Search Results (614)

A new approach to the synthesis of a nanosized and hierarchical titanosilicate, TS-1, is presented. Instead of using specific solid or additional mesoporous templates or individual additives to slow down the hydrolysis of titanium alkoxides, it is proposed that the titanosilicate TS-1 can be obtained from gels synthesized with hydrolysis catalysts (HNO₃ and tetrapropylammonium hydroxide). When nitric acid catalyzes tetraethyl orthosilicate (TEOS) hydrolysis, the resulting crystalline TS-1 that can be obtained has uniform particle sizes (150–180 nm), is anatase-free, and contains up to 46–67% of mesopores. When a base catalyst is applied, the obtained material’s features are opposite. Moreover, acid-promoted TS-1 samples catalyze cyclohexene H₂O₂-oxidation via a heterolytic route to the cyclohexane epoxide with 67% selectivity, which is non-typical. Full article

This study evaluates the production of base oils for biolubricants using fatty acid methyl esters (FAMEs) derived from sunflower oil as the raw material. The production process involved the synthesis of oleochemical esters through a single-step alkaline transesterification reaction with a high-molecular-weight polyol, such as trimethylolpropane (TMP). To assess the effectiveness of the developed catalytic system in conducting the transesterification reactions and its impact on the properties of the final product, two types of alkaline catalysts were used. Specifically, the reactions were carried out using either Ca/TEA alkoxide or sodium methoxide as catalysts in various configurations and concentrations to determine the optimal catalyst concentration and reaction conditions. Sodium methoxide served as the commercial benchmark catalyst, while the Ca/TEA alkoxide was prepared in the laboratory. The optimal concentration of Ca/TEA was determined to be 3.0% wt. in the presence of iso-octane and 3.5% wt. under vacuum, while the corresponding concentrations of CH₃ONa for both cases were determined to be 2.0% wt. The synthesized biolubricant esters exhibit remarkable performance characteristics, such as high kinematic viscosities and low pour points—ranging from 33–48 cSt at 40 °C, 7.68–10.03 cSt at 100 °C, to −14 to −7 °C, respectively—which are comparable to or improved over those of mineral oils such as SN-150 or SN-500, with the Ca/TEA alkoxide-catalyzed systems showing superior oxidation stability and reduced byproduct formation. Full article

Over efficient photocatalysts, CO₂ photoreduction typically converts CO₂ into low-carbon chemicals, which serve as raw materials for downstream synthesis processes. Here, an efficient composite photocatalyst heterojunction (Cu₂O-u/g-C₃N₄) has been fabricated to reduce CO₂. Graphitic carbon nitride (g-C₃N₄) was synthesized via thermal polymerization of urea at 550 °C, while pre-dispersed Cu₂O derived from urea pyrolysis (Cu₂O-u) was prepared by thermal reduction of urea and CuCl₂·2H₂O at 180 °C. The heterojunction Cu₂O-u/g-C₃N₄ was subsequently constructed through hydrothermal treatment at 180 °C. This heterojunction exhibited a bandgap of 2.10 eV, with dual optical absorption edges at 485 nm and above 800 nm, enabling efficient harvesting of solar light. Under 175 W mercury lamp irradiation, the heterojunction catalyzed liquid-phase CO₂ photoreduction to formic acid, acetic acid, and methanol. Its formic acid production activity surpassed that of pristine g-C₃N₄ by 3.14-fold and TiO₂ by 8.72-fold. Reaction media, hole scavengers, and reaction duration modulated product selectivity. In acetonitrile/isopropanol systems, formic acid and acetic acid production reached 579.4 and 582.8 μmol·h⁻¹·g_cat⁻¹. Conversely, in water/triethanolamine systems, methanol production reached 3061.6 μmol·h⁻¹·g_cat⁻¹, with 94.79% of the initial conversion retained after three cycles. Finally, this work ends with the conclusions of the CO₂ photocatalytic reduction to formic acid, acetic acid, and methanol, and recommends prospects for future research. Full article

In this work, we described the synthesis of 4-(methoxycarbonyl)phenyl 5-bromofuran-2-carboxylate by reacting 5-bromofuroic acid with methylparaben in the incorporation of DCC/DMAP (Steglich esterification) as coupling agents. Later on, we subsequently synthesized a series of 4-(methoxycarbonyl)phenyl 5-aryl furan-2-carboxylates (5a–5e) through Suzuki coupling catalyzed by palladium (0) between 4-(methoxycarbonyl)phenyl 5-bromofuran-2-carboxylate (3) with several substituted arylated and heteroaryl boronic acids (4). DFT calculations were computed to elucidate electronic structural features of synthesized molecules (5a–5e) and to validate these findings by correlating with theoretical and experimental spectroscopic analysis. Furthermore, geometrical optimization, thermodynamic features, as FMO orbitals, MESP maps, NLO behavior and reactivity descriptors, were also determined from the PBE0 D3BJ/def2-TZVP/SMD_1,4-dioxane theory level to confirm the structural features of synthesized molecules. Full article

Background/Objectives: As an essential polyunsaturated fatty acid, linoleic acid (LA) plays an important role in maintaining the integrity of cellular membranes, modulating inflammatory responses, and mediating intracellular signaling. This review explores the structure, properties, and nutritional significance of LA and its bioactive derivatives, with particular attention to sustainable production methods and their potential applications. Methods: A comprehensive review of the recent literature was conducted, emphasizing the use of green synthesis techniques, such as enzyme-catalyzed biocatalysis and microbiological transformations, in order to obtain LA-derived nutraceuticals. Analyses were conducted on the key aspects related to food industry applications, regulatory frameworks, and emerging market trends. Results: Through green synthesis strategies, LA derivatives with antioxidant, anti-inflammatory, and antimicrobial properties have been developed. There is potential for these compounds to be incorporated into health-oriented food products. In spite of this, challenges remain regarding their stability and bioavailability. Furthermore, there are inconsistencies in international regulatory standards which prevent these compounds from being widely adopted. Conclusions: The development of functional and sustainable food products based on linoleic acid derivatives obtained using ecological methods offers significant potential. Research is required to optimize production processes, enhance compound stability, and clinically validate health effects. The integration of the market and the safety of consumers will be supported by addressing regulatory harmonization. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

This study reports an improved diastereoselective synthesis of substituted spiro[chromane-2,4′-pyrimidin]-2′(3′H)-ones via the acid-catalyzed condensation of 6-styryl-4-aryldihydropyrimidin-2-ones with resorcinol, 2-methylresorcinol, and pyrogallol. The optimized method allows for the isolation of diastereomerically pure products, with stereoselectivity controlled by varying acid catalysts (e.g., methanesulfonic acid vs. toluenesulfonic acid) and solvent conditions. The synthesized compounds were evaluated for antimicrobial and antioxidant activities. Notably, the (2S*,4R*,6′R*)-diastereomers exhibited significant antibacterial activity against both Gram-positive and Gram-negative bacterial strains with minimal inhibition concentration down to 2 µg/mL, while derivatives containing vicinal bisphenol moieties demonstrated potent antioxidant activity, with IC₅₀ values (12.5 µg/mL) comparable to ascorbic acid. Pharmacokinetic analysis of selected hit compounds revealed favorable drug-like properties, including high gastrointestinal absorption and blood-brain barrier permeability. These findings highlight the potential of spirochromane-pyrimidine hybrids as promising candidates for further development in the treatment of infectious diseases and oxidative stress-related pathologies. Full article

Adipic acid (AA), a pivotal precursor for nylon-6,6 and polyurethane, was synthesized via an innovative catalytic electrocatalytic oxidation strategy in this study. Four distinct MnO_x/CNT nanocatalysts were prepared by hydrothermal and co-precipitation methods and fabricated into electrodes for the oxidation of cyclohexanol (Cy-OH) in a K₂SO₄ neutral solution. Comprehensive characterization revealed that the catalytic performance depended on both crystalline phase configuration and manganese valence states. MnO(OH) and MnO_x were identified as the main active species, with the synergy between MnO species and carbon nanotubes significantly enhancing catalytic activity. Mechanistic investigations demonstrated that under Mn⁴⁺-dominant conditions, low-valence manganese species facilitated Cy-OH-to-cyclohexanone (Cy=O) conversion, while an optimal O_ads/O_lat ratio (≈1) effectively promoted subsequent Cy=O oxidation to AA. Under optimized conditions (1.25 V vs. Ag/AgCl, 80 °C, 15 h), complete Cy-OH conversion was achieved with 56.4% AA yield and exceptional Faradaic efficiency exceeding 94%. This work elucidates manganese-based electrocatalytic oxidation mechanisms, proposes a sequential reaction pathway, and establishes an environmentally benign synthesis protocol for AA, advancing sustainable industrial chemistry. Full article

The covalent conjugation of pharmaceutical compounds to polymeric carriers represents an effective strategy for enhancing drug properties, including improved bioavailability, targeted delivery, and sustained release, while reducing systemic toxicity and adverse effects. By exploiting the physicochemical characteristics of biopolymers—particularly molecular charge and weight—we engineered a polymeric platform for glucocorticoid delivery with precisely controlled parameters including particle size, surface charge, targeting capability, and release kinetics. This study reports a linker-free synthesis of hyaluronic acid-dexamethasone (HA-DEX) conjugates through Steglich esterification, catalyzed by 4-dimethylaminopyridine (DMAP), which facilitates the acylation of sterically hindered alcohols. The reaction specifically couples carboxyl groups of hyaluronic acid with the C21 hydroxyl group of dexamethasone. Incorporation of hydrophobic dexamethasone moieties induced self-assembly into nanoparticles featuring a hydrophobic core and negatively charged hydrophilic shell (−20 to −25 mV ζ-potential). In vitro characterization revealed pH-dependent release profiles, with 80–90% dexamethasone liberated in mildly acidic phosphate buffer (pH 5.2) versus 50–60% in phosphate-buffered saline (pH 7.4) over 35 days, demonstrating both sustained release and inflammation-responsive behavior. The conjugates exhibited potent anti-inflammatory activity in a human tumor necrosis factor-α (TNFα)-induced inflammation model. These findings position HA-DEX conjugates as promising candidates for targeted glucocorticoid delivery to specific anatomical sites including ocular, articular, and tympanic tissues, where their combination of CD44-targeting capability, enhanced permeability and retention effects, and stimulus-responsive release can optimize therapeutic outcomes while minimizing off-target effects. Full article

Monoterpenes and their derivatives are important starting compounds in the design of new biologically active substances. In particular, cineole, isolated from eucalyptus essential oil, exhibits a wide range of biological activities. Here, the synthesis of new heterocyclic compounds containing a cineole fragment by the acid-catalyzed condensation of α-pinene-derived 8-hydroxy-6-hydroxymethyllimonene with monoterpene aldehydes was carried out for the first time. The reactions of 8-hydroxy-6-hydroxymethyllimonene with cuminaldehyde, perillylaldehyde, myrtenal, citral, and geranial were studied in the presence of heterogeneous K10 clay or Lewis acid BF₃·Et₂O. The main products of these reactions were compounds with the methanopyrano[4,3-b]pyran scaffold having a 1,8-cineole fragment. As a result of this work, five new compounds with the methanopyrano[4,3-b]pyran scaffold were synthesized. The use of BF₃·Et₂O led to an increase in the yields of target products, compared with the results obtained on K10 clay. Full article

Bioconversion of cortisone leads to the synthesis of the steroid derivatives 1,9β,17,21-tetrahydroxy-4-methyl-19-nor-9β-pregna-1,3,5(10)-trien-11,20-dione (SCA) and 1,9β,17,20β,21-pentahydroxy-4-methyl-19-nor-9β-pregna-1,3,5(10)-trien-11-one (SCB), which have been identified as biologically active molecules in affections associated with oxidative stress and inflammation, particularly in the skin and eye. To date, the synthesis of SCA and SCB can only be achieved through a biocatalytic approach, following a biotransformation process catalyzed by Rhodococcus rhodnii DSM 43960, a synthetic pathway that adheres to the principles of green chemistry. To further enhance the sustainability of this process, this study demonstrated that SCA and SCB can be synthesized by bioconversion in a complex medium derived from a dual upcycling process involving olive leaves (UOLM). By formulating a medium based on olive leaves, a by-product derived from the previously reported biotechnological production of lactic acid, and using a concentration of 10% v/v UOLM and 1 g/L cortisone at pH 7.5, bioconversion yields of 90 ± 4.5% were achieved, with a predominance of SCB. Investigations into the addition of supplements, such as tryptone, peptone, and corn steep liquor (CSL), to assess potential improvements in yield were conducted, but no significant positive variations were observed. For the first time, bioactive steroids were synthesized from a medium obtained through a dual upcycling process of olive leaves, introducing an innovative method that opens new possibilities for the investigation of a second generation of biosteroids synthesized from lignocellulosic feedstocks. Full article

Seed development plays a critical role in determining both crop yield and grain quality in rice. As a key nutrient storage organ, the rice endosperm development not only contributes to grain filling but also plays an essential role during the early stages of seed germination. Amino acid metabolism is active during the process of seed development and seed germination. Asparagine is a primary amino acid responsible for long-distance organic nitrogen transport in plants. Asparagine synthetase catalyzes the synthesis of asparagine from aspartate and glutamine. In this study, CRISPR/Cas9-mediated knockout mutants of the OsASN2 gene of rice were generated. Homozygous mutants exhibited complete failure of seed germination, and heterozygotes could not produce homozygous offspring. Endosperm development of homozygous mutant seeds showed severe defects. Additionally, interacting protein screening combined with pull-down and co-immunoprecipitation (Co-IP) assays confirmed that OsASN2 physically interacted with pyruvate phosphate dikinase OsPPDKB, the mutants of which showed impaired endosperm development. These findings collectively indicate that OsASN2 plays a critical role in seed development and germination in rice. Full article

The linear polymer polyphosphate (polyP) is found across all three domains of life and fulfills diverse physiological functions, including phosphorus storage, chaperone activity, and stress tolerance. In bacteria, polyP synthesis is catalyzed by polyphosphate kinase (Ppk), whereas its degradation is carried out by exopolyphosphatases (Ppx). Intracellular polyP levels are determined by the balance between these opposing enzymatic activities, although the regulatory mechanisms governing this balance remain incompletely understood. In higher eukaryotes, polyP participates in diverse physiological processes from cell signaling to blood clotting. In relation to this, polyP from Levilactobacillus brevis has been identified as a protective factor against intestinal damage in a mouse model of acute colitis. Subsequent evidence has confirmed that polyP can confer beneficial effects on human intestinal health, prompting an increased interest in the production of polyP by probiotic lactic acid bacteria. Furthermore, polyP is extensively used in the food industry to enhance food quality, preservation, and nutritional value. This review summarizes the current knowledge on polyP metabolism in these bacteria and explores its functional properties and potential applications. Full article

We report the synthesis of pyrrolo[3′,2′:3,4]fluoreno[9,1-gh]quinoline and pyrrolo[2′,3′,4′:4,10]anthra[1,9-fg]quinoline derivatives. This novel class of N-doped polycyclic heteroaromatic compounds was synthesized by a site-selective cross-coupling reaction followed by acid-mediated cycloisomerization and Pd-catalyzed CH arylation as the final ring-closing reactions. Preliminary optical and aromatic properties were studied by means of steady-state absorption and fluorescence spectroscopy and DFT calculation. Special emphasis was placed on the impact of ring alternation and position of the N-doping within the scaffold. Full article

A novel and general approach to the practical ROMP polymerization of cinchona alkaloid derivatives providing novel hybrid materials having quinine attached on a poly(norbornene-5,6-dicarboxyimide) matrix is presented. The concept involves an easy modification of quinine (in general, any cinchona alkaloid) toward clickable 9-azide that reacts with N-propargyl-cis-5-norbornene-exo-2,3-dicarboxylic imide in Cu(I)-catalyzed Huisgen cycloaddition (click chemistry). The resulting monomers undergo a controllable ROMP reaction that leads to novel polymers of a desired length and solubility. This sequence allows for the facile preparation of a regularly decorated polymeric material having one quinine moiety per single mer of the polymer chain inaccessible using typical immobilization methods. A poly(norbornene-5,6-dicarboxyimide) type of polymeric matrix was selected due to the high reactivity of the exo-norbornene motif in Ru(II)-catalyzed ROMP and its chemical and thermal stability as well as convenient, scalable access from inexpensive cis-5-norbornene-exo-2,3-dicarboxylic anhydride (‘one-pot’ Diels–Alder reaction of dicyclopentadiene and maleic anhydride). An appropriate combination of a Grubbs catalyst, Ru(II) (G1, G2), and ROMP conditions allowed for the efficient synthesis of well-defined soluble polymers with mass parameters in the range Mn = 2.24 × 10⁴ – 2.26 × 10⁴ g/mol and Mw = 2.90 × 10⁴–3.05 × 10⁴ g/mol with good polydispersity, Đ_M = 1.32–1.35, and excellent thermal stability (up to 309°C T_d10). Spectroscopic studies (NMR and electronic circular dichroism (ECD)) of these products revealed a linear structure with the slight advantage of a trans-configuration of an olefinic double bond. The resulting short-chain polymer discriminates mandelic acid enantiomers with a preference for the (R)-stereoisomer in spectrofluorimetric assays. This concept seems to be rather general with respect to other molecules dedicated to incorporation into the poly(norbornene-5,6-dicarboxyimide) chain. Full article