Search Results (82)

1-Butyl-3-methylimidazolium (bmim) ionic liquids (ILs) are widely used for lignocellulose fractionation, yet their role extends beyond mere solvents. This study revealed that bmim-based ILs act as active chemical reagents, modifying the lignin structure in an anion-dependent manner. Thermal treatment (80–150 °C) of spruce dioxane lignin with [bmim]OAc, [bmim]Cl, and [bmim]MeSO₄ resulted in two distinct transformation pathways. In [bmim]MeSO₄, acidic catalysis dominates, leading to lignin condensation (increase in weight-average molecular weight, M_w, to 15.2 kDa at 150 °C) and intense sulfur incorporation (up to 9.9%) via anion-derived methylation/sulfation. Conversely, [bmim]OAc promotes depolymerization (decrease in M_w to 3.6 kDa) and efficient covalent bonding of the bmim cation to lignin (up to 10.8 cations per 100 aromatic units and a 6.5% nitrogen content at 150 °C), preventing condensation. Two-dimensional NMR and HPLC-HRMS analyses revealed the formation of a C–C bond between the C₂ atom of the imidazole ring and the α-carbon of the phenylpropane lignin fragments and allowed for the identification of a number of individual nitrogen-containing lignin oligomers in the [bmim]OAc-treated samples. Their formation likely proceeds via nucleophilic addition of the N-heterocyclic carbene (NHC), derived from the bmim cation by deprotonation with the highly basic acetate anion, to aldehyde groups. The action of [bmim]Cl primarily induces acid-catalyzed transformations of lignin with minimal covalent modification. These findings redefine imidazolium ILs as reactive media in biorefining, where their covalent interactions can influence the properties of lignin but complicate its native structure and the recyclability of the IL. Full article

Watermelon soy sauce (WSS) is a liquid condiment usually prepared using watermelon juice, soybeans, and wheat flour through the process of making koji and natural fermentation. It is widely used in Chinese culinary art, despite the lack of knowledge about its aromatic compound content. Here, we characterized the physicochemical properties, free amino acid composition, and volatile compounds of WSS using SPME-GC/MS and E-nose. We noticed that WSS had the highest total acid content but the lowest amino nitrogen and reducing sugar contents compared with commercial soy sauce. Moreover, the highest amounts of Glu and Pro were observed in WSS. A total of 173 volatile compounds were identified in WSS, including alcohols, hydrocarbons, esters, ketones and aldehydes. The E-nose analysis showed a good capacity of differentiating braised samples mainly through W5S, W1S, W1W, W2W, and W3S sensors. The analysis of relationships between flavor components and free amino acids in soy sauce samples showed that Ser, Gly, Val, Ile, Leu, Ph,e and Lys had a strong positive correlation with alcohol and acidic compounds. Moreover, Pro was found to be correlated with aldehyde, ketone, heterocyclic compounds, sulfur compounds, and benzene, while Glu was correlated with hydrocarbons, aldehyde, and benzene. This study could provide important information regarding WSS quality control, characterization, and aroma improvement. Full article

Unsymmetrical dimethylhydrazine (UDMH) was previously used as a rocket propellant in launch vehicles. During the operation and accidents of launch vehicles, hundreds of tons of UDMH were released. While these launch vehicles are gradually being phased out, UDMH continues to be used in space technology and other industries. When released into the environment, UDMH forms numerous transformation products. Several dozen have been reliably identified, and hundreds are believed to exist, many of which are highly toxic and quite persistent in the environment. Gas chromatography–mass spectrometry (GC-MS) is one of the primary methods for identifying these compounds. Library searches using mass spectra and retention indices are often used. However, UDMH transformation products are highly specific—they are organic compounds, typically aromatic heterocycles, with unusually high nitrogen content. Such compounds are poorly represented in GC-MS databases, while existing data are often of poor quality and were obtained back in the 1980s. A database of such compounds was presented, containing information on retention indices for non-polar (5%-phenylpolydimethylsiloxane) and polar (polyethylene glycol) stationary phases, as well as electron ionization mass spectra (70 eV) for 104 nitrogen-containing compounds: derivatives of triazoles, pyrazoles, imidazoles, pyridines, diazines, and triazines, as well as amides and other compounds. Many of the compounds presented in the database are proven UDMH transformation products, while many of the other compounds are probable. Derivatives of triazoles and triazines are also used as pesticides, and our database can be useful in detecting their derivatives. The database is free and available online. Full article

Oxadiazoles, nitrogen-containing heterocycles, are attracting interest due to their promising biological activities. This study focuses on the synthesis of oxadiazole derivatives from functionalized intermediates derived from terephthalic acid, a versatile and readily available aromatic precursor widely used for the construction of nitrogen heterocycles and advanced organic structures. Different synthetic approaches were explored to evaluate the feasibility of these processes. Full article

Five-membered nitrogen heterocycles exhibit a diverse range of applications across various fields, including medicine, agrochemicals, and materials science. Worldwide industries have exploited hazardous organic solvents and catalysts to afford key bioactive heterocycles, which in turn have a devastating impact on the aqueous environment. The tremendous rise in environmental contamination has shifted the focus of the scientific community towards sustainable alternatives. In line with this, ionic liquids have received the attention of investigators and are widely preferred in organic transformations as catalysts, solvents, ligands, and co-catalysts. Ionic liquids exhibit superior physicochemical properties, such as non-volatility, excellent conductivity, low vapour pressure, non-flammability, and electrochemical and thermal stability, thereby emerging as a clean and efficient alternative to the hazardous volatile organic solvents. The ionic-liquid-assisted synthetic approach has become a popular, greener method owing to high efficiency and product yield with notable purity. Thus, the present article aimed at highlighting catalytic applications of ionic liquids in the synthesis of aromatic five-membered nitrogen heterocycles such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, and tetrazole. This article will provide an insight into ionic liquids for their further exploration in organic transformations and related applications. Full article

This review summarises the possible applications and basic methodologies for the synthesis of six-membered polyazo heterocycles, namely, diazines, triazines, and tetrazines. The time period covered by the analysed works ranges from the beginning of the 20th century to the present day. This period was chosen because it was during this time that synthetic chemistry, as defined by physicochemical research methods, became capable of solving such complex problems as efficiently as possible. The first part of the review describes the applications of polyazo heterocyclic compounds, whose frameworks are found in the composition of drugs, dyes, and functional molecules for materials chemistry, as well as in a wide variety of natural compounds and their synthetic analogues. The review also systematises the methods for assembling six-membered aromatic polyazo heterocycles, including intramolecular and sequential cyclisation, which determine the possible structural and functional diversity based on the presence and arrangement of nitrogen atoms and the position of the corresponding substituents. Full article

Oil spills in inland rivers pose a significant threat to the surrounding environment, and the emergency response differs greatly from that in ocean or coastal areas. In this study, we focused on several commonly used emergency water treatment strategies in China’s inland oil spills, as well as the spilled washing oil in a serious accident case. We investigated the changes in oil-related chemical components before and after water treatment using GCxGC-TOF MS (Comprehensive Two-dimensional Gas Chromatography Time of Flight Mass Spectrometer). We tracked the shifts of microbial communities in the microcosms incubated with clean river water, simulated oil-contaminated water, and the treatment effluent. The results revealed that typical components, especially nitrogen-containing heterocyclic compounds, had different removal efficiencies among treatments. The diversity, composition, and potential functions of microbial communities responded differently to the treatments, and could be related to various substances, including PAHs (polycyclic aromatic hydrocarbons) and heterocyclic compounds. A few genera, such as SC-I-84, exhibited a high correlation with washing oil-related components and could serve as an indicator in such an oil spill emergency response. Our findings indicated that simply using petroleum oil or PAHs to evaluate oil spills was likely to underestimate the ecological impact, especially when the spilled substances were coal chemical products widely used in China. This will provide an important scientific basis for decision-making and strategy evaluation in emergency responses to inland oil spills. Full article

Hongqujiu, one of the three principal varieties of yellow wine, is a traditional fermented beverage originating from China that employs Hongqu as the fermentation agent. In this study, an untargeted metabolomics approach based on gas chromatography–mass spectrometry (GC-MS) and liquid chromatography–mass spectrometry (LC-MS) was applied to systematically analyze the volatile compounds (VOCs) and non-volatile compounds (NVCs) in Hongqujiu across different aging years for the first time. The analysis identified a total of 262 VOCs and 2564 NVCs in samples of Hongqujiu aged for six distinct years. Based on metabolic differences, the samples were categorized into two groups: the low-year group (5-year, 6-year) and the high-year group (8-year, 10-year, 15-year, 20-year). Nineteen VOCs (e.g., 4-amino-butyric acid and diethanolamine) and thirty NVCs (e.g., palmitoylethanolamide and erinacine D) were identified as key differential metabolites distinguishing the low-year group from the high-year group. The higher-year group is enriched with a variety of substances with different flavors or biological activities, such as sugar derivatives, amino acids and their complexes, organic acids and their intermediate metabolites, steroids and terpenoid compounds, lipids and their derivatives, nitrogen-containing heterocycles, and aromatic compounds. The accumulation of these substances not only shapes the unique and rich flavor characteristics of aged red rice wine (such as the caramel aroma and umami peptide flavor), but also endows red rice wine with potential health benefits due to the physiological regulatory functions of some active ingredients. This study contributes to a deeper understanding of the composition and dynamic variations in metabolites in Hongqujiu, offering a scientific foundation for identifying aged Hongqujiu and conducting further research to enhance its quality. Full article

Background: Carbazoles represent one of the most important classes of nitrogen-based tricyclic aromatic heterocycles and are present in natural sources and chemically obtained drugs. Recently, several research groups disclosed their large biological and chemical applications in different fields, leading to an increased interest towards this class of molecules. Some of the obtained derivatives have been successfully employed in the clinical treatment of different tumor types, but the onset of heavy side effects impaired their efficacy and discouraged their use. Pursuing the aim of obtaining carbazoles with less negative features, a lot of chemically modified compounds have been produced and evaluated. Objectives/Methods: In this paper, we describe the in vitro and in vivo evaluation of a bis-carbazole derivative with strong anticancer properties against two breast cancer cell lines. Results: This compound has been found to impact the cell cytoskeleton dynamics, triggering the activation of some key proteins playing a role in the intrinsic and extrinsic apoptotic pathways. Equally important, this derivative has been found to be selective for cancer cells and has shown a safe profile in Balb/c-treated mice. Conclusions: Overall, the disclosed outcomes represent an important landmark for encouraging further studies directed toward the potentiation of this lead to be potentially exploited in both preclinical and clinical applications. Full article

With the acceleration of urbanization, the disposal of dewatered sewage sludge (DSS) has become an urgent environmental issue worldwide. Hydrothermal conversion (HC) of DSS is an important method for sludge sustainable utilization due to its combination of efficiency and economic and environmental advantages. This study investigates the product distribution and composition of products during the HC of DSS under subcritical and supercritical water conditions (200–450 °C, 5–90 min), with a particular focus on the formation and conversion mechanisms of steroid compounds. The results indicate that increasing temperature and reaction time leads to a rise in gas-phase products (GPs) and a corresponding decline in solid-phase products (SPs), with phenolic compounds identified as the predominant constituents. In the water-soluble products (WSPs), nitrogen-containing cyclic compounds are the major products. Saturated nitrogen heterocycles dominate at lower temperatures (200 °C), while at elevated temperatures (300–350 °C), saturated azapolycyclic compounds emerge, ultimately transitioning into unsaturated aromatic nitrogen heterocycles at 450 °C. Steroids are primarily concentrated in the oil-phase products (OPs). The conversion process involves the initial conversion of lipids in the DSS to long-chain olefins at 200 °C, which are then converted to steroids at 250–350 °C. At higher temperatures (400–450 °C), these steroids might decompose into gaseous products or undergo polymerization to form char. This suggests the potential for steroids to act as precursor compounds in the process of char formation. This work could contribute to a deeper understanding of the HC mechanism of DSS and provide valuable technical insights for improving bio-oil quality. Full article

The thermal characterisation and toxicity profile of a class of disubstituted heterofused triazinones were revealed in this article for the first time. The thermal behaviour of molecules 1–12 was investigated by means of TG and DSC analyses performed in an air atmosphere and by the coupled TG/FTIR technique in a nitrogen atmosphere. The heating atmosphere affects both the stability of compounds and the degradation mechanism. A two-step degradation occurs in air, while a one-step degradation takes place in nitrogen, both preceded by a melting process. Compound 3 shows the highest thermal stability, while molecule 10—the lowest. The thermal decomposition of the studied heterocyclic molecules begins with the degradation of the bicyclic system, resulting in the formation of volatile gaseous products such as ammonia/hydrazine, hydrogen cyanide, carbon dioxide, and isocyanates. In the further stage, mainly aromatic compounds are released, and their chemical composition depends on the presence and type of substituents at the phenyl and benzyl moieties. In addition, the toxicity profiles of molecules were assessed in the animal (zebrafish) and cellular (erythrocytes) models, and the antihaemolytic activity was evaluated in the AAPH- and H₂O₂-induced haemolysis inhibition assays. It was found that all the tested compounds are safe for the developing zebrafish and red blood cells, and they are able to effectively protect erythrocytes from oxidative damage. These favourable properties make them promising drug candidates suitable for further in vivo studies. Full article

The U.S. Food and Drug Administration (FDA) has authorized 50 new drugs in 2024, which matches the average figure for recent years (2018–2023). The approval of 13 monoclonal antibodies (mAbs) sets a new record, with these molecules accounting for more than 25% of all drugs authorized this year. Three proteins have been added to the list of biologics, and with the inclusion of four TIDES (two oligonucleotides and two peptides), only one in three approved drugs this year is a small molecule. As of 2023, no antibody-drug conjugates (ADCs) have reached the market this year. Two deuterated drugs have been approved, bringing the total approvals for this class of compounds to four. This year saw the authorization of two more PEGylated drugs—both peptides—highlighting a renewed interest in this strategy for extending drug half-life, despite the setback caused by the withdrawal of peginesatide from the market in 2014 due to adverse side effects. N-aromatic heterocycles and fluorine atoms are present in two-thirds of all the small molecules approved this year. Herein, the 50 new drugs authorized by the FDA in 2024 are analyzed exclusively on the basis of their chemical structure. They are classified as the following: biologics (antibodies, proteins), TIDES (oligonucleotides and peptides), combined drugs, natural products, F-containing molecules, nitrogen aromatic heterocycles, aromatic compounds, and other small molecules. Full article

A new approach to 1,2,5-trisubstituted 1H-indole-3-carboxylic esters has been developed and studied. The method begins with the preparation of imines from aldehyde and primary amine derivatives. Treatment of these imines with the K₂CO₃-derived anion from methyl 2-(2-fluoro-5-nitrophenyl)acetate or methyl 2-(5-cyano-2-fluorophenyl)acetate in DMF initiates a [3+2] cyclization by addition of the anion to the imine followed by ring closure of the adduct nitrogen to the activated aromatic moiety via an S_NAr process. Twenty-one examples are reported. Temperatures required for the conversion range from 90 to 95 °C for the nitro-activated substrates to 125 to 130 °C for the cyano-activated precursors. Though efficient and atom economical, limitations arise from steric hindrance in the reacting partners. The initial indoline formed is not observed but instead undergoes spontaneous air oxidation to the give the aromatic heterocycle. Imines from nonaromatic aldehydes and amines are also possible, but these give slightly lower yields of 1H-indoles and only react with the nitro-activated substrates. The results are presented with a discussion of the mechanism and the factors important to the success of the reaction. Full article

Nitrogen-rich heterocycles constitute a family of high energy density materials (HEDMs) that have been developing intensively in recent years. A representative of this class is 1,2,4,5-tetrazine, a six-membered aromatic compound containing four nitrogen atoms in the ring. Many energetic compounds with this scaffold exhibit thermal stability, high density, and insensitivity to various stimuli, including friction, impact, and electrostatic discharge. This review presents methods for constructing 1,2,4,5-tetrazine precursors from acyclic reagents and describes their chemical modifications, leading to new energetic compounds with potential applications in the industry as explosives, propellants, or pyrotechnics. Synthetic procedures and reaction conditions are discussed, along with the detonation parameters of new nitrogen-rich tetrazine-based products, which allow estimation of their application potential. Full article

Obesity is a chronic disease that profoundly impacts human health, and the role of plant-based formulas (PBFs) in combating obesity has garnered significant interest. Studies have revealed that fermentation significantly enhances the taste, aroma, quality, and health benefits of PBF water extract, with pasteurization being the preferred sterilization technology. However, few studies have investigated the effects of pasteurization on the active components and potential functions of PBF water extract fermentation broth. To examine the impact of pasteurization on fermented water extract of Millettia speciosa Champ (FH08F) and its potential anti-obesity properties, the components of FH08F and thermal-pasteurized FH08F (FH08FS) were analyzed in this study. The analysis revealed a substantial rise in ester content following sterilization. This can be attributed to the acidic environment that promotes the esterification reaction during the heating phase. Network pharmacology was employed to thoroughly examine seven active components of upregulated compounds (URCs) with potential obesity targets, which constituted 92.97% of the total URC content, and four of them were nitrogen-containing aromatic heterocyclic compounds (NAHCs), which accounted for 90.33% of the total URC content. Upregulated NAHCs appear to actively contribute to efficacy against obesity. Molecular docking analyses have shown that theophylline, an NAHC, has the strongest binding affinity with the obesity-related target PTGS2 (Prostaglandin G/H synthase 2, 5FLG). These results imply that theophylline may directly activate PKA/PKG-mediated phosphorylated hormone-sensitive lipase (p-HSL), thereby promoting lipolysis through the cAMP signaling pathway and stimulating the catabolism of triglycerides (TGs) to combat obesity. In conclusion, pasteurization substantially alters the composition of FH08F, and NAHCs are likely to play a significant role in its potential anti-obesity function. These findings provide a scientific foundation for the potential therapeutic effect of FH08FS on obesity and associated metabolic diseases. Full article