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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, 30 min). 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 0.2-15 µg/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.
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Water treatment for most public pools involves disinfection with active chlorine leading to the formation of disinfection by-products (DBPs). Among them, nitrogen-containing compounds (N-DBPs) having increased toxicity and adverse effects on human health are of the greatest concern. Being the major component of various body washers for swimmers, cocamidopropyl betaine (CAPB) represents a potential and still underestimated anthropogenic precursor of N-DBPs in pool water. The purpose of this study was to investigate CAPB transformation pathways and mechanisms under the aqueous chlorination conditions. High-performance liquid and two-dimensional gas chromatography hyphenated with high-resolution mass spectrometry were used for the search and tentative identification of the primary and final CAPB transformation products. A wide range of DBPs containing up to five chlorine atoms including these in combination with hydroxyl and additional carbonyl groups has been revealed in model chlorination experiments for the first time. The proposed mechanism of their formation involves nucleophilic substitution of the secondary amide hydrogen atom at the first stage with subsequent free radical and electrophilic addition reactions resulting in non-selective introduction of halogen atoms and hydroxyl groups in the alkyl chain. The deep transformation products include short-chain chlorinated hydrocarbons and their oxidation products as well as dimethylcarbamoyl chloride possessing high toxicity and carcinogenic properties. Targeted analysis of real swimming pool water samples confirmed the results of model experiments enabling semi-quantitative determination of CAPB (0.8 µg L-1) and 18 primary DBPs, including 10 chlorine-containing compounds with the total concentration of 0.1 µg L-1. Among them, monochloro (50%) and hydroxydichloro (25%) derivatives predominate. The toxicity and health of the main DBPs has been estimated using QSAR/QSTR approach. Thus, the possibility of formation of new classes of potentially toxic chlorine-containing DBPs associated with the widespread use of detergents and cosmetics was shown.
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Betaína/análogos & derivados , Compostos Clorados , Desinfetantes , Hidrocarbonetos Clorados , Piscinas , Poluentes Químicos da Água , Purificação da Água , Humanos , Desinfecção , Desinfetantes/química , Cloro/química , Nitrogênio/análise , Hidrocarbonetos Clorados/análise , Compostos Clorados/análise , Halogenação , Compostos de Nitrogênio , Cloretos , Poluentes Químicos da Água/análiseRESUMO
Lignans constitute a large group of phenolic plant secondary metabolites possessing high bioactivity. Their accurate determination in plant extracts with a complex chemical composition is challenging and requires advanced separation techniques. In the present study, a new approach to the determination of lignans in coniferous knotwood extracts as the promising industrial-scale source of such compounds based on comprehensive two-dimensional liquid chromatography separation and UV spectrophotometric detection is proposed. First and second-dimension column screening showed that the best results can be obtained using a combination of non-polar and polar hydroxy group embedded octadecyl stationary phases with moderate (~40%) "orthogonality". The optimization of LC × LC separation conditions allowed for the development of a new method for the quantification of the five lignans (secoisolariciresinol, matairesinol, pinoresinol, 7-hydroxymatairesinol, and nortrachelogenin) in knotwood extracts with limits of quantification in the range of 0.27-0.95 mg L-1 and a linear concentration range covering at least two orders of magnitude. Testing the developed method on coniferous (larch, fir, spruce, and pine) knotwood extracts demonstrated the high selectivity of the analysis and the advantages of LC × LC in the separation and accurate quantification of the compounds co-eluting in one-dimensional HPLC.
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Lignanas , Lignanas/química , Cromatografia Líquida de Alta Pressão/métodos , Plantas/químicaRESUMO
Arctic brown algae are considered a promising industrial-scale source of bioactive sub-stances as polysaccharides, polyphenols, and low-molecular secondary metabolites. Conventional technologies for their processing are focused mainly on the isolation of polysaccharides and involve the use of hazardous solvents. In the present study a "green" approach to the fractionation of brown algae biomass based on the dissolution in ionic liquids (ILs) with 1-butil-3-methylimidazolium (bmim) cation with further sequential precipitation of polysaccharides and polyphenols with acetone and water, respectively, is proposed. The effects of IL cation nature, temperature, and treatment duration on the dissolution of bladderwrack (Fucus vesiculosus), yields of the fractions, and their chemical composition were studied involving FTIR and NMR spectroscopy, as well as size-exclusion chromatography and monosaccharide analysis. It was shown that the use of bmim acetate ensures almost complete dissolution of plant material after 24 h treatment at 150 °C and separate isolation of the polysaccharide mixture (alginates, cellulose, and fucoidan) and polyphenols (phlorotannins) with the yields of ~40 and ~10%, respectively. The near-quantitative extraction of polyphenolic fraction with the weight-average molecular mass of 10-20 kDa can be achieved even under mild conditions (80-100 °C). Efficient isolation of polysaccharides requires harsh conditions. Higher temperatures contribute to an increase in fucoidan content in the polysaccharide fraction.
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Fucus , Líquidos Iônicos , Phaeophyceae , Fucus/química , Biomassa , Phaeophyceae/química , Polissacarídeos/química , Polifenóis/análise , CátionsRESUMO
Lignin is considered a promising renewable source of valuable chemical compounds and a feedstock for the production of various materials. Its suitability for certain directions of processing is determined by the chemical structure of its macromolecules. Its formation depends on botanical origin, isolation procedure and other factors. Due to the complexity of the chemical composition, revealing the structural differences between lignins of various origins is a challenging task and requires the use of the most informative methods for obtaining and processing data. In the present study, a combination of two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy and multivariate analysis of heteronuclear single quantum coherence (HSQC) spectra is proposed. Principal component analysis and hierarchical cluster analysis techniques demonstrated the possibility to effectively classify lignins at the level of belonging to classes and families of plants, and in some cases individual species, with an error rate for data classification of 2.3%. The reverse transformation of loading plots into the corresponding HSQC loading spectra allowed for structural information to be obtained about the latent components of lignins and their structural fragments (biomarkers) responsible for certain differences. As a result of the analysis of 34 coniferous, deciduous, and herbaceous lignins, 10 groups of key substructures were established. In addition to syringyl, guaiacyl, and p-hydroxyphenyl monomeric units, they include various terminal substructures: dihydroconiferyl alcohol, balanopholin, cinnamic acids, and tricin. It was shown that, in some cases, the substructures formed during the partial destruction of biopolymer macromolecules also have a significant effect on the classification of lignins of various origins.
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Pentacyclic triterpenoids (PCTs), which possess a number of bioactive properties, are considered one of the most important classes of secondary plant metabolites. Their chromatographic determination in plant biomass is complicated by the need to separate a large number of structurally similar compounds belonging to several classes that differ greatly in polarity (monools, diols, and triterpenic acids). This study proposes a rapid, sensitive, and low-cost method for the simultaneous quantification of ten PCTs (3ß-taraxerol, lupeol, ß-amyrin, α-amyrin, betulin, erythrodiol, uvaol, betulinic, oleanolic, and ursolic acids) by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) using porous graphitic carbon (Hypercarb) as a stationary phase capable of hydrophobic retention and specific interactions with analytes. Revealing the effects of the mobile phase composition, pH, ionic strength, and column temperature on retention and selection of chromatographic conditions on this basis allowed for the effective separation of all target analytes within 8 min in gradient elution mode and attaining limits of detection in the range of 4-104 µg L-1. The developed method was fully validated and successfully tested in the determination of PCTs in common haircap (Polytrichum commune) and prairie sphagnum (Sphagnum palustre) mosses, and fireweed (Chamaenerion angustifolium) stems and leaves.
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Grafite , Espectrometria de Massas em Tandem , Carbono , Biomassa , Porosidade , Cromatografia Líquida/métodos , Triterpenos Pentacíclicos/química , Cromatografia Líquida de Alta Pressão/métodos , Grafite/química , PlantasRESUMO
Cloudberry (Rubus chamaemorus L.) is a circumpolar boreal plant rich in bioactive compounds and is widely used in food and in folk medicine. In this study, a combination of two-dimensional NMR spectroscopy and liquid chromatography-high-resolution mass spectrometry was used for the comprehensive characterization of secondary metabolites in cloudberry lipophilic and hydrophilic extracts. Special attention was paid to the leaf extractives, which are highly enriched in polyphenolic compounds, the content of which reaches 19% in the extract (in gallic acid equivalent). The chemical composition of the polyphenolic fraction is represented mainly by the glycosylated derivatives of flavonoids, hydroxycinnamic (primarily caffeic), gallic (including the structure of galloyl ascorbate) and ellagic acids, catechin, and procyanidins. The contents of aglycones in the polyphenolic fraction were 64 and 100 mg g-1 for flavonoids and hydroxycinnamic acids, respectively, while the content of free caffeic acid was 1.2 mg g-1. This determines the exceptionally high antioxidant activity of this fraction (750 mg g-1 in gallic acid equivalent) and the ability to scavenge superoxide anion radicals, which is 60% higher than that of Trolox. The lower polar fractions consist mainly of glycolipids, which include polyunsaturated linolenic acid (18:3), pentacyclic triterpenic acids, carotenoid lutein, and chlorophyll derivatives, among which pheophytin a dominates. Along with the availability, the high antioxidant and biological activities of cloudberry leaf extracts make them a promising source of food additives, cosmetics, and pharmaceuticals.
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The marine environment has a significant impact on life on Earth. Organisms residing in it are vital for the ecosystem but also serve as an inexhaustible source of biologically active compounds. Herein, the biodiversity of two brown seaweeds, Dictyota dichotoma and Dictyota fasciola from the Adriatic Sea, was evaluated. The aim of the study was the determination of differences in compound composition while comparing their activities, including antioxidant, antimicrobial, and enzyme inhibition, in connection to human digestion, dermatology, and neurological disorders. Chemical analysis revealed several terpenoids and steroids as dominant molecules, while fucoxanthin was the main identified pigment in both algae. D. dichotoma had higher protein, carbohydrate, and pigment content. Omega-6 and omega-3 fatty acids were identified, with the highest amount of dihomo-γ-linolenic acid and α-linolenic acid in D. dichotoma. Antimicrobial testing revealed a dose-dependent inhibitory activity of methanolic fraction against Escherichia coli and Staphylococcus aureus. Moderate antioxidant activity was observed for both algae fractions, while the dietary potential was high, especially for the D. fasciola dichloromethane fraction, with inhibition percentages of around 92% for α-amylase and 57% for pancreatic lipase at 0.25 mg/mL. These results suggest that Dictyota species might be a potent source of naturally derived agents for obesity and diabetes.
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A knotwood of coniferous trees containing large amounts of polyphenolic extractives is considered a promising industrial-scale source of lignans possessing antioxidant properties and other bioactivities. The present study is aimed at a detailed characterization of the chemical composition and antioxidant activity of lignan-rich extractives obtained from the knotwood of the Norway spruce, Scotch pine, Siberian fir, and Siberian larch growing in the European North of Russia as a region with a highly developed forest industry. To achieve this, a comprehensive approach based on a combination of two-dimensional NMR spectroscopy with high-performance liquid chromatography-high-resolution Orbitrap mass spectrometry, and the determination of antioxidant activity by the three complementary methods were proposed. The studied knotwood samples contained from 3.9 to 17% of extractive substances and were comparable to Trolox's antioxidant activity in the single-electron transfer processes and superoxide radical scavenging, which is associated with the predominance of polyphenolic compounds. The latter was represented by 12 tentatively identified monolignans and 27 oligolignans containing 3-5 phenylpropane units in their structure. The extracts were characterized by an identical set of lignans and differed only in the ratios of their individual compounds. Other components of the knotwood were flavonoids taxifolin, quercetin (Siberian larch), and three stilbenes (pinosylvin, its methyl ester, and pterostilbene), which were identified in the Scotch pine extractives. Sesquiterpene juvabione and its derivatives were found in extracts of Siberian larch knotwood.
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One of the most widespread representatives of mosses in the temperate and boreal latitudes of the Northern Hemisphere is common haircap (Polytrichum commune), which is known as the largest moss in the world and widely used in traditional herbal medicine. Polyphenolic compounds constitute one of the most important groups of biologically active secondary metabolites of P. commune, however, the available information on their chemical composition is still incomplete and contradictory. In the present study, a group of dihydrochalcone polyphenolic derivatives that were not previously found in mosses was isolated from P. commune biomass using pressurized liquid extraction with aqueous acetone. The combination of two-dimensional NMR spectroscopy and high-performance liquid chromatography-high-resolution mass spectrometry allowed for identifying them as 3-hydroxyphloretin oligomers formed through a carbon-carbon bond between phloroglucinol and pyrocatechol moieties ("head-to-tail" coupling), with a polymerization degree of 2-5. The individual compounds isolated by preparative reverse-phase HPLC had a purity of 71 to 97% and demonstrated high radical scavenging activity (17.5-42.5% with respect to Trolox) determined by the photochemiluminescence method. Along with the low toxicity predicted by QSAR/QSTR algorithms, this makes 3-hydroxyphloretin oligomers a promising source for the production of biologically active food additives and pharmaceuticals.
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One of the most promising applications of ionic liquids (ILs) with 1-butyl-3-methylimidazolium (bmim) cation is based on their unique ability to dissolve and fractionate lignocellulosic biomass, allowing for the development of green biorefining technologies. A complete dissolution of lignocellulose requires prolonged treatment at elevated temperatures, which can cause the partial degradation of ILs. In the present study, a combination of various analytical techniques (GC-MS, HPLC-HRMS, 2D-NMR, synchronous thermal analysis) was used for the comprehensive characterization of bmim acetate, chloride, and methyl sulfate degradation products formed at 150 °C during 6- and 24-h thermal treatment. A number of volatile and non-volatile products, including monomeric and dimeric alkyl substituted imidazoles, alcohols, alkyl amines, methyl and butyl acetates, and N-alkylamides, was identified. By thermal lability, ILs can be arranged in the following sequence, coinciding with the decrease in basicity of the anion: [bmim]OAc > [bmim]Cl > [bmim]MeSO4. The accumulation of thermal degradation products in ILs, in turn, affects their physico-chemical properties and thermal stability, and leads to a decrease in the decomposition temperature, a change in the shape of the thermogravimetric curves, and the formation of carbon residue during pyrolysis.
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Líquidos Iônicos , Aminas , Carbono , Cátions , Cloretos , Imidazóis/química , Líquidos Iônicos/químicaRESUMO
Phthalic acid esters are widely used as components of industrial and consumer products including paper and cardboard packaging materials in contact with food or human skin. Being endocrine-disrupting chemicals, phthalic acid esters have a negative effect on human health and must be controlled in pulp and paper products. In the present study, supercritical fluid chromatography-tandem mass spectrometry in combination with pressurized liquid extraction was proposed for phthalic acid esters determination in such objects. Octadecyl stationary phase with non-endcapped silanol groups ensured rapid (4 min) separation of the 10 priority phthalic acid esters in isocratic elution mode and allowed for effective elimination of interferences from the trace impurities of phthalic acid esters in the mobile phase. The attained limits of quantitation are in the range of 0.7-10 µg/L in extracts and 0.02-0.3 µg/g in paper and cardboard samples. The developed method is distinguished by analysis rapidity, easy sample preparation procedure, high selectivity, low susceptibility to mobile phase contamination with analytes, low cost, and environmental friendliness due to the use of carbon dioxide as a main component of the mobile phase. The method was successfully tested on real samples of toilet paper and food packaging paper and cardboard in which eight analytes were found at the levels of 0.03-43.5 µg/g.
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Cromatografia com Fluido Supercrítico , Ácidos Ftálicos , Humanos , Espectrometria de Massas em Tandem/métodos , Ácidos Ftálicos/análise , Embalagem de Alimentos , Cromatografia Líquida de Alta Pressão , Extração em Fase SólidaRESUMO
When released to the environment, the rocket fuel unsymmetrical dimethylhydrazine (UDMH) undergoes oxidative transformations, resulting in the formation of an extremely large number of nitrogen-containing transformation products, including isomeric compounds which are difficult to discriminate by common chromatography techniques. In the present work, supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS) was proposed for resolving the problem of fast separation and simultaneous quantification of 1-formyl-2,2-dimethylhydrazine (FADMH) as one of the major UDMH transformation products, and its isomers-1,1-dimethylurea (UDMU) and 1,2-dimethylurea (SDMU). 2-Ethylpyridine stationary phase provided baseline separation of analytes in 1.5 min without the distortion of the chromatographic peaks. Optimization of SFC separation and MS/MS detection conditions allowed for the development of rapid, sensitive, and "green" method for the simultaneous determination of FADMH, UDMU, and SDMU in environmental samples with LOQs of 1-10 µg L-1 and linear range covering three orders of magnitude. The method was validated and successfully tested on the real extracts of peaty and sandy soils polluted with rocket fuel and UDMH oxidation products. It was shown that both UDMU and SDMU are formed in noticeable amounts during UDMH oxidation. Despite relatively low toxicity, UDMU can be considered one of the major UDMH transformation products and a potential marker of soil pollution with toxic rocket fuel.
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Cromatografia com Fluido Supercrítico , Cromatografia com Fluido Supercrítico/métodos , Dimetilidrazinas/análise , Dimetilidrazinas/química , Solo/química , Espectrometria de Massas em Tandem/métodosRESUMO
Reactions of 3-(furan-2-yl)propenoic acids and their esters with arenes in Brønsted superacid TfOH affords products of hydroarylation of the carbon-carbon double bond, 3-aryl-3-(furan-2-yl)propenoic acid derivatives. According to NMR and DFT studies, the corresponding O,C-diprotonated forms of the starting furan acids and esters should be reactive electrophilic species in these transformations. Starting compounds and their hydroarylation products, at a concentration of 64 µg/mL, demonstrate good antimicrobial activity against yeast-like fungi Candida albicans. Apart from that, these compounds suppress Escherichia coli and Staphylococcus aureus.
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Anti-Infecciosos , Propionatos , Anti-Infecciosos/química , Carbono , Escherichia coli , Ésteres/farmacologia , Furanos/farmacologia , Testes de Sensibilidade MicrobianaRESUMO
Pentacyclic triterpenoids (PCTs) are a widely distributed class of plant secondary metabolites. These compounds have high bioactive properties, primarily antitumor and antioxidant activity. In this study, a method was developed for the quantitative analysis of pentacyclic triterpenoids in plants using supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS). Separation of ten major PCTs (friedelin, lupeol, ß-amyrin, α-amyrin, betulin, erythrodiol, uvaol, betulinic, oleanolic and ursolic acids) was studied on six silica-based reversed stationary phases. The best results (7 min analysis time in isocratic elution mode) were achieved on an HSS C18 SB stationary phase using carbon dioxide-isopropanol (8%) mobile phase providing decisive contribution of polar interactions to the retention of analytes. It was shown that the use of atmospheric pressure chemical ionization (APCI) is preferred over atmospheric pressure photoionization (APPI). The combination of SFC with APCI-MS/MS mass spectrometry made it possible to achieve the limits of quantification in plant extracts in the range of 2.3-20 µg·L-1. The developed method was validated and tested in the analyses of birch outer layer (Betula pendula) bark, and licorice (Glycyrrhiza glabra) root, as well as lingonberry (Vaccinium vitis-idaea), cranberry (Vaccinium oxycoccos), apple (Malus domestica "Golden Delicious" and Malus domestica "Red Delicious") peels.
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This work is dedicated to the investigation of additives effects on retention mechanisms in supercritical fluid chromatography. Additives are compounds which are added to the mobile phase in small quantities and greatly affect retention factors, peak shape, separation selectivity and other chromatographic parameters. Linear free energy relationship (LFER) method with an expanded set of descriptors including the ones taking ionic interactions into account was used to probe the effect of four types of additive: trifluoroacetic acid, diethylamine, ammonium acetate and water - on retention on four polar stationary phase bearing different functional groups: bare silica, cyano, 2-ethylpyridine and zwitter-ionic sulfobetaine. Effects of all additives were shown to be complex, involving different intermolecular interactions and not uniform. The direction and magnitude of retention change depends not only on additive concentration, but on all other component of a chromatography system: type of a stationary phase, mobile phase composition and the nature of the solute. Various subtle effects were registered, the most peculiar among them being the fact that diethylamine and ammonium acetate provide identical changes of LFER constants. We hypothesize that this is caused by the convergence of diethylamine into a methylcarbamate via reaction with carbon dioxide and methanol, which then behaves as a salt additive.
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Cromatografia com Fluido Supercrítico , Dióxido de Carbono , Metanol , Soluções , ÁguaRESUMO
An indole derivative umifenovir (Arbidol) is one of the most widely used antiviral drugs for the prevention and treatment of COVID-19 and some other viral infections. The purpose of the present study was to shed light on the transformation processes of umifenovir in municipal wastewater, including disinfection with active chlorine, as well as to assess the levels of the antiviral drug and its metabolites entering and accumulating in natural reservoirs under conditions of the SARS-CoV-2 pandemic. The combination of high-performance liquid chromatography with electrospray ionization high-resolution mass-spectrometry and inductively coupled plasma mass spectrometry was used for tentative identification and quantification of umifenovir and its transformation products in model reaction mixtures and real samples of wastewater, river water, biological sludge and bottom sediments taken at the wastewater treatment plant in Arkhangelsk, a large cultural and industrial center at the Russian North. Laboratory experiments allowed identifying fifteen bromine-containing transformation products, forming at the initial stages of the chlorination and fourteen classic volatile and semi volatile disinfection by-products with bromoform as the dominant one. Chlorinated derivatives are only the minor disinfection by-products forming by substitution of alkylamine group in the aromatic ring. The schemes of umifenovir transformation in reactions with dissolved oxygen and sodium hypochlorite are proposed. Two established primary transformation products formed by oxidation of the thioether group to sulfoxide and elimination of thiophenol were detected in noticeable concentrations in the wastewater together with their precursor. The level of umifenovir reached 1.3 mg kg-1 in the sludge and municipal wastewater treat contained 1 µg L-1 of that drug, while its removal during biological wastewater treatment was about 40%. Pronounced accumulation of umifenovir and its transformation products in biological sludge and bottom sediments of natural reservoirs may be a source of the future secondary pollution of the environment.
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COVID-19 , Poluentes Químicos da Água , Antivirais , Humanos , Indóis , Pandemias , SARS-CoV-2 , Águas Residuárias , Poluentes Químicos da Água/análiseRESUMO
The use of highly toxic rocket fuel based on 1,1-dimethylhydrazine (UDMH) in many types of carrier rockets poses a threat to environment and human health associated with an ingress of UDMH into wastewater and natural reservoirs and its transformation with the formation of numerous toxic nitrogen-containing products. Their GC-MS quantification in aqueous samples requires matrix change and is challenging due to high polarity of analytes. To overcome this problem, accelerated water sample preparation (AWASP) based on the complete removal of water with anhydrous sodium sulfate and transferring analytes into dichloromethane was used. Twenty-nine UDMH transformation products including both the acyclic and heterocyclic compounds of various classes were chosen as target analytes. AWASP ensured attaining near quantitative extraction of 23 compounds with sample preparation procedure duration of no more than 5 min. Combination of AWASP with gas chromatography-mass spectrometry and using pyridine-d5 as an internal standard allowed for developing the rapid, simple, and low-cost method for simultaneous quantification of UDMH transformation products with detection limits of 1-5 µg L-1 and linear concentration range covering 4 orders of magnitude. The method has been validated and successfully tested in the analysis of aqueous solutions of rocket fuel subjected to oxidation with atmospheric oxygen, as well as pyrolytic gasification in supercritical water modelling wastewater from carrier rockets launch sites.
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Lignin is the second most abundant biopolymer in nature and is considered an important renewable source of aromatic compounds. One of the most promising analytical methods for molecular characterization of lignin is Orbitrap high-resolution mass spectrometry with atmospheric pressure photoionization (APPI), proved itself in the study of lignins of various origins and their depolymerization products. In this work, the photoionization of lignin using acetone, 1,4-dioxane, and THF as solvents for the biopolymer and APPI dopants providing the generation of protonated and deprotonated molecules of lignin oligomers has been studied. The ionization conditions were optimized on the basis of the dependences of the total ion current on temperature and the flow rate of the solution into the ion source. Lignin degradation processes under APPI conditions occur mainly with the cleavage of ether ß-O-4 bonds between phenylpropane structural units, demethylation (negative ion mode), as well as the loss of water and formaldehyde (positive ion mode). Negative ion mode APPI provides a higher ionization efficiency in the region of high molecular weights, however, it is characterized by an increased fragmentation of ß-O-4 ether bonds compared to APPI(+) leading to a partial depolymerization of lignin in the ion source. The combination of APPI with Orbitrap high-resolution mass spectrometry allows obtaining mass spectra of coniferous and deciduous wood lignins with resolved fine structure and containing signals of up to 3000 oligomers in the mass range of 300-1800 Da. This can be used for comprehensive characterization of lignins at molecular level and tracking changes in biopolymer chemical composition in various processes.
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Pressão Atmosférica , Lignina , Espectrometria de Massas , Compostos Orgânicos , MadeiraRESUMO
With everyday advances in the field of pharmaceuticals, medicinal plants have high priority regarding the introduction of novel synthetic compounds by the usage of environmentally friendly extraction technologies. Herein, a supercritical CO2 extraction method was implemented in the analysis of four plants (chamomile, St. John's wort, yarrow, and curry plant) after which the non-targeted analysis of the chemical composition, phenolic content, and antioxidant activity was evaluated. The extraction yield was the highest for the chamomile (5%), while moderate yields were obtained for the other three plants. The chemical composition analyzed by gas chromatography-high-resolution mass spectrometry (GC-HRMS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS) demonstrated extraction of diverse compounds including terpenes and terpenoids, fatty acids, flavonoids and coumarins, functionalized phytosterols, and polyphenols. Voltammetry of microfilm immobilized on a glassy carbon electrode using square-wave voltammetry (SWV) was applied in the analysis of extracts. It was found that antioxidant activity obtained by SWV correlates well to 1,1-diphenyl-2-picrylhidrazine (DPPH) radical assay (R2 = 0.818) and ferric reducing antioxidant power (FRAP) assay (R2 = 0.640), but not to the total phenolic content (R2 = 0.092). Effective results were obtained in terms of activity showing the potential usage of supercritical CO2 extraction to acquire bioactive compounds of interest.