Quadrupole Mass Spectrometric Detection Research Articles

Investigation of the Cholesterol Biosynthesis by Heart-Cut Liquid Chromatography and Mass Spectrometric Detection

The biosynthesis and homeostasis of cholesterol are essential for cellular function. Cholesterol is a major lipid with multiple roles in membrane stability, signaling, or as a precursor for other molecules. Because of the structural similarity of the sterols involved in the biosynthesis, their accurate identification and quantification is still challenging. Moreover, the huge difference in the concentration of cholesterol and its precursors can cause interferences during the detection. To overcome these problems, a heart-cut liquid chromatographic method was developed by evaluating 38 different columns to achieve optimal separation. The method efficiently separates all sterol biosynthesis intermediates, with detection limits in the low nmol/L-range and an upper limit of quantification of 9 mmol/L for cholesterol by using triple quadrupole mass spectrometric detection. Investigation of lung carcinoma cells treated with statins demonstrated the capability to detect a biological response, showing inhibition of sterol synthesis. This technique offers a robust tool for studying cholesterol biosynthesis and its role in disease.

Routine oxygen heterocyclic compounds analysis of fragrances using an eco-friendly liquid chromatography coupled to tandem mass spectrometry method

ABSTRACT Coumarin and furocoumarins characterization in cosmetics plays an important role in protecting consumer health. The analytical technique mostly employed for the analysis of these molecules is certainly liquid chromatography coupled to photodiode array or mass spectrometer detectors. The aim of this article was to investigate on the oxygen heterocyclic compounds content in fifty hydro alcoholic fragrances using a fast, sensitive and eco-friendly liquid chromatography coupled to a triple quadrupole mass spectrometer detector analytical method without any sample pre-treatment. To the best of the author’s knowledge, this is the first research article on the quantification of thirty-six oxygen heterocyclic compounds in hydro alcoholic fragrances in less than 4 min and with the use of water/ethanol as mobile phase. Thanks to the good performance of the analytical method used, this can be proposed among the routine methods for the quality control of cosmetics and finished products.

Macrocystis pyrifera: A Potential Source of Bioactive Compounds

Background: The Mexican brown seaweed Macrocystis pyrifera is currently unexploited. While this seaweed harvested in other regions has been characterized, changes in the composition can be observed, making it relevant to have a better understanding of the Mexican variety. Objective: The objective of this study was to perform a characterization of the Mexican seaweed M. pyrifera in terms of phenolic and carotenoid profiles, mineral content, antioxidant activity, and chemical composition. Methods: Chemical composition, mineral content, total phenolic content (TPC), and antioxidant activity (ORAC) were measured. Also, the phenolic compounds and carotenoids were quantified using an HPLC coupled with a triple quadrupole mass spectrometer detector. Results: Carbohydrates (48.81 ± 0.05%) were the most abundant macronutrient, while lipids represented only 0.23 ± 0.01 % of the total. From the analyzed minerals (Na, Ca, P, K, and Mg), K was the most abundant with 15,545.23 ± 23.72 mg/100 g. To quantify the phenolic compounds, TPC, and ORAC, two extracts were used (water, and methanol: water (90:10 v/v)), for the carotenoid profile only the latter was used. The most abundant phenolic compound was phloroglucinol (4.45 ± 0.21 μg/g). Ten carotenoids were identified, fucoxanthin the most abundant (1,124.93 ± 3.4 μg/g). Finally, while there was no significant difference (p > 0.05) in the TPC, with values ranging between 16.07 and 17.01 mg GAE/ g, the methanol: water (90:10 (v/v)) extract presented a significantly higher (p < 0.05) antioxidant activity. Conclusion: The characterization of this seaweed can help to determine its potential for several applications.

Methodical support for controlling safety of cereals for children (exemplified by furan and methylfuran)

Introduction. The study addresses issues related to developing a procedure for identification of chemicals in food products in practical instrumental investigations. We have validated the method for quantification of a heterocyclic compound (furan) and sylvan (methylfuran) in grain-based cereals for children.
 The aim of this study was to develop a precise GC-MS-method for quantifying a heterocyclic compound and sylvan in food products to control their safety for children, especially infants.
 Materials and methods. The research objects were quantification means (QM) as a certain amount of an analyzed heterocyclic compound and sylvan (the mass share of the analyzed compound is 99%) provided by Sigma Aldrich Corporation (USA), as well as milk and milk-free dry cereals for babies. The study involved using an Agilent 7890А gas chromatographer with 5975С quadrupole mass-spectrometric detector. Sample preparation involved extraction and concentration of furan and methylfuran from food samples by statistical vapour-liquid equilibrium analysis and subsequent gas-chromatographic analysis of vapour phase.
 Results. The procedure for quantification of furan and methylfuran is an original scientific and technical development based on experimental data. It gives an opportunity to identify furan and methylfuran micro-admixtures in food samples with high precision and sensitivity with a range of concentrations between 0.93 and 9.37 ng and between 0.91 and 9.13 ng accordingly. The ultimate indicators describing acceptability of the results obtained by furan and methylfuran quantification included error not higher than 24%, пintra-laboratory precision (σRл ) not higher than 10%, correctness (± σCл ) not higher than 22%.
 Conclusion. The developed technique has shown high selectivity, sensitivity, reliability and satisfactory accuracy. The methodology meets the criteria of the State Standard of the Russian Federation GOST R ISO 5725-1-6-2002 and can be used for laboratory studies of food safety by enterprises and institutions engaged in quality control and research of food products and food raw materials.

Coumarins of Ferulopsis hystrix: LC–MS Profiling and Gastroprotective and Antioxidant Activities of Skimmin and Peucenidin

Ferulopsis hystrix is a perennial plant of the Apiaceae family. In Buryat and Mongolian medicine, it is used as a substitute for Costus speciosus roots (ru rta), and in Tibetan medicine, it is used to cure digestive system diseases and used as a wound-healing agent. However, its metabolites and their bioactivities are still poorly understood. High-performance liquid chromatography with photodiode array detection and electrospray ionization triple quadrupole mass-spectrometric detection (HPLC–PDA–ESI–tQ–MS/MS) were used to identify approximately 42 phenolic compounds in F. hystrix, and 30 coumarins were characterized and quantified. The major compounds in F. hystrix roots were skimmin (umbelliferone 7-O-glucoside) and peucenidin (vaginidiol 3′-O-acetyl-4′-O-senecioyl ester), of which, gastroprotective and antioxidant effects were found for the first time. The abovementioned compounds exhibit a gastroprotective effect against indomethacin and steroid gastropathy by reducing the amount of damage (point, large, and strip-like erosions) in the gastric mucosa and lowering the corresponding Paul’s index. The most pronounced gastroprotective effect was exhibited by skimmin at a dose of 1 mg/kg and by peucenidin at doses of 16 and 48 mg/kg; these compounds help to limit the development of pronounced erosive–necrotic processes in the gastric mucosa. In pathological conditions, these compounds reduce malondialdehyde, increase the activity of catalase, and increase the content of reduced glutathione in the blood. Thus, this study demonstrates that F. hystrix roots are a good source of bioactive coumarins with gastroprotective potential, which supports earlier ethnopharmacological studies.

Metabolites of Geum aleppicum and Sibbaldianthe bifurca: Diversity and α-Glucosidase Inhibitory Potential.

α-Glucosidase inhibitors are essential in the treatment of diabetes mellitus. Plant-derived drugs are promising sources of new compounds with glucosidase-inhibiting ability. The Geum aleppicum Jacq. and Sibbaldianthe bifurca (L.) Kurtto & T.Erikss. herbs are used in many traditional medical systems to treat diabetes. In this study, metabolites of the G. aleppicum and S. bifurca herbs in active growth, flowering, and fruiting stages were investigated using high-performance liquid chromatography with photodiode array and electrospray ionization triple quadrupole mass spectrometric detection (HPLC-PDA-ESI-tQ-MS/MS). In total, 29 compounds in G. aleppicum and 41 components in S. bifurca were identified including carbohydrates, organic acids, benzoic and ellagic acid derivatives, ellagitannins, flavonoids, and triterpenoids. Gemin A, miquelianin, niga-ichigoside F1, and 3,4-dihydroxybenzoic acid 4-O-glucoside were the dominant compounds in the G. aleppicum herb, while guaiaverin, miquelianin, tellimagrandin II2, casuarictin, and glucose were prevailing compounds in the S. bifurca herb. On the basis of HPLC activity-based profiling of the G. aleppicum herb extract, the most pronounced inhibition of α-glucosidase was observed for gemin A and quercetin-3-O-glucuronide. The latter compound and quercetin-3-O-arabinoside demonstrated maximal inhibition of α-glucosidase in the S. bifurca herb extract. The obtained results confirm the prospects of using these plant compounds as possible sources of hypoglycemic nutraceuticals.

Hogweed Seed Oil: Physico-Chemical Characterization, LC-MS Profile, and Neuroprotective Activity of Heracleum dissectum Nanosuspension.

The seeds of dissected hogweed (Heracleum dissectum Ledeb., Apiaceae) are the source of hogweed oil (HSO), which is still underexplored and requires careful chemical and biological studies. The performed physico-chemical analysis of HSO elucidated basic physical characteristics and revealed the presence of fatty acids, essential oil components, pigments, and coumarins. High-performance liquid chromatography with photodiode array detection and electrospray ionization triple quadrupole mass spectrometric detection (HPLC-PDA-ESI-tQ-MS/MS) identified 38 coumarins that were characterized and quantified. Various furanocoumarins were the major components of HSO polyphenolics, including imperatorin, phellopterin, and isoimperatorin, and the total coumarin content in HSO varied from 181.14 to 238.42 mg/mL. The analysis of storage stability of the selected compounds in HSO indicated their good preservation after 3-year storage at cold and freezing temperatures. The application of the CO2-assisted effervescence method allowed the production of an HSO nanosuspension, which was used in a brain ischemia model of rats. The HSO nanosuspension enhanced cerebral hemodynamics and decreased the frequency of necrotic processes in the brain tissue. Thus, H. dissectum seeds are a good source of coumarins, and HSO nanosuspension promotes neuroprotection of the brain after lesions, which supports earlier ethnopharmacological data.

Influence of plasma ionization on the elastic modulus and tribology behavior of carbon films deposited by the HiPIMS technique

This work reveals the influence of discharge current on carbon-ion energies of plasma, elastic modulus, and friction coefficient at the nano- and macroscale of carbon films deposited via high-power impulse magnetron sputtering. Three applied discharge current conditions in deposition processes were employed to obtain three-carbon films of interest. The number of carbon ions with their energies was obtained via mimic tests of the deposition process using three similar discharge currents through a quadrupole mass spectrometer detector based on the time-averaged ion energy distribution function. The bonding structure of the films was evaluated using Raman spectroscopy, fitting the Diamond and Graphite peaks to obtain a semiquantitative analysis. The elastic modulus of the carbon films was determined from atomic force acoustic microscopy measurements avoiding the influence of the substrates. The friction coefficient was analyzed at the nanoscale via atomic force microscopy and at the macroscale via tribometry. Significant alterations were observed in the number and energy level of the carbon ions with the variation of discharge current. These alterations significantly influenced the bonding properties, elastic modulus, and tribology behavior. A higher elastic modulus and higher sp3 bond content were observed for the film with a lower number of carbon ions and less energy.

Extraction of anabolic steroids with aqueous-organic mixtures from hexanic solutions

The extraction of anabolic steroids (1,4-androstadiene-3,17-dione; 17α-methyltestosterone; 19-norethiocholanolone; 4-hydroxytestosterone; 4-androstene-3,17-dione; 5α-androstane-3β,17β-diol; dehydroepiandrosterone; calusterone; clostebol; methandienone; methyldienolone; nandrolone; testosterone; epitestosterone; tibolone; 19-norandrostenedione; 1-methylene-5α-androstan-3α-ol-17-one) by aqueous-organic mixtures from hexane solutions was studied at the temperature (20 ± 1) °C. Based on the experimental data obtained, the partition ratios of anabolic steroids were calculated, which were used to optimise the standard sample preparation procedure in the process of determining the compounds under study in biologically active dietary supplements and specialised sports nutrition. It was found that the most effective and selective extractants from hydrocarbon solutions are water-acetonitrile mixtures containing from 10 to 20 % by volume of water. An extraction technique has been developed for sample preparation of biologically active dietary supplements for subsequent gas chromatographic determination of anabolic steroids in them using a triple quadrupole mass spectrometric detector. The proposed method is characterised by a standard deviation of 10–15 % and a detection limit about 10 μg/kg of biologically active dietary supplements, which makes it possible to reliably determine impurities of prohibited anabolic steroids in them.

Phytohormones and Elicitors Enhanced the Ecdysteroid and Glycosylflavone Content and Antioxidant Activity of Silene repens

In the course of the ongoing chemical study of species of Silene genus, S. repens Patrin as a common species of the genus, was selected as the object of this study. Using high-performance liquid chromatography with photodiode array detection and electrospray ionization triple quadrupole mass spectrometric detection (HPLC-PDA-ESI-tQ-MS), the presence of 12 ecdysteroids and 6 glycosylflavones was established in S. repens introduced seedlings. 20-Hydroxyecdysone and polypodine B, as well as sileneside E and schaftoside, were the dominant compounds in introduced seedlings of S. repens. The effect of exogenous phytohormones and elicitors on the productivity and accumulation of ecdysteroids and glycosylflavones in introduced seedlings of S. repens was investigated for the first time. It was found that the use of ethyl arachidonate (100 mg/L) to increase the productivity of S. repens is justified. To obtain S. repens with a high content of ecdysteroids and glycosylflavones, it is recommended to apply epibrassinolide (100 mg/L) and 4-chlorophenoxyacetic acid (100 mg/L), respectively. Antioxidant activity of S. repens against 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·) was determined, and it was revealed that sileneside E and schaftoside, as well as meloside A and isovitexin had the highest antioxidant activity among the studied compounds of S. repens.

Metabolites of Prickly Rose: Chemodiversity and Digestive-Enzyme-Inhibiting Potential of Rosa acicularis and the Main Ellagitannin Rugosin D.

Prickly rose (Rosa acicularis Lindl.) is the most distributed rose species in the Northern Hemisphere, used by indigenous people for various food purposes. The lack of detailed information about the chemical composition of R. acicularis has led us to study the phytochemical composition and metabolic profile of prickly rose extracts using chromatographic techniques. Many groups of phenolic and non-phenolic compounds were quantified in the leaves, flowers, roots and fruits of R. acicularis. Phenolic compounds were the dominant phytochemicals in the aerial parts and roots of R. acicularis. A precise study by high-performance liquid chromatography with photodiode array detection and electrospray ionization triple quadrupole mass spectrometric detection showed the presence of 123 compounds, among which ellagic acid derivatives, ellagitannins, gallotannins, catechins, catechin oligomers, hydroxycinnamates and flavonoid glycosides of kaempferol, quercetin and dihydroquercetin were all identified for the first time. The most abundant phenolic compounds were ellagitannins and flavonoid glycosides, with a maximal content of 70.04 mg/g in leaves and 66.72 mg/g in flowers, respectively, indicating the great ability of R. acicularis organs to accumulate phenolic compounds. By applying a standardized static, simulated gastrointestinal digestion method, we found the inhibitory potential of the leaf extract against digestive α-amylases. A pancreatic α-amylase activity-inhibiting assay coupled with HPLC microfractionation demonstrated high inhibition of enzyme activity by ellagitannin rugosin D, which was later confirmed by a microplate reaction with mammalian α-amylases and the simulated digestion method. This study clearly demonstrates that R. acicularis leaf extract and its main component, ellagitannin rugosin D, strongly inhibit digestive α-amylase, and may be a prospective antidiabetic agent.

Metabolites of Siberian Raspberries: LC-MS Profile, Seasonal Variation, Antioxidant Activity and, Thermal Stability of Rubus matsumuranus Phenolome.

Rubus matsumuranus H. Lev. & Vaniot, a famous Siberian shrub of the Rosaceae family, is used in the folk medicine of nomads (Buryats, Yakuts, Soyots, and Mongols) as a remedy for the treatment of diseases of the respiratory and hepatobiliary systems. The lack of scientific information on R. matsumuranus leaves contributed to the investigation of the metabolomic profile and biological activity of this plant. In this study, metabolites of R. matsumuranus leaves in three stages (active growth, flowering, and fruiting) were characterised using high-performance liquid chromatography with photodiode array and electrospray ionisation triple quadrupole mass spectrometric detection (HPLC-PDA-ESI-tQ-MS). In total, 63 compounds were identified, including gallic acid derivatives, hydroxycinnamates, catechins, procyanidins, flavonols, and ellagitannins. Lambertianin C (57.11 mg/g of dry weight, DW), miquelianin (39.63 mg/g DW), and kaempferol-3-O-glucuronide (31.18 mg/g DW) were the major compounds in R. matsumuranus leaves. As a result of the HPLC-PDA-based assay to determine the antioxidant activity, it was revealed that lambertianin A, sanguiin H6, lambertianin C, and sanguiin H11 were effective scavengers of free radicals (2,2-diphenyl-1-picrylhydrazyl, DPPH•) and possessed Fe2+-chelating activity. After an investigation of the phenolic content in infusions and decoctions obtained by extraction with water at different temperatures, it was revealed that a hot infusion (80 °C) is a phenolic-rich preparation of R. matsumuranus leaves. Our research suggests that R. matsumuranus leaves are a rich source of phenolic compounds with high antioxidant properties and that this could be a prospective plant for new functional products.

Water-Soluble Melanoidin Pigment as a New Antioxidant Component of Fermented Willowherb Leaves (Epilobium angustifolium).

Willowherb (Epilobium angustifolium L., family Onagraceae) is a well-known food and medicinal plant used after fermentation as a source of beverages with high antioxidant potential. Despite this long history of use, only a few papers have described the chemical profile and bioactivity of fermented willowherb tea in general. To understand the basic metabolic differences of non-fermented and fermented E. angustifolium leaves, we used general chemical analysis, high-performance liquid chromatography with photodiode array detection and electrospray ionization triple quadrupole mass spectrometric detection assay, and an isolation technique. As a result, the content of 14 chemical groups of compounds was compared in the two plant materials; 59 compounds were detected, including 36 new metabolites; and a new water-soluble phenolic polymer of melanoidin nature was isolated and characterized. The fundamental chemical shifts in fermented E. angustifolium leaves relate mainly to the decrease of ellagitannin content, while there is an increase of melanoidin percentage and saving of the antioxidant potential, despite the significant changes detected. The strong antioxidative properties of the new melanoidin were revealed in a series of in vitro bioassays, and a simulated gastrointestinal and colonic digestion model demonstrated the stability of melanoidin and its antioxidant activity. Finally, we concluded that the new melanoidin is a basic antioxidant of the fermented leaves of E. angustifolium, and it can be recommended for additional study as a promising food and medicinal antioxidant agent.

A new functional food ingredient enriched by Phytoecdisteroids and Polyphenols from quinoa grains (Chenopodium quinoa Willd.)

Objective: Quinoa grains (Chenopodium quinoa Willd.) contain a large number of secondary metabolites. Phytoecdysteroids and polyphenols, secondary metabolites, are of great interest for research today. The aim of the study is a method development for the extraction of biologically active substances (BAS) from quinoa grains to obtain a functional food ingredient (FFI) enriched with phytoecdysteroids and polyphenols. Materials and methods: The content of phytoecdysteroids at each stage of quinoa extract production was determined by two methods: HPLC with a spectrophotometric detector and HPLC with a mass spectrometer. The content of total polyphenols was determined by the Folin-Ciocalteu method. The flavonoid profile was determined using a liquid chromatography system with a diode array spectrophotometric detector and a triple quadrupole mass spectrometric detector. Results: The chosen technological scheme for the production of FFI can concentrate more than 200 times the major phytoecdysteroid 20-hydroxyecdysone major in quinoa in the final product relative to the raw material. The maximum yield of flavonoids in the final product was observed in cases of 20 and 40% ethanol extraction. Conclusion: These results lead to the conclusion that highly enriched sources of BAS can be obtained using fairly simple technological approaches and commercially available reagents from quinoa grains.

Chromato-mass-spectrometric identification of asymmetric dimethylhydrazine and N-nitrosodimethylamine

Introduction. Environmental safety is one of the main priorities of state policy. It ensures the legal regulation of relations in space activities to strengthen the defense and security of the Russian Federation and further extension of the international cooperation of the Russian Federation. Material and methods. In the fall areas of the stages of the booster rockets, screening studies were carried out to identify the propellant component 1.1-unsymmetrical dimethylhydrazine in atmospheric air (n=14) and drinking water (n=23), determine its metabolite N-nitrosodimethylamine quantitatively in the residents’ blood (n = 90) living in the surveyed areas before the rocket launch (n = 45) and after the launch (n = 45). Also quantitative determination of the N-nitrosodimethylamine metabolite in the residents’ urine in the observation group (n = 108) was performed. For comparison, there was selected a group of residents not related to rocket and space activities (n = 13). Identification and analysis of samples of atmospheric air, drinking water, and biological media (blood, urine) was performed using Agilent 7890A gas chromatograph (USA) with a 5975C quadrupole mass spectrometric detector (MCD) and a capillary column of the HP-FFAP 30m • 0.25mm • 0.25µm series. Results. The study revealed the absence of asymmetric 1.1-dimethylhydrazine in 100% of analyzed atmospheric air samples. During the observation period, the concentrations of N-nitrosodimethylamine in the range of 0.00039 to 0.001 mg/dm3 were found in drinking water samples that did not exceed the hygienic standard (LOCNDMA 0.01 mg/dm3). N-nitrosodimethylamine in a concentration range of 0.00095-0.346 mg/dm3 was determined in the blood samples of the population. The studies revealed that after the rocket launch, the N-NDMA concentration in the blood was 1.8 times higher than the concentration registered before the rocket launch. In the urine sample of the resident living in the surveyed area, N-nitrosodimethylamine was detected with a high degree of reliability according to the essential ion with mass 74 m/z and confirmatory ion of 42 m/z, and the concentration was quantitatively calculated at a level of C N-DMA = 0.23 μg/ml. The detection of N-nitrosodimethylamine in blood and urine, even in trace amounts, indicates the possibility of exposure. Conclusion. Performed comprehensive studies made it possible to prove the relative safety of the ecological situation in the fall areas of the booster rockets that are located close to settlements when considering the environmental pollution with unsymmetrical dimethylhydrazine and can be used for systematic monitoring.

Old School Techniques with Modern Capabilities: Kinetics Determination of Dynamical Information Such as Barriers, Multiple Entrance Channel Complexes, Product States, Spin Crossings, and Size Effects in Metallic Ion-Molecule Reactions.

We show how the powerful combination of temperature-dependent kinetics coupled with detailed statistical modeling can be used to derive dynamical information about transition state barrier heights, the importance of multiple entrance channel complexes, crossings between spin surfaces, energetics, product states, and other information for metal-ion reactions. The methods are not new, but with improved computers, ion sources, ion transport, and better detection techniques, the ability to derive such parameters from the combination of methods has improved greatly. Temperature-dependent kinetics is very sensitive to the above list of parameters because the energy is varied in a controlled way that can be easily modeled. The present measurements, performed in our variable-ion source temperature-adjustable selected-ion flow tube (VISTA-SIFT), have been enabled by advances in ion transport and injection improvements so that dim sources can be used. Replacing the quadrupole mass spectrometer detector with a time-of-flight mass spectrometer solved additional problems. Quantum chemical calculations have improved greatly and provide details about the surfaces, as well as frequencies, to use as starting points for the statistical modeling. For ion-molecule reactions, incorporation of both energy and angular momentum effects are important and we have developed an in-house computer program, based on the work of Juergen Troe, to rapidly compare statistical modeling predictions to the experimental data. As we show, modeling the kinetics data can often determine the most important parameters controlling the reactivity and deriving them is much simpler and usually more accurate than detailed ab initio calculations or dynamical modeling. Additionally, we show that even without statistical modeling, temperature-dependent rate constants as a function of metal anion cluster size can be used to show that such species react by the same mechanism as surfaces. In this review, we discuss reactions of metallic atomic ions, small metal oxide ions, mixed metal oxide ions, and a series of metallic anionic cluster reactions with small molecules such as CO, O2, CO2, N2O, CH4, and several other species. Particular attention was paid to reactions involving bond activation pertinent to catalysis.

Chemical changes in thirdhand smoke associated with remediation using an ozone generator

Ozonation is a common remediation approach to eliminate odors from mold, tobacco and fire damage in buildings. Little information exists to: 1) assess its effectiveness; 2) provide guidance on operation conditions; and 3) identify potential risks associated with the presence of indoor ozone and ozonation byproducts. The goal of this study is to evaluate chemical changes in thirdhand smoke (THS) aerosols induced by high levels of ozone, in comparison with THS aerosols aged under similar conditions in the absence of ozone. Samples representing different stages of smoke aging in the absence of ozone, including freshly emitted secondhand smoke (SHS) and THS, were collected inside an 18-m3 room-sized chamber over a period of 42 h after six cigarettes were consumed. The experiments involved collection and analysis of gas phase species including volatile organic compounds (VOCs), volatile carbonyls, semivolatile organic compounds (SVOCs), and particulate matter. VOC analysis was carried out by gas chromatography/mass spectrometry with a thermal desorption inlet (TD-GC/MS), and volatile carbonyls were analyzed by on-line derivatization with dinitrophenylhydrazine (DNPH), followed by liquid chromatography with UV/VIS detection. SVOCs were extracted from XAD-coated denuders and Teflon-coated fiberglass filters in the absence of ozone. In those extracts, tobacco-specific nitrosamines (TSNAs) and other SVOCs were analyzed by gas chromatography with positive chemical ionization-triple quadrupole mass spectrometric detection (GC/PCI-QQQ-MS), and polycyclic aromatic hydrocarbons (PAHs) were quantified by gas chromatography with ion trap mass spectrometric detection (GC/IT-MS) in selected ion monitoring mode. Particulate matter concentration was determined gravimetrically. In a second experiment, a 300 mg h−1 commercial ozone generator was operated during 1 h, one day after smoke was generated, to evaluate the remediation of THS by ozonation. VOCs and volatile carbonyls were analyzed before and after ozonation. Extracts from fabrics that were exposed in the chamber before and after ozonation as surrogates for indoor furnishings were analyzed by GC/IT-MS, and aerosol size distribution was studied with a scanning mobility particle sizer. Ozone concentration was measured with a photometric detector. An estimated 175 mg ozone reacted with THS after 1 h of treatment, corresponding to 58% of the total O3 released during that period. Fabric-bound nicotine was depleted after ozonation, and the surface concentration of PAHs adsorbed to fabric specimens decreased by an order of magnitude due to reaction with ozone, reaching pre-smoking levels. These results suggest that ozonation has the potential to remove harmful THS chemicals from indoor surfaces. However, gas phase concentrations of volatile carbonyls, including formaldehyde, acetaldehyde and acetone were higher immediately after ozonation. Ultrafine particles (UFP, in most cases with size <60 nm) were a major ozonation byproduct. UFP number concentrations peaked shortly after ozonation ended, and remained at higher-than background levels for several hours. Based on these results, minimum re-entry times after ozone treatment were predicted for different indoor scenarios. Clearly defining re-entry times can serve as a practical measure to prevent acute exposures to ozone and harmful ozonation byproducts after treatment. This study evaluated potential benefits and risks associated with THS remediation using ozone, providing insights into this technology.

Phenolome of Asian Agrimony Tea (Agrimonia asiatica Juz., Rosaceae): LC-MS Profile, α-Glucosidase Inhibitory Potential and Stability.

Functional beverages constitute the rapidly increasing part of the functional food section and represent an area with a wide range of products including herbal-based beverages. We carried out screening investigations of the extracts of 85 Rosaceous tea plants. Among the extracts analyzed Agrimonia asiatica herb extract demonstrated the highest inhibitory activity against the enzyme α-glucosidase (20.29 µg/mL). As a result of chromato-mass-spectrometric profiling of A. asiatica herb with high-performance liquid chromatography with photodiode array and electrospray triple quadrupole mass-spectrometric detection (HPLC-PDA-ESI-tQ-MS) 60 compounds were identified, including catechins, ellagitannins, flavones, flavonols, gallotannins, hydroxycinnamates, procyanidins, most for the very first time. The analysis of the seasonal variation of metabolites in A. asiatica herb demonstrated that the phenolic content was highest in summer samples and lower in spring and autumn. HPLC activity-based profiling was utilized to identify compounds of A. asiatica herb with the maximal α-glucosidase inhibitory activity. The most pronounced inhibition of α-glucosidase was observed for agrimoniin, while less significant results of inhibition were revealed for ellagic acid and isoquercitrin. The evaluation of phenolic content in A. asiatica herbal teas with the subsequent determination of α-glucosidase inhibiting potential was discovered. Maximum inhibition of α-glucosidase was observed for hot infusion (75.33 µg/mL) and the minimum for 30 min decoction (159.14 µg/mL). Our study demonstrated that A. asiatica herbal tea is a prospective functional beverage in which dietary intake may help to reduce blood glucose.

Fragaria viridis Fruit Metabolites: Variation of LC-MS Profile and Antioxidant Potential during Ripening and Storage.

Fragaria viridis Weston or creamy strawberry is one of the less-known species of the Fragaria genus (Rosaceae family) with a wide distribution in Eurasia and is still in the shadow of more popular relatives F. ananassa (garden strawberry) or F. vesca (wild strawberry). Importantly, there is a lack of scientific knowledge on F. viridis compounds, their stability in the postharvest period, and bioactivity. In this study, metabolites of F. viridis fruits in three ripening stages were characterized with high-performance liquid chromatography with photodiode array and electrospray ionization triple quadrupole mass spectrometric detection (HPLC-PAD-ESI-tQ-MS). In total, 95 compounds of various groups including carbohydrates, organic acids, phenolics, and triterpenes, were identified for the first time. The quantitative content of the compounds varied differently during the ripening progress; some of them increased (anthocyanins, organic acids, and carbohydrates), while others demonstrated a decrease (ellagitannins, flavonols, etc.). The most abundant secondary metabolites of F. viridis fruits were ellagitannins (5.97–7.54 mg/g of fresh weight), with agrimoniin (1.41–2.63 mg/g) and lambertianin C (1.20–1.86 mg/g) as major components. Antioxidant properties estimated by in vitro assays (2,2-diphenyl-1-picrylhydrazyl radical (DPPH), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) cation radical (ABTS), ferric reducing antioxidant power (FRAP), and oxygen radical absorbance capacity (ORAC)) showed good antioxidant potential in all ripening stages of F. viridis fruits. The pilot human experiment on the effect of F. viridis fruit consumption on the serum total antioxidant capacity confirmed the effectiveness of this kind of strawberry. Postharvest storage of ripe fruits at 4 °C and 20 °C lead to declining content in the majority of compounds particularly ascorbic acid, ellagitannins, and flavonols, with the most significant loss at room temperature storage. These results suggest that F. viridis fruits are a prospective source of numerous metabolites that have potential health benefits.

Chromato-mass spectrometric identification of asymmetric dimethylhydrazine and its derivatives in environmental objects and biological media in the population residing near the fall areas of separated rocket vehicles parts

Introduction. The issue of presence/absence of the consequences of technogenic space and rocket activity over the long period is on the agenda of the professional, social, and political communities, especially in regions were the certain territories have been appointed as the fall areas for the separated rocket vehicles parts, including the Republic of Altai.Aim of study. Identification of the chemical composition of snow samples, drinking water, and blood in the population residing in the fall areas of the separated rocket vehicle parts in the Republic of Altai.Material and methods. Identification of the chemical composition has been performed along with the quantitative determination of the content of N-nitrosamines in blood samples (n=50) in n the population who constantly live near to the fall areas of the separated rocket vehicles, as well snow samples (n=7), and drinking water (n=9). The samples were examined by a hybrid method using an Agilent gas chromatograph with a quadrupole mass spectrometric detector. In order to decrypt the results of the mass spectrometric analysis, we used the NIST Mass Spectrometry Data Library 08.L, WILEY275.L, PMW_TOX2.L., libraries of the United States Environmental Protection Agency, narcotic, herbal, toxic and contaminated substances. The quantitative determination of N-nitrosamines in the blood samples was performed by the method of chromatography-mass spectrometry.Results. During the library search, 94% of the studied blood samples in the population registered substances that can be identified as unsymmetric dimethylhydrazine and 6% of the samples contain its decomposition product N-nitrosodimethylamine. However, the probability of categorizing these impurities to the desired substances was of 4-26%. In the blood samples of residents in whom there were identified asymmetric dimethylhydrazine and N-NDMA by quantitative chromatography-mass spectrometric analysis, the tag (Alt+2) N-nitrosodimethylamine and N-nitrosodiethylamine was found in the concentration range of 0.00095-0.346 mg/dm3. In 100% of the studied drinking water samples, residual amounts of asymmetric dimethylhydrazine were identified with a low probability of matching the library mass spectrum of 12-33%.Conclusion. The conducted chromatography-mass spectrometry studies of snow samples, samples of the water, and blood of the population living near to the fall area of the separated rocket vehicle parts in the Republic of Altai allowed establishing the signs of residual quantities of dimethylhydrazine and N-nitrozodimethylamine.