Search Results (78)

The reaction of CuCl₂∙2H₂O, (E)-2-hydroxy-1,2-di(pyridin-2-yl)ethanone oxime (α-pyroxH₂) and Et₃N in refluxing MeOH gave complex [Cu₁₂Cl₁₂(mpydol)₄(pydox)₂(MeOH)₄] (1), where mpydol²⁻ is the dianion of 1,2-dimethoxy-1,2-di(pyridin-2-yl)ethane-1,2-diol and pydox²⁻ is the dianion of (E,E)-1,2-di(pyridin-2-yl)ethanedione dioxime. “Blind” experiments have proven that the transformation of α-pyroxH₂ is copper(II)-assisted. By changing the solvent from MeOH to MeCN, the polymeric compound {[Cu₄Cl₄(pic)₄]}_n (2) was isolated; pic⁻ is the pyridine-2-carboxylato(-1) ligand. The observed α-pyroxH₂ → pic⁻ transformation is also copper(II)-assisted. The topology of the metal ions in 1 can be described as consisting of four consecutive isosceles triangles in a zigzag configuration. Complex 2 is a 2D coordination polymer consisting of Cu^II₄ squares. Complete mechanistic views for the α-pyroxH₂ → mpydol²⁻, pydox²⁻ and pic⁻ transformations are critically discussed. In 1, the six Cu^II ions of the “central” triangles seem to be strongly antiferromagnetically coupled, thus cancelling out their spins ($S_{{\mathrm{Cu}}_6}$ = 0). The two local spins of S = 1/2 for each of the antiferromagnetically coupled “terminal” Cu^II₃ triangles result in an overall S = 1 ground state spin value for 1. In 2, the four Cu^II ions within each tetrameric unit are practically isolated and ferromagnetic interactions occur between these units through Cu^II–(μ-Cl)–Cu^II bridges. Full article

Pesticides, essential for controlling pests and weeds, significantly boost agricultural productivity. However, their excessive use leads to substantial contamination of environmental matrices, including soil and water. Organophosphorus compounds, which constitute more than 30% of the global use of insecticides and herbicides, are particularly concerning, and their widespread application raises alarms among environmentalists and regulatory agencies due to their high toxicity to aquatic organisms. Therefore, to avoid the spread of these compounds within the environment, the contaminated sites may be treated with various methods. This study explored a soil detoxification procedure utilizing gaseous ozone. As a representative of organophosphorus pesticides, chlorfenvinphos was utilized as soil contaminant. This compound is still reported to occur in a number of environmental matrixes. The method used in this study involved the exposure of the soil matrix in a fluidized state to an ozone-enriched atmosphere. The ozonation procedure enabled the removal of the pesticide from the soil matrix. During its oxidation, some degradation products were detected; in particular, they included 2,4-dichlorobenzoic acid and 2-chloro-1-(2,4-dichloro-phenyl)-ethanone, whose presence was confirmed by a GC-MS system and the NIST database. However, they also underwent degradation. Moreover, on the basis of stereoselective reaction of Z and E isomers, the pesticide degradation pathway was proposed. Additionally, the efficacy of this detoxication method was evaluated using a combination of chronic and acute toxicity tests, employing Eisenia foetida earthworms as bioindicators. On the basis of the obtained results, it can be concluded that organophosphorus herbicides containing unsaturated bonds in their structure, including glyphosate, can be removed using this method. Full article

Background/Objectives: Reference materials are essential for ensuring the accuracy and traceability of measurements in the quality control of medicinal products. This study explores new principles for the preparation of impure materials of active pharmaceutical substances, focusing on 1-(3-benzoylphenyl)ethanone ketoprofen impurity A (European Pharmacopoeia) as the reference material. Methods: The reference material was synthesised from commercially available acetanilide and benzoyl chloride. The obtained product was purified using preparative chromatography and characterised by infrared spectroscopy (IR), 1H and 13C nuclear magnetic resonance (NMR), and mass spectrometry. The structure was verified using primary research methods to confirm its identity as the target product. Results: The characterisation confirmed the structure and purity of 1-(3-benzoylphenyl)ethanone, achieving a purity of 99.86%, meeting regulatory documentation requirements. The synthesised product was demonstrated to be identical to the target compound and suitable for use as a reference material. Conclusions: The developed method provides a robust approach for the preparation and characterisation of 1-(3-benzoylphenyl)ethanone, enabling its use as a certified reference material in the quality control of medicinal products. This approach ensures compliance with regulatory standards and enhances the reliability of pharmaceutical quality assurance practices. Full article

Root-knot nematodes (RKNs) are pathogens that endanger a wide range of crops and cause serious global agricultural losses. In this study, we investigated metabolites of the endoparasitic fungus Harposporium anguillulae YMF1.01751, with the expectation of discovering valuable Meloidogyne incognita biocontrol compounds. Based on results obtained by a liquid chromatograph coupled to a mass spectrometer (LC-MS) of crude extracts under five culture conditions and their nematicidal activity against M. incognita, corn meal agar (CMA) medium was determined as the scale-up fermentation medium. Twelve metabolites (1–12) were isolated from the fermentation products, and compound 1 was identified to be a new cyclic tetrapeptide. The activity assay results showed that phenylacetic acid (11) had good nematicidal activity at 400 μg/mL, and the mortalities of M. incognita were 89.76% and 96.05% at 12 and 24 h, respectively, while the mortality of canthin-6-one (2) against M. incognita was 44.26% at 72 h. In addition, the results of chemotaxis activity showed that 1-(1H-indol-3-yl)ethanone (10) possessed attraction activity towards M. incognita. At the tested concentrations, cyclo-(Arg-Pro) (4) and cyclo-(Val-Ile) (7) showed an avoidant response to M. incognita. This study provides insight into the nematode-active compounds of H. anguillulae origin and offers new opportunities for the development of RKN biocontrol products. Full article

Fragrance is a valuable trait in rice varieties, with its aroma significantly influencing consumer preference. In this study, we conducted comprehensive metabolome and transcriptome analyses to elucidate the genetic and biochemical basis of fragrance in the Shangsixiangnuo (SSXN) variety, a fragrant indica rice cultivated in Guangxi, China. Through sensory evaluation and genetic analysis, we confirmed SSXN as strongly fragrant, with an 806 bp deletion in the BADH2 gene associated with fragrance production. In the metabolome analysis, a total of 238, 233, 105 and 60 metabolic compounds exhibited significant changes at the seedling (S), reproductive (R), filling (F), and maturation (M) stages, respectively. We identified four compounds that exhibited significant changes in SSXN across all four development stages. Our analyses revealed a significant upregulation of 2-acetyl-1-pyrroline (2AP), the well-studied aromatic compound, in SSXN compared to the non-fragrant variety. Additionally, correlation analysis identified several metabolites strongly associated with 2AP, including ethanone, 1-(1H-pyrrol-2-yl)-, 1H-pyrrole, and pyrrole. Furthermore, Weighted Gene Co-expression Network Analysis (WGCNA) analysis highlighted the magenta and yellow modules as particularly enriched in aroma-related metabolites, providing insights into the complex aromatic compounds underlying the fragrance of rice. In the transcriptome analysis, a total of 5582, 5506, 4965, and 4599 differential expressed genes (DEGs) were identified across the four developmental stages, with a notable enrichment of the common pathway amino sugar and nucleotide sugar metabolism in all stages. In our correlation analysis between metabolome and transcriptome data, the top three connected metabolites, phenol-, 3-amino-, and 2AP, along with ethanone, 1-(1H-pyrrol-2-yl)-, exhibited strong associations with transcripts, highlighting their potential roles in fragrance biosynthesis. Additionally, the downregulated expression of the P4H4 gene, encoding a procollagen-proline dioxygenase that specifically targets proline, in SSXN suggests its involvement in proline metabolism and potentially in aroma formation pathways. Overall, our study provides comprehensive insights into the genetic and biochemical mechanisms underlying fragrance production in rice, laying the foundation for further research aimed at enhancing fragrance quality in rice breeding programs. Full article

The steric hindrance in molecules of 1-(2,4,6-trimethylphenyl)ethanone and 1-(2,4,6-triisopropylphenyl)ethanone were shown to substantially differentiate the options of synthesis of the respective alcohols. The former was obtained with a yield of 12% with a mild reducing agent, i.e., NaBH₄, as well as in vapor phase transfer hydrogenation (22% yield at 673 K) over MgO, whereas the latter was not formed at all under those conditions. The only agent that was able to reduce both ketones was LiAlH₄. The single crystals of the two alcohols were obtained and their structures were determined. The symmetry of the 0-D hydrogen-bonded networks of molecules in these crystals was analyzed. It was shown that the methyl substituent allows the molecules to form hexameric rings, whereas the isopropyl-substituted molecules formed tetrameric ones. In both cases, there were two types of rings in the cell, but four types of molecules forming tetramers and only three types of molecules in the hexamers. These structures were compared to similar structures formed by other molecules found in the Cambridge Structural Database via hydrogen bonding. Moreover, the single crystal of 1-(2,4,6-triisopropylphenyl)ethanone was obtained to explain if either the hydrogen bonding or the presence of isopropyl groups influences the angles in the molecules. Full article

The present study explores the potential of four NHC-palladium(II) complexes derived from (Z)- or (E)-styryl-N-alkylbenzimidazolium salts, namely trans-dichloro-[(Z)-1-styryl- 3-benzyl-benzimidazol-2-yliden]pyridine palladium(II) (6), trans-dichloro-[(E)-1-styryl-3-benzyl- benzimidazol-2-yliden]pyridine palladium(II) (7), trans-dichloro-[(Z)-1-styryl-3-(3-fluorobenzyl)- benzimidazol-2-yliden]pyridine palladium(II) (8) and trans-dichloro-[(E)-1-styryl-3- (3-fluorobenzyl)-benzimidazol-2-yliden]pyridine palladium(II) (9), to be use as pre-catalysts for the cross-coupling reactions between furanyl or thiofuranyl derivatives and arylbromides via the C–H activation of the heterocycles. The structures of the four Pd(II) complexes have been elucidated through the use of multinuclear NMR, FT-IR and mass spectroscopy. Furthermore, the cis or trans conformation of the styryl substituents and the geometry of two different compounds was substantiated by single-crystal X-ray diffraction, which was carried out on organometallic species 6, 8 and 9. After the optimization of catalytic conditions, which was carried out with 1 mol% of pre-catalyst with KOAc as a base in dimethylacetamide at 120 °C for 3 h, complex 6 proved to be the most effective pre-catalyst agent, with full or quasi full conversions being observed in the cross-coupling of 4-bromoacetophenone with 2-butylfuran, 1-(2-furanyl)-ethanone, furfuryl acetate, furfural, 1-(2-thienyl)-ethanone, thenaldehyde and 2-methylthiophene. Full article

Spirulina, a cyanobacterium widely used as a food supplement due to its high nutrient value, contains volatile organic compounds (VOCs). It is crucial to assess the presence of VOCs in commercial spirulina products, as they could influence sensory quality, various processes, and technological aspects. In this study, the volatile profiles of seventeen commercial spirulina food supplements were determined using headspace solid-phase microextraction (HS-SPME), coupled with gas chromatography-mass spectrometry (GC-MS). The identification of volatile compounds was achieved using a workflow that combined data processing with software tools and reference databases, as well as retention indices (RI) and elution order data. A total of 128 VOCs were identified as belonging to chemical groups of alkanes (47.2%), ketones (25.7%), aldehydes (10.9%), alcohols (8.4%), furans (3.7%), alkenes (1.8%), esters (1.1%), pyrazines (0.8%), and other compounds (0.4%). Major volatiles among all samples were hydrocarbons, especially heptadecane and heptadec-8-ene, followed by ketones (i.e., 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one, β-ionone, 2,2,6-trimethylcyclohexan-1-one), aldehydes (i.e., hexanal), and the alcohol oct-1-en-3-ol. Several volatiles were found in spirulina dietary supplements for the first time, including 6,10-dimethylundeca-5,9-dien-2-one (geranylacetone), 6,10,14-trimethylpentadecan-2-one, hept-2-enal, octanal, nonanal, oct-2-en-1-ol, heptan-1-ol, nonan-1-ol, tetradec-9-en-1-ol, 4,4-dimethylcyclohex-2-en-1-ol, 2,6-diethylpyrazine, and 1-(2,5-dimethylfuran-3-yl) ethanone. The methodology used for VOC analysis ensured high accuracy, reliability, and confidence in compound identification. Results reveal a wide variety of volatiles in commercial spirulina products, with numerous newly discovered compounds, prompting further research on sensory quality and production methods. Full article

Hydrophobic cryogels with monolithic supermacropores based on poly-trimethylolpropane trimethacrylate (pTrim) containing 1-(2-Hydroxyl-5-nonyphenyl)ethanone oxime (LIX84-I) were successfully prepared by a cryo-polymerization technique using organic solvents with freezing points between room temperature and around 0 °C as solvents. The prepared cryogels were characterized in terms of macroscopic shape and porous structure. The cryogels had a monolithic supermacroporous structure and high contents of LIX84-I depending on the added amount of the extractant to the monomer solution. The amount of LIX84-I impregnated in the cryogel had a linear relationship with the added amount of LIX84-I in the monomer solution for cryo-polymerization. Cu(II) in the aqueous solution was immediately adsorbed into the cryogel containing LIX84-I. Full article

The intramuscular fat (IMF) content is considered an important factor for assessing meat quality, and is highly related to meat flavor. However, in donkey meat, the influences of IMF content on lipid and volatile profiles remain unclear. Thus, we conducted lipidomic and volatilomic investigations on high- and low-IMF samples from donkey longissimus dorsi muscle. When the IMF level increased, the monounsaturated fatty acid (especially oleic acid) content significantly increased but the saturated fatty acid content decreased (p < 0.05). Twenty-nine of 876 lipids showed significant differences between the two groups. Volatile profiles from differential IMF content samples were also distinct. Five differential volatile odorants were identified in the two groups: 2-acetyl-2-thiazoline, octanal, 2-pentylfuran, pentanal, and 1-(2-pyridinyl) ethanone. Additionally, strong correlations were found between differential fatty acids and lipids with differential odorants. Thus, the difference in volatile odorants may result from the change in the fatty acid composition and lipid profiles induced by different IMF contents, highlighting the urgent need to increase IMF levels in donkey meat. Full article

Many literature reports revealed the anticancer activity of pyridine and thiazole derivatives, especially in lung cancer. Therefore, a new series of thiazolyl pyridines linked with thiophene moiety via hydrazone group was prepared by one-pot multi-component reaction of (E)-1-(4-methyl-2-(2-(1-(thiophen-2-yl)ethylidene)hydrazinyl)thiazol-5-yl)ethanone with benzaldehyde derivatives and malononitrile in a good yield. Then, compound 5 and the thiazolyl pyridines were investigated for their in vitro anticancer activity against lung cancer (A549) cell line using MTT assay compared to doxorubicin as a reference drug. The structure of all the newly synthesized compounds was established based on spectroscopic data and elemental analyses. For better insight to investigate their mechanism of action on A549 cell line, docking studies were performed, targeting epidermal growth factor receptor (EGFR) tyrosine kinase. The results obtained revealed that the tested compounds displayed excellent anticancer activities against lung cancer cell line except 8c and 8f compared to reference drug. Based on the data obtained, it can be inferred that the novel compounds, as well as their key intermediate, compound 5, demonstrated potent anticancer activity against lung carcinoma by inhibiting EGFR. Full article

Plant essential oils, as biological pesticides, have been reviewed from several perspectives and play a key role in chemical ecology. However, plant essential oils show rapid degradation and vulnerability during actual usage. In this study, we conducted a detailed analysis of the compounds present in the essential oils of A. stechmanniana using gas chromatography–mass spectrometry (GC-MS). The results showed seventeen terpenoid compounds in the A. stechmanniana oil, with four major terpenoid compounds, i.e., eucalyptol (15.84%), (+)-2-Bornanone (16.92%), 1-(1,2,3-Trimethyl-cyclopent-2-enyl)-ethanone (25.63%), and (-)-Spathulenol (16.38%), in addition to an amount of the other terpenoid compounds (25.26%). Indoor toxicity assays were used to evaluate the insecticidal activity of Artemisia stechmanniana essential oil against Aphis gossypii, Frankliniella occidentalis, and Bactericera gobica in Lycium barbarum. The LC₅₀/LD₅₀ values of A. stechmanniana essential oils against A. gossypii, F. occidentalis, and B. gobica were 5.39 mg/mL, 0.34 mg/L, and 1.40 μg/insect, respectively, all of which were highly efficient compared with azadirachtin essential oil. Interestingly, A. stechmanniana essential oil embedded in β-cyclodextrin (microencapsule) remained for only 21 days, whereas pure essential oils remained for only 5 days. A field efficacy assay with the A. stechmanniana microencapsule (AM) and doses at three concentrations was conducted in Lycium barbarum, revealing that the insecticidal activities of AM showed high efficiency, maintained a significant control efficacy at all concentrations tested, and remained for 21 days. Our study identified terpenoid compounds from untapped Artemisia plants and designed a novel method against pests using a new biopesticide on L. barbarum. Full article

The use of computational methods that allow us to perform characterization on new compounds is not a novelty; nevertheless, the degree of complexity of the structures makes their study more challenging since new techniques and methods are required to adjust to the new structural model. The case of nuclear magnetic resonance characterization of boronate esters is fascinating because of its widespread use in materials science. In this paper, we use density functional theory to characterize the structure of the compound 1-[5-(4,5-Dimethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]ethanonea by means of nuclear magnetic resonance. We studied the compound in its solid form with the PBE–GGA and PBEsol–GGA functionals, with a set of plane wave functions and an augmented wave projector, which included gauge in CASTEP and its molecular structure with the B3LYP functional using the package Gaussian 09. In addition, we performed the optimization and calculation of the chemical shifts and isotropic nuclear magnetic resonance shielding of ${}^1$H, ${}^{13}$C, and ${}^{11}$B. Finally, we analyzed and compared the theoretical results with experimental diffractometric data observing a good approximation. Full article

In this study, we speculate that the hydroxyl-containing benzo[b]thiophene analogs, 1-(3-hydroxybenzo[b]thiophen-2-yl) ethanone (BP) and 1-(3-hydroxybenzo[b]thiophen-2-yl) propan-1-one hydrate (EP), might possess antiproliferative activity against cancer cells. Hydroxyl-containing BP and EP show selectivity towards laryngeal cancer cells (HEp2), with IC₅₀ values of 27.02 ± 1.23 and 35.26 ± 2.15 µM, respectively. The hydroxyl group present in the third position is responsible for the anticancer activity and is completely abrogated when the hydroxyl group is masked. BP and EP enhance the antioxidant enzyme activity and reduce the ROS production, which are correlated with the antiproliferative effect in HEp-2 cells. An increase in the BAX/BCL-2 ratio occurs during the BP and EP treatment and activates the caspase cascade, resulting in apoptosis stimulation. It also arrests the cells in the Sub-G1 phase, indicating the induction of apoptosis. The molecular docking and simulation studies predicted a strong interaction between BP and the CYP1A2 protein, which could aid in combinational therapy by enhancing the bioavailability of the drugs. BP and EP possess an antioxidant property with low antiproliferative effects (~5.18 µg/mL and ~7.8 µg/mL) as a standalone drug, therefore, they can be combined with other drugs for effective chemotherapy that might trigger the effect of pro-oxidant drug on healthy cells. Full article

French tamarisk, Tamarix gallica L. (family Tamaricaceae) is a deciduous tree that, like other halophytes, grows in a wide variety of saline habitats thanks to its powerful phenolics-based antioxidant system. Given that antioxidant properties are usually linked to the presence of compounds with antifungal properties, in the work presented herein the antimicrobial activity of T. gallica bark extract was investigated against four phytopathogenic species of genus Fusarium. According to the results of gas chromatography–mass spectroscopy, the phytochemical profile of the aqueous ammonia extract included 1-(2,4,6-trihydroxyphenyl)-2-pentanone; 3,5-dimethoxy-4-hydroxycinnam aldehyde; trans-squalene; 4-hydroxy-3,5-dimethoxy-benzaldehyde; dihydro-3-methylene-2,5-furandione; 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone; and 4-hydroxy-3,5-dimethoxy-benzoic acid as main constituents. Concerning in vitro antifungal activity, EC₉₀ effective concentrations in the 335–928 μg·mL⁻¹ range were obtained against F. acuminatum, F. culmorum, F. equiseti, and F. graminearum, remarkably lower than those of two conventional fungicides (viz. mancozeb and fosetyl-Al). The antifungal activity of the extract was tested further in wheat and maize grain protection bioassays, confirming that the treatment effectively controlled F. graminearum at a concentration of 375 µg·mL⁻¹. Given this promising activity, T. gallica bark extracts may be susceptible to valorization as a natural and sustainable biorational for Fusarium spp. control. Full article