by pyrethroid insecticides and the thiocarbamate herbicide s-Ethyl dipropylthiocarbamate (EPTC), while the U.S.-banned organochlorine pesticides were dominated by chlordanes, dieldrin, and dichlorodiphenyltrichloroethane (DDT) and its degradation byproducts. Polychlorinated biphenyl (PCB) concentrations were greatest at the site closest to the U.S.-Mexico border but in the low nanogram-per-gram range. Phthalates were only found at the same site, with relatively high concentrations of bis(2-ethylhexyl) phthalate. This study provides positive identification and quantitative concentrations for organic pollutants in TRE sediments. Our data suggest that there are multiple sources of chemical contamination in the estuary, including possible transboundary movement of pollutants from Mexico.

Spatial distribution, source identification, and risk assessment of polychlorinated organic pollutants (PCDD/Fs and DL-PCBs) in the sediments of the largest urban water supply area (Iznik lake) in the Marmara region, Bursa, Türkiye

Iznik lake is the biggest lake in the Marmara region, which is the most industrialized and populated area of Türkiye. The lake is one of Türkiye's most important water supply areas and is located nearby the Iznik district of Bursa, with a population of about 45,000. It is being used for irrigation and fishery production, but not for drinking water. In this paper, the distribution, pollution source, and risk assessment of polychlorinated dibenzodioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in the surface sediments of Iznik lake and streams (both flowing to and flowing from the lake) were investigated. Six surface sediments collected from the lake and four surface sediments collected from the streams were analyzed in high-resolution gas chromatography-mass spectrometry (HR/GC–MS) system in accordance with EPA 1613 and EPA 1668 methods. The concentration ranges of the ∑PCDD/Fs is 21.4 pg/g d.w. (inside the lake (IZ-6)) – 54.5 pg/g d.w. (Gülayağı stream (IZ-8)) and ∑DL-PCBs is 13.5 pg/g d.w. (inside the lake (IZ-3)) – 46.3 pg/g d.w. (Olukdere (IZ-7)) respectively, with 2.68 pg TEQ/g d.w. on average. The results showed that the high chlorinated (Hepta – Octa CDD/Fs) dioxins/furans and pentachlorinated PCBs (PCB 118 and 105) are dominant in the sediments. A detailed assessment of PCDD/F congener profiles observed in the lake sediments speculated that the wastewater discharges to the lake could be the main pollution source, while other sources such as open burning activities, runoff of pesticide residues from agricultural areas and atmospheric deposition may have some contribution also. The health risk assessment performed for polluted sediment demonstrated that, in the worst case, dioxin-like (PCDD/Fs and DL-PCBs) concentration was a total intake of 0.37 pg TEQ/kg body weight/day, no exceeds the tolerable daily intake amount, where fish consumption accounts for nearly all of the total intake.

Development of Simplified and Efficient Sample Preparation Methods for the Analysis of Problem Material within the Diesel Fuel Delivery System.

A new approach for the analysis of diesel engine fuel filters has been developed. This method involves minimal to no sample preparation, allowing rapid and unbiased analysis of diesel fuel filters. In recent years, diesel fuel filter plugging incidences have increased in parallel with changing emissions legislation. Fuel filter blockages can result in increased emissions, reduced efficiency, and engine failure. It is not fully understood why fuel filter blockages occur; as a result, there has been an international increase in research into the cause of fuel filter plugging. The method discussed in this paper utilizes a thermal desorption (TD) style sample introduction technique that can be used in conjunction with gas chromatography-mass spectrometry (GC-MS) and presents a fast, simple, and more sustainable approach to the analysis of fuel filters. When required, an efficient and straightforward sample cleanup process was developed and was used to simplify and improve confidence in the data identification and assignment; this method is up to three orders of magnitude faster than some procedures adopted in the literature. Further complementary analytical techniques, such as ultrahigh-performance supercritical fluid chromatography-mass spectrometry (UHPSFC-MS) and high-resolution GC-MS, were used to access additional sample-specific information. This new approach has been successful in the identification of problematic materials deposited on blocked fuel filters, concurrent with recent research. This information can aid in the development of mitigation strategies to combat fuel filter plugging.

A rapid method for the determination of alkenylbenzenes in spices by gas chromatography - high resolution mass spectrometry (GC-HRMS)

Alkenylbenzene is a group of natural toxins that can cause genetic damage and cancer in rodents. These toxins are found in high amounts in common spices such as pepper, basil, cinnamon, dill, and others. This study aimed to develop a method for measuring eight alkenylbenzenes (eugenol, methyl eugenol, acetyl eugenol, trans-isoeugenol, safrole, estragole, myristicin and trans-anethole) in various spices using gas chromatography high-resolution mass spectrometry (GC–HRMS) with a simple ultrasonic vibration sample extraction method. The method was validated according to AOAC standards. The method had detection and quantification limits of 0.05 mg/kg and 0.15 mg/kg, respectively. The recovery ranged from 90.1% to 107% and the repeatability (RSD) ranged from 1.00% to 6.60% for all eight compounds, meeting the AOAC requirements. The analysis of 90 different dried and fresh spice samples revealed that eugenol (1.86–3581 mg/kg), trans-anethole (0.89–45.6 × 103 mg/kg) and estragole (0.19-248 mg/kg) were the main alkenylbenzenes, while trans-isoeugenol (0.69–7.86 mg/kg) and safrole (0.15–0.42 mg/kg) were the minor ones.

Deeper insights into the effects of low dietary levels of polychlorinated biphenyls on pig metabolism using gas chromatography-high resolution mass spectrometry metabolomics

Polychlorinated biphenyls (PCBs) are a class of contaminants of great concern, linked to the development of many chronic diseases. Adverse effects of PCBs have been documented in humans after accidental and massive exposure. However, little is known about the effect of chronic exposure to low-dose PCB mixtures, and studies regarding scattered lifetime exposures to non-dioxin-like (NDL)-PCBs are especially missing. In this work, serum samples from pigs chronically exposed through their diet during 22 days to Aroclor 1260 (i.e. a commercially available mixture of NDL-PCBs) underwent a metabolomics analysis using gas chromatography-high resolution mass spectrometry (GC-HRMS), with the objective to investigate the effect of exposure to low doses of NDL-PCBs (few ng/kg body weight (b.w.) per day). The study showed that the serum profiles of 84 metabolites are significantly altered by the administration of Aroclor 1260, of which 40 could be identified at level 1. The aggregate interpretation of the results of this study, together with the outcome of a previous one involving LC-HRMS profiling, provided a substantial and concise overview of the effect of low dose exposure to NDL-PCBs, reflecting the hepatotoxic and neurotoxic effects already reported in literature at higher and longer exposures. These results are intended to contribute to the debate on the current toxicological reference values for these substances.

Rethinking the Role of Formerly Sub-Sufficient Industrial/Synthesized SEI Additive Compounds - a New Perspective

In order to improve the performance of lithium-ion batteries (LIBs), novel electrolytes are of primary importance. Recently, fluorinated cyclic phosphazene derivatives in combination with fluoroethylene carbonate (FEC) are mentioned in the literature as a promising electrolyte additive combination, which can decompose to form a dense, uniform, and thin protective layer on the surface of the anode and cathode electrode.[1,2] Additionally, suppressing further electrolyte decomposition and electrode corrosion, thus protecting the structural destruction of the electrodes, are mentioned within this electrolyte composition.[1–3] Furthermore, galvanostatic charge and discharge experiments with different cell composition materials demonstrate that fluorinated cyclic phosphazene compounds as additional additive material tend to improve cycling stability.[1,3,4] Although the electrochemical aspects of cyclic fluorinated phosphazene compounds combined with FEC are briefly introduced, it is still not fully clear how these two compound classes interact constructively during operation mode. Thus, the positive synergistic effect of FEC/Hexafluorocyclotriphosphazene (HFPN)-derivatives on the electrochemical performance during cell operation is not enlightened. The focus of this study is to investigate the complementary effect of FEC and ethoxy(pentafluoro)cyclotriphosphazene (EtPFPN) as additive compounds in an aprotic organic electrolyte in LiNi0.5Co0.2Mn0.3O (NCM523) SiOx/C full cells. Furthermore, the formation mechanism of lithium ethyl methyl carbonate (LEMC)-EtPFPN interfacial products and the reaction mechanism of lithium alkoxide with EtPFPN are proposed and supported with DFT measurements. Additionally, a new effect of FEC regarding the SEI formation will be introduced. The EtPFPN decomposition compounds in the electrolyte after the SEI formation have been investigated via gas chromatography-mass spectrometry (GC-MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS). The electrode electrolyte interface investigation of the SEI has been performed via in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) and scanning electron microscopy (SEM). Constant current cycling is conducted, and in-situ Raman measurements characterize the deposition of electrolyte components and LEMC-EtPFPN traces on the SiOx/C anode material during the SEI formation. Finally, the interplay between EC, EMC, Li-alkoxide, LEMC, FEC, and EtPFPN has been visualized schematically via a reaction mechanism postulated based on analytical data of the electrolyte.[1] A. Ghaur, C. Peschel, I. Dienwiebel, L. Haneke, L. Du, L. Profanter, A. Gomez‐Martin, M. Winter, S. Nowak, T. Placke, Adv Energy Mater 2023, 2203503.[2] J. Liu, X. Song, L. Zhou, S. Wang, W. Song, W. Liu, H. Long, L. Zhou, H. Wu, C. Feng, Z. Guo, Nano Energy 2018, 46, 404–414.[3] Q. Liu, Z. Chen, Y. Liu, Y. Hong, W. Wang, J. Wang, B. Zhao, Y. Xu, J. Wang, X. Fan, L. Li, H. bin Wu, Energy Storage Mater 2021, 37, 521–529.[4] Y.-H. Liu, M. Okano, T. Mukai, K. Inoue, M. Yanagida, T. Sakai, J Power Sources 2016, 304, 9–14.

Temporal trends of lipophilic organic contaminants in blue mussel (1994–2017) and eelpout (1994–2017) from the southern Baltic Sea

A time-trend study was carried out for two important Baltic Sea species, blue mussel (1994–2017, 11 samples) and eelpout (1994–2017, 11 samples), to track the changes in levels of regulated persistent organic pollutants (POPs) and show potential increases in the levels of the contaminants of emerging concern (CECs). It was carried out utilizing gas chromatography–high-resolution mass spectrometry (GC-HRMS) based non-target screening (NTS). Data were acquired in two modes – electron ionization (EI) and electron capture negative ion chemical ionization (ECNI) – to widen the contaminant coverage, and treated using a fast semi-automated NTS data processing workflow. The study revealed that >250 tentatively identified compounds show statistically significant temporal trends in Baltic blue mussel and eelpout. A large number of regulated substances, including but not limited to PCBs, DDTs and other organochlorine pesticides (OCPs), chlorobenzenes, and many polybrominated diphenyl ethers (PBDEs), showed significant declining trends, as was expected. Their rates of decline were in good agreement with previously reported data. In contrast, increasing trends were observed for many CECs, some polycyclic aromatic compounds (PAHs), and hydrocarbons. The CEC group included, among others, four compounds, namely, one personal care product ingredient, 2-ethylhexyl stearate, one brominated compound 1,2,3,5-tetrabromobenzene and two intermediates 4-isopropoxyaniline and bilobol dimethyl ether, that were reported in marine biota for the first time to the best of our knowledge. Several compounds, including four CECs and two unknown brominated compounds, showed levels considerably higher than the common legacy pollutants (CB-153 and BDE-99), which might be taken into consideration for future monitoring and risk assessment. In addition, this work revealed the presence of a plethora of organoiodinated compounds that exhibited statistically significant temporal trends in the samples under study, which could be of future interest.

Exploring Phytochemical Composition and In Vivo Anti-Inflammatory Potential of Grape Seed Oil from an Alternative Source after Traditional Fermentation Processes: Implications for Phytotherapy.

This study aimed to analyze the composition of grape seed oil (GSO) derived from an alternative source after traditional fermentation processes and its potential anti-inflammatory effects using an in vivo model of carrageenan-induced inflammation in mice. Gas chromatography high-resolution electron ionization mass spectrometry (GC-HR-EIMS) analysis identified eight main components in the GSO extract, including myristic acid methyl ester, palmitoleic acid methyl ester, methyl isoheptadecanoate, cis-linoleic acid, oleic acid methyl ester, linoleic acid stereoisomer, linoleic acid ethyl ester, and methyl (6E, 9E, 12E, 15E)-docose-6,9,12,15-tetraenoate. No significant differences were observed in the main fatty acids between commercially available grape seed oil and GSO extract obtained from fermented grape seeds. In the carrageenan-induced inflammation model, treatment with GSO resulted in a significant reduction in paw edema at 180 min, as in the reduction observed with diclofenac treatment. Combined treatment with GSO and diclofenac showed enhanced anti-inflammatory effects. Additionally, GSO exhibited antioxidative effects by decreasing the levels of glutathione (GSH) and malondialdehyde (MDA) in the serum. Chronic treatment with GSO for ten days did not provide a protective effect on inflammation. These findings suggest that GSO could be used as an alternative raw material and could possess anti-inflammatory and antioxidative properties. Further studies are needed to explore its potential therapeutic applications.

A non-target geographical origin screening of botrytized wines through comprehensive two-dimensional gas chromatography coupled with high-resolution mass spectrometry.

One of the most effective methods for gaining insight into the composition of trace-level volatile organic characteristics of wine products is through the use of a comprehensive two-dimensional gas chromatography-high resolution mass spectrometry (GC × GC-HRMS) technique. The vast amount of data generated by this method, however, can often be overwhelming requiring exhaustive and time-consuming analysis to identify significant statistical characteristics. The use of advanced chemometric software can achieve the same or even higher efficiency. This study aimed to identify differences based on geographical locations by analyzing the volatile organic compounds in the composition of botrytized wines from Slovakia, Hungary, France, and Austria. The volatile organic compounds were extracted by solid-phase microextraction and analyzed using GC × GC-HRMS. The data obtained from the analysis underwent Fisher-ratio (F-ratio) tile-based analysis to identify statistically significant differences. Principal component analysis demonstrated a significant distinction between wine samples based on geographical location, using only 10 statistically significant features with the highest F-ratio. In the samples, the following compounds were analyzed: methyl-octadecanoate, 2-cyanophenyl-β-phenylpropionate, α-ionone, n-octanoic acid, 1,2-dihydro-1,1,6-trimethyl-naphthalene, methyl-hexadecanoate, ethyl-pentadecanoate, ethyl-decanoate, and γ-nonalactone. These, all play an important role in cluster pattern observed on principal component analysis results. Additionally, hierarchical cluster analysis confirmed this.

A comparison of high- and low-resolution gas chromatography-mass spectrometry for herbal product classification: A case study with Ocimum essential oils.

Selection of marker compounds for targeted chemical analysis is complicated when considering varying instrumentation and closely related plant species. High-resolution gas chromatography-mass spectrometry (GC-MS), via orbitrap detection, has yet to be evaluated for improved marker compound selection. This study directly compares high- and low-resolution GC-MS for botanical maker compound selection using Ocimum tenuiflorum L. (OT) and Ocimum gratissimum L. (OG) for botanical ingredient authentication. The essential oils of OT and OG were collected via hydrodistillation before untargeted chemical analysis with gas chromatography coupled to single-quadrupole (GC-SQ) and orbitrap (GC-Orbitrap) detectors. The Global Natural Products Social Molecular Networking (GNPS) software was used for compound annotation, and a manual search was used to find the 41 most common Ocimum essential oil metabolites. The GC-Orbitrap resulted in 1.7-fold more metabolite detection and increased dynamic range compared to the GC-SQ. Spectral matching and manual searching were improved with GC-Orbitrap data. Each instrument had differing known compound concentrations; however, there was an overlap of six compounds with higher abundance in OG than OT and three compounds with a higher abundance in OT than OG, suggesting consistent detection of the most variable compounds. An unsupervised principal component analysis (PCA) could not discern the two species with either dataset. GC-Orbitrap instrumentation improves compound detection, dynamic range, and feature annotation in essential oil analysis. However, considering both high- and low-resolution data may improve reliable marker compound selection, as GC-Orbitrap analysis alone did not improve unsupervised separation of two Ocimum species compared to GC-SQ data.

Feed as a source of polybrominated diphenyl ethers (PBDEs)

One of the most important routes for human exposure to polybrominated diphenyl ethers (PBDEs) is the ingestion of contaminated food. Food of animal origin safety is strongly related to feed quality. The aim of the study was the assessment of feeds and feed materials quality associated with ten PBDE congeners (BDE-28, 47, 49, 99, 100, 138, 153, 154, 183 and 209) contamination. The quality of 207 feed samples divided into eight categories (277/2012/EU) was checked using the gas chromatography–high resolution mass spectrometry (GC-HRMS). At least one congener was identified in 73% of the samples. All investigated fish oil, animal fat, and feed for fish were contaminated, and 80% of plant-origin feed samples were free of PBDEs. The highest median content of ∑10PBDE was found in fish oils (2260 ng kg−1) followed by fishmeal (530 ng kg−1). The lowest median was found in mineral feed additives, plant materials excluding vegetable oil and compound feed. BDE-209 was the most frequently detected congener (56%). All congeners except BDE-138 and BDE-183 were detected in 100% of the fish oil samples. Except for BDE-209, the congener detection frequencies did not exceed 20% in compound feed, feed of plant origin, and vegetable oils. Excluding BDE-209, similar congener profiles were found for fish oils, fishmeal and feed for fish, with BDE-47 in the highest concentration, followed by BDE-49 and BDE-100. Another pattern appeared in animal fat, with a higher median concentration of BDE-99 than BDE-47. Time-trend analysis of PBDE concentrations in fishmeal (n = 75) showed a 63% decrease in ∑10PBDE (p = 0.077) and a 50% decrease in the ∑9PBDE (p = 0.008) between 2017 and 2021. It proves the international legislation implemented to reduce PBDE environmental levels has been effective.