Precursor Compounds Research Articles

Automated simultaneous identification of methamphetamine, precursor compounds to methamphetamine and their metabolites in urine for proof of methamphetamine use

Automated simultaneous identification of methamphetamine, precursor compounds to methamphetamine and their metabolites in urine for proof of methamphetamine use

Héjon erjesztett natúrborok vizsgálata

The ancient white wine making technology, the “qvevri”, is gaining more and more attention among consumers, not only because it is unique and special, but also because sustainability and closeness to nature are fundamental characteristics of this winemaking process. All of this is demonstrated by the fact that this ancient Georgian process using traditional clay vessels was added to the UNESCO List of Intangible Cultural Heritage of Humanity in 2013, and in 2020, The International Organisation of Vine and Wine (OIV) included skin-fermented white wine in the category of special wines. This wave is also present in Hungary, since “natural” wine and “orange wine” have already appeared in a 2021 law as „Other restricted terms”. The essence of the winemaking process is skin-contact fermentation and microoxidation, for which a number of vessels can be used: amphoras or qvevris, ceramic eggs or spin barrels, as a function of which the chemical composition of the wines may vary, as well as the formation of the precursor compounds of the aroma components. In this study, natural wines produced in the Tokaj wine region, using amphoras and ceramic egg vessels were examined.

Molecular Docking Studies of Halogenated Bicyclo[4.2.0] Inositols with SARS-CoV-2 Proteins

Cyclic sulfate is the precursor compound that can adapt well to the binding sites of the docked proteins of SARS-CoV-2. Cyclic sulfate showed very strong molecular interactions for the 6lu7, 6zb5, and 6vww proteins of SARS-CoV-2, with binding energies of -7.33, -7.29, and -7.29 kcal mol-1, respectively. Besides, acetate showed very strong molecular interactions with -7.45 kcal mol-1 for the 6lu7 protein of SARS-CoV-2. Therefore, according to our results, cyclic sulfate and acetate should be investigated as promising drug candidates for the treatment of COVID-19.

Genesis and Properties of MOx/CNTs (M = Ce, Cu, Mo) Catalysts for Aerobic Oxidative Desulfurization of a Model Diesel Fuel

Aerobic oxidative desulfurization of a model diesel fuel over MOx/CNTs catalysts (M = Ce, Cu, Mo) was studied to develop innovative technology for cleaning motor fuels to EURO-5 standard. It was shown that the thermal stability of catalysts improves in the following order of metal Сu < Сe < Мо. The disordering of the carbon matrix of support increases in the next row of M: Mo < Ce < Cu, which is accompanied by an increase in the specific surface area of the samples (40 → 105 m2/g). The forms of stabilization of the active component (CeO2, CuO/Cu2O/ Cu, or MoO3/MoO2) were revealed, indicating a partial reduction of the metal cations during the thermal decomposition of copper and molybdenum precursor compounds deposited on CNTs. In oxidative desulfurization of a model diesel fuel over MOx/CNTs catalysts at 150 °C the total conversion of dibenzothiophene increased in the next row of M: Се < Сu < Мо. It was found that at 150 °C over the optimum MoOx/CNTs catalyst the highest dibenzothiophene conversion 95–99% is observed. It was assumed that the high activity of MoOx/CNTs is associated with both the oxidizing ability and the tendency of MoOx to chemosorption of sulfur compounds.

Determination of 18 Intact Glucosinolates in Brassicaceae Vegetables by UHPLC-MS/MS: Comparing Tissue Disruption Methods for Sample Preparation.

Glucosinolates (GSLs) are important precursor compounds with anticancer activities in Brassicaceae vegetables and are readily hydrolyzed by myrosinase. Given the diversity of these species, establishing an accurate and universal method to quantify intact GSLs in different plant tissues is necessary. Here, we compared and optimized three tissue disruption methods for sample preparation. After microwave treatment for 90 s, 13 GSLs in homogenized Chinese cabbage samples were recovered at 73–124%. However, a limitation of this method was that different tissues could not be processed under the same microwave conditions. Regarding universality, GSLs in Brassicaceae vegetables could be extracted from freeze-dried sample powder with 70% methanol (v/v) or frozen-fresh sample powder with 80% methanol (v/v). Moreover, heating extraction is necessary for GSLs extracted from frozen-fresh sample powder. Average recoveries of the two optimized methods were 74–119% with relative standard deviations ≤ 15%, with the limits of quantification 5.72–17.40 nmol/g dry weight and 0.80–1.43 nmol/g fresh weight, respectively. Notably, the method for analyzing intact GSLs was more efficient than that for desulfo-GSLs regarding operational complexity, detection speed and quantification accuracy. The developed method was applied to identify the characteristic GSLs in 15 Brassicaceae vegetables, providing a foundation for further research on GSLs.

Transformation Pathways in Colloidal CdTeSe Magic-Size Clusters.

A rarely studied transformation in colloidal ternary magic-size clusters (MSCs) is addressed. We report the first observation of the transformation from ternary CdTeSe MSC-399 to MSC-422, which occurs at room temperature. These two MSC types display sharp optical absorption resonances at 399 and 422 nm, respectively, and are related in that they are quasi isomers, together with their counterpart precursor compounds (PCs). Binary CdTe and CdSe samples were prepared in the prenucleation stage also called the induction period (IP). After they were mixed and placed in a mixture of toluene and octylamine, the transformation was found to take place and to be assisted by the addition of the CdSe IP sample. A binary IP sample contains corresponding binary PCs and monomers (Mo) and fragments (Fr). We argue that the transformation pathway is enabled by the corresponding ternary PCs, involving the substitution reaction, namely CdTeSe PC-399 + CdSe (Mo/Fr)-1 ⇒ CdTeSe PC-422 + CdSe (Mo/Fr)-2. The present study provides an in-depth understanding of the formation characteristics of the MSCs.

Transformation Pathways in Colloidal CdTeSe Magic‐Size Clusters

AbstractA rarely studied transformation in colloidal ternary magic‐size clusters (MSCs) is addressed. We report the first observation of the transformation from ternary CdTeSe MSC‐399 to MSC‐422, which occurs at room temperature. These two MSC types display sharp optical absorption resonances at 399 and 422 nm, respectively, and are related in that they are quasi isomers, together with their counterpart precursor compounds (PCs). Binary CdTe and CdSe samples were prepared in the prenucleation stage also called the induction period (IP). After they were mixed and placed in a mixture of toluene and octylamine, the transformation was found to take place and to be assisted by the addition of the CdSe IP sample. A binary IP sample contains corresponding binary PCs and monomers (Mo) and fragments (Fr). We argue that the transformation pathway is enabled by the corresponding ternary PCs, involving the substitution reaction, namely CdTeSe PC‐399 + CdSe (Mo/Fr)‐1 ⇒ CdTeSe PC‐422 + CdSe (Mo/Fr)‐2. The present study provides an in‐depth understanding of the formation characteristics of the MSCs.

Generation of Cobalt-Containing Nanoparticles on Carbon via Pyrolysis of a Cobalt Corrole and Its Application in the Hydrogenation of Nitroarenes

We report on the manufacture of a state-of-the-art heterogeneous non-noble metal catalyst, which is based on a molecularly well-defined phosphine-tagged cobalt corrole complex. This precursor compound is readily synthesized from convenient starting materials while the active material is obtained through wet-impregnation of the pertinent metalliferous macrocycle onto carbon black followed by controlled pyrolysis of the loaded carrier material under an inert gas atmosphere. Thus, the obtained composite was then applied in the heterogeneous hydrogenation of various nitroarenes to yield a vast array of valuable aniline derivatives that were conveniently isolated as their hydrochloride salts. The introduced catalytic protocol is robust and user-friendly with the entire assembly of the reaction set-up enabling the conduction of the experiments on the laboratory bench without any protection from air.

Influence of biogenic emissions from boreal forests on aerosol–cloud interactions

Boreal forest acts as a carbon sink and contributes to the formation of secondary organic aerosols via emission of aerosol precursor compounds. However, these influences on the climate system are poorly quantified. Here we show direct observational evidence that aerosol emissions from the boreal forest biosphere influence warm cloud microphysics and cloud–aerosol interactions in a scale-dependent and highly dynamic manner. Analyses of in situ and ground-based remote-sensing observations from the SMEAR II station in Finland, conducted over eight months in 2014, reveal substantial increases in aerosol load over the forest one to three days after aerosol-poor marine air enters the forest environment. We find that these changes are consistent with secondary organic aerosol formation and, together with water-vapour emissions from evapotranspiration, are associated with changes in the radiative properties of warm, low-level clouds. The feedbacks between boreal forest emissions and aerosol–cloud interactions and the highly dynamic nature of these interactions in air transported over the forest over timescales of several days suggest boreal forests have the potential to mitigate climate change on a continental scale. Our findings suggest that even small changes in aerosol precursor emissions, whether due to changing climatic or anthropogenic factors, may substantially modify the radiative properties of clouds in moderately polluted environments. Emissions from the boreal forest biosphere can substantially increase aerosol load above the forest and influence the radiative properties of clouds, according to analysis of observations from a monitoring station in Finland.

Synthesis and analytical differentiation of a novel synthetic cathinone 1-(2,3-dihydro-1H-inden-5-yl)-2-(pyrrolidin-1-yl)butan-1-one (5-PPDI) and its regioisomers

The differentiation of a controlled drug from uncontrolled novel compounds related to regioisomers is a significant issue in forensics. The compound 1-(2,3-dihydro-1H-inden-5-yl)-2-(pyrrolidin-1-yl)butan-1-one (5-PPDI) is a novel synthetic cathinone first identified in 2015 as a new psychoactive substance. 5-PPDI is the indanyl analog of α-PBP, a typical synthetic cathinone, as well as the aliphatic ring analog of MDPBP, a synthetic cathinone with a heterocyclic ring. 5-PPDI can have three possible regioisomers, 1-(2,3-dihydro-1H-inden-1-yl)-2-(pyrrolidin-1-yl)butan-1-one (1-PPDI), 1-(2,3-dihydro-1H-inden-2-yl)-2-(pyrrolidin-1-yl)butan-1-one (2-PPDI), and 1-(2,3-dihydro-1H-inden-4-yl)-2-(pyrrolidin-1-yl)butan-1-one (4-PPDI), differing by the substituted position of the alkyl side-chain. In this study, 5-PPDI and its three regioisomers were synthesized from commercially available precursor compounds and analyzed by gas chromatography/electron ionization–quadrupole mass spectrometry (GC/EI–Q-MS) and by liquid chromatography/electrospray ionization–linear ion trap mass spectrometry (LC/ESI–LIT–MS). The four PPDI isomers could be differentiated by GC/EI–Q-MS with three types of separation columns and by 2nd generation product ion spectra (MS3) analysis using ESI–LIT–MS.

Mass Balance of Perfluoroalkyl Acids, Including Trifluoroacetic Acid, in a Freshwater Lake.

Perfluoroalkyl acids (PFAAs) are highly persistent chemicals that are ubiquitously found in the environment. The atmospheric degradation of precursor compounds has been identified as a source of PFAAs and might be an important pathway for contamination. Lake Vättern is one of Sweden’s largest lakes and is an important source for drinking water. In addition to contamination via atmospheric deposition, the lake is subject to several potential contamination sources via surface water inflow. The relevance of different sources is not well understood. A mass balance of selected PFAAs was assembled based on measured concentrations in atmospheric deposition, surface water from streams that constitute the main inflow and outflow, and surface water in the lake. The largest input was seen for trifluoroacetic acid (150 kg/year), perfluoropropanoic acid (1.6 kg/year), perfluorobutanoic acid (4.0 kg/year), and perfluoro-octanoic acid (1.5 kg/year). Both atmospheric deposition and surface water inflow was found to be important input pathways. There was a positive correlation between the input of most perfluoroalkyl carboxylic acids via atmospheric deposition and global radiation and between the input via surface water inflow and catchment area. These findings highlight the importance of atmospheric oxidation of volatile precursor compounds for contamination in surface waters.

Triggered and controlled release of active gaseous/volatile compounds for active packaging applications of agri-food products: A review.

Gaseous and volatile active compounds are versatile to enhance safety and preserve quality of agri-food products during storage and distribution. However, the use of these compounds is limited by their high vapor pressure and/or chemical instability, especially in active packaging (AP) applications. Various approaches for stabilizing and controlling the release of active gaseous/volatile compounds have been developed, including encapsulation (e.g., into supramolecular matrices, polymer-based films, electrospun nonwovens) and triggered release systems involving precursor technology, thereby allowing their safe and effective use in AP applications. In this review, encapsulation technologies of gases (e.g., CO2 , ClO2 , SO2 , ethylene, 1-methylcyclopropene) and volatiles (e.g., ethanol, ethyl formate, essential oils and their constituents) into different solid matrices, polymeric films, and electrospun nonwovens are reviewed, especially with regard to encapsulation mechanisms and controlled release properties. Recent developments on utilizing precursor compounds of bioactive gases/volatiles to enhance their storage stability and better control their release profiles are discussed. The potential applications of these controlled release systems in AP of agri-food products are presented as well.

Sea Spray Aerosol (SSA) as a Source of Perfluoroalkyl Acids (PFAAs) to the Atmosphere: Field Evidence from Long-Term Air Monitoring.

The effective enrichment of perfluoroalkyl acids (PFAAs) in sea spray aerosols (SSA) demonstrated in previous laboratory studies suggests that SSA is a potential source of PFAAs to the atmosphere. In order to investigate the influence of SSA on atmospheric PFAAs in the field, 48 h aerosol samples were collected regularly between 2018 and 2020 at two Norwegian coastal locations, Andøya and Birkenes. Significant correlations (p < 0.05) between the SSA tracer ion, Na+, and PFAA concentrations were observed in the samples from both locations, with Pearson’s correlation coefficients (r) between 0.4–0.8. Such significant correlations indicate SSA to be an important source of atmospheric PFAAs to coastal areas. The correlations in the samples from Andøya were observed for more PFAA species and were generally stronger than in the samples from Birkenes, which is located further away from the coast and closer to urban areas than Andøya. Factors such as the origin of the SSA, the distance of the sampling site to open water, and the presence of other PFAA sources (e.g., volatile precursor compounds) can have influence on the contribution of SSA to PFAA in air at the sampling sites and therefore affect the observed correlations between PFAAs and Na+.

Optimisation of a Side Inlet for H2 Entry into an Ultrasonic Spray Pyrolysis Device

An ultrasonic spray pyrolysis (USP) device consists of an evaporation and two reaction zones of equal length, into which an aerosol with a precursor compound enters, and where nanoparticles are formed in the final stage. As part of this research, we simulated the geometry of a side inlet, where the reaction gas (H2) enters into the reaction tube of the device by using numerical methods. Mixing with the carrier gas (N2) occurs at the entry of the H2. In the initial part, we performed a theoretical calculation with a numerical simulation using ANSYS CFX, while the geometries of the basic and studied models were prepared with Solidworks. The inlet geometry of the H2 included a study of the position and radius of the inlet with respect to the reaction tube of the USP device, as well as a study of the angle and diameter of the inlet. In the simulation, we chose the typical flows of both gases (N2, H2) in the range of 5 L/min to 15 L/min. The results show that the best geometry is with the H2 side inlet at the bottom, which the existing USP device does not allow for. Subsequently, temperature was included in the numerical simulation of the basic geometry with selected gas flows; 150 °C was considered in the evaporation zone and 400 °C was considered in the other two zones—as is the case for Au nanoparticle synthesis. In the final part, we performed an experiment on a USP device by selecting for the input parameters those that, theoretically, were the most appropriate—a constant flow of H2 5 L/min and three different N2 flows (5 L/min, 10 L/min, and 15 L/min). The results of this study show that numerical simulations are a suitable tool for studying the H2 flow in a UPS device, as the obtained results are comparable to the results of experimental tests that showed that an increased flow of N2 can prevent the backflow of H2 effectively, and that a redesign of the inlet geometry is needed to ensure proper mixing. Thus, numerical simulations using the ANSYS CFX package can be used to evaluate the optimal geometry for an H2 side inlet properly, so as to reconstruct the current and improve future USP devices.

Nitro Fatty Acids (NO2-FAs): An Emerging Class of Bioactive Fatty Acids.

Unsaturated nitro fatty acids (NO2-FAs) constitute a category of molecules that may be formed endogenously by the reaction of unsaturated fatty acids (UFAs) with secondary species of nitrogen monoxide and nitrite anions. The warhead of NO2-FAs is a nitroalkene moiety, which is a potent Michael acceptor and can undergo nucleophilic attack from thiol groups of biologically relevant proteins, showcasing the value of these molecules regarding their therapeutic potential against many diseases. In general, NO2-FAs inhibit nuclear factorκ-B (NF-κB), and simultaneously they activate nuclear factor (erythroid derived)-like 2 (Nrf2), which activates an antioxidant signaling pathway. NO2-FAs can be synthesized not only endogenously in the organism, but in a synthetic laboratory as well, either by a step-by-step synthesis or by a direct nitration of UFAs. The step-by-step synthesis requires specific precursor compounds and is in position to afford the desired NO2-FAs with a certain position of the nitro group. On the contrary, the direct nitration of UFAs is not a selective methodology; thus, it affords a mixture of all possible nitro isomers.

Defects and Phase Formation in Non-Stoichiometric LaFeO3: a Combined Theoretical and Experimental Study

The defect chemistry of perovskite compounds is directly related to the stoichiometry and to the valence states of the transition-metal ions. Defect engineering has become increasingly popular as it offers the possibility to influence the catalytic properties of perovskites for applications in energy storage and conversion devices such as solid-oxide fuel- and electrolyzer cells. LaFeO$_3$ (LFO) can be regarded as a base compound of the family of catalytically active perovskites La$_{1-x}$A$_x$Fe$_{1-y}$B$_y$O$_{3-\delta}$, for which the defect chemistry as well as the electronic and ionic conductivity can be tuned by substitution on cationic sites. Combining theoretical and experimental approaches, we explore the suitability for A-site vacancy engineering, namely the feasibility of actively manipulating the valence state of Fe and the concentration of point defects by synthesizing La-deficient LFO. Formation energies and concentrations of point defects were determined as a function of processing conditions by first-principles DFT+U calculations. Based on the results, significant compositional deviations from stoichiometric LFO cannot be expected by providing rich or poor conditions of the oxidic precursor compounds (Fe$_2$O$_3$ and La$_2$O$_3$) in a solid-state processing route. In the experimental part, LFO was synthesized with a targeted La-site deficiency. We analyze the resulting phases by X-ray diffraction and scanning electron microscopy, (scanning) transmission electron microscopy in combination with energy-dispersive X-ray spectroscopy, and electron energy-loss spectrometry. Instead of a variation of the La/Fe ratio, a mixture of the two phases Fe$_2$O$_3$ and LFO was observed, resulting in an invariant charge state of Fe, in line with the theoretical results. We discuss our findings with respect to partly differing assumptions made in previous studies on this material system.

A simple, fast, and direct electrochemical determination of tyramine in Brazilian wines using low-cost electrodes

Biogenic amines are a class of organic compounds formed in foods and beverages by enzymatic reactions or microbial decarboxylation of amino acids. Despite their benefits, in unusual concentrations, they are associated with hypertensive crises, neurological disorders and are precursors of compounds with cancer risk. Their abnormal levels are criteria for food spoilage and food safety. Tyramine is a biogenic amine found mainly in fermented foods as wine. Spoilage in the wine production process can increase tyramine concentration resulting in a harmful product to consumers. A fast, simple, and reliable method of tyramine detection in wine samples is necessary to ensure quality control. As this analyte presents electroactivity, three electrochemical techniques and ten different brands of pencil carbon graphite electrodes were used to explore and optimize its oxidation. Differential pulse voltammetry and square wave voltammetry were efficient electrochemical techniques in the determination of tyramine with excellent linear range and low limit of detection. The method was tested for tyramine determination during the grape fermentation process. There are differences regarding tyramine concentration with different varieties of grapes and during the fermentation steps. The method was validated regarding precision, robustness, specificity, accuracy and provided excellent recovery rates (94.4–106.0%) for Brazilian red wines.

Synthesis and in vitro antifungal activity of new Michael-type amino derivatives of xanthatin, a natural sesquiterpene lactone from Xanthium strumarium L.

Structural optimization using plant secondary metabolites as templates is one of the important approach to discover pesticide molecules with novel skeletons. Xanthatin, a natural sesquiterpene lactone isolated from the Xanthium plants (Family: Compositae), exhibits important biological properties. In this work, a series of Michael-type amino derivatives were prepared from xanthatin and their structures were characterized by 1H NMR, 13C NMR and HR-MS, and their antifungal activities against several phytopathogenic fungi were evaluated according to the spore germination method and mycelium growth rate method in vitro. The results illustrated that compounds 2g (IC50 = 78.91 µg/mL) and 2o (IC50 = 64.51 µg/mL) exhibited more promising inhibition activity against spores of F. solani than precursor xanthatin, compounds 2g, 2l, and 2r exhibited remarkable antifungal effect on C. mandshurica with the average inhibition rates (AIRs) >90%, whereas the AIR of xanthatin was only 59.34%. Meanwhile, the preliminary structure–activity relationships suggested that the amino containing 2-methoxyethyl or 4-chlorophenylmethyl group appended in the C-13 position of xanthatin could yield potential compounds against fungal spores, and the exocyclic double bond of xanthatin is essential to maintain its mycelial growth inhibitory activity. Therefore, the aforementioned findings indicate that partial xanthatin amino-derivatives could be considered for further exploration as the potential lead structures toward development of the new environmentally friendly fungicidal candidates for sustainable crop protection.

Manipulation of Continuous and End-of-Day Red/Far-Red Light Ratios Affects Glucobrassicin and Gluconasturtiin Accumulation in Cabbage (Brassica oleracea) and Watercress (Nasturtium officinale), Respectively.

Cabbage (Brassica oleracea) and watercress (Nasturtium officinale) produce glucobrassicin (GBS) and gluconasturtiin (GNST), precursors of chemopreventive compounds. Their accumulation is affected by environmental signals. We studied the impact of the red to far-red light (R/FR) ratio on GBS concentration in red ″Ruby Ball″ and green ″Tiara″ cabbage. Foliar shading, via weed surrogates that competed with cabbage plants for specific durations, induced R/FR variation among treatments. ″Ruby Ball″ GBS concentrations were the highest when R/FR within the canopy was the lowest. ″Tiara″ was unaffected by competition. The same trend was observed in a controlled environment using R and FR LEDs without weeds present. ″Ruby Ball″ subjected to an R/FR = 0.3 treatment had 2.5- and 1.4-fold greater GBS concentration compared to R/FR = 1.1 and 5.0 treatments combined. Watercress given end-of-day (EOD) R and/or FR pulses after the main photoperiod had the lowest GNST concentrations after an EOD FR pulse but the highest concentrations after an R followed by FR pulse.

Prunetin 4'-O-Phosphate, a Novel Compound, in RAW 264.7 Macrophages Exerts Anti-Inflammatory Activity via Suppression of MAP Kinases and the NFκB Pathway.

Biorenovation, a microbial enzyme-assisted degradation process of precursor compounds, is an effective approach to unraveling the potential bioactive properties of the derived compounds. In this study, we obtained a new compound, prunetin 4′-O-phosphate (P4P), through the biorenovation of prunetin (PRN), and investigated its anti-inflammatory effects in lipopolysaccharide (LPS)-treated RAW 264.7 macrophage cells. The anti-inflammatory effect of P4P was evaluated by measuring the production of prostaglandin-E2 (PGE2), nitric oxide (NO), which is an inflammation-inducing factor, and related cytokines such as tumor necrosis factor-α (TNFα), interleukin-1β (IL1β), and interleukin-6 (IL6). The findings demonstrated that P4P was non-toxic to cells, and its inhibition of the secretion of NO—as well as pro-inflammatory cytokines—was concentration-dependent. A simultaneous reduction in the protein expression level of pro-inflammatory proteins such as cyclooxygenase-2 (COX-2) and inducible nitric oxide synthase (iNOS) was observed. Moreover, the phosphorylation of mitogen-activated protein kinases (MAPKs) such as extracellular signal-regulated kinases (ERKs), c-Jun N-terminal kinase (JNK), p38 MAPK (p38), and nuclear factor kappa B (NFκB) was downregulated. To conclude, we report that biorenovation-based phosphorylation of PRN improved its anti-inflammatory activity. Cell-based in vitro assays further confirmed that P4P could be applied in the development of anti-inflammatory therapeutics.