Search Results (170)

Unsaturated carbon–carbon bonds are fundamental building blocks in organic compounds. The difunctionalization of olefins allows for the rapid construction of drugs and complex molecular architectures. This transformation, which simultaneously installs two distinct functional groups across a carbon–carbon double bond, has therefore emerged as prominent research frontier in organic chemistry. In recent years, the synergy between photoredox and transition metal catalysis has emerged as a powerful and sustainable platform for constructing C-X bonds. This review covers advances since 2018 in the asymmetric difunctionalization of olefins enabled by synergistic visible light photoredox and transition metal catalysis, encompassing the construction of both carbon–carbon and carbon–heteroatom bonds. It systematically summarizes the reaction conditions, substrate scope, mechanisms, and merits and limitations of these catalytic systems, aiming to provide a useful reference for researchers in this field. Full article

The photocatalytic degradation of the pharmaceutical compound nadolol over TiO₂ under UV-LED irradiation was investigated, with particular emphasis on the inhibitory effects of common low-molecular-weight organic acids. Due to its aromatic (tetralin-like) motif and multiple heteroatom-containing functional groups, nadolol serves as a representative model for aromatic micropollutants whose fate can be governed by surface competition and noncovalent interactions. While TiO₂ showed high photocatalytic activity in ultrapure water, achieving complete nadolol degradation within 120 min, the presence of citric, oxalic, and acetic acids markedly reduced the degradation efficiency by approximately 72%, 62%, and 29%, respectively. Experimental results demonstrated that this inhibition could not be attributed solely to pH changes, indicating the contribution of additional molecular-level effects. To elucidate the underlying mechanism, molecular and periodic density functional theory (DFT) calculations were performed. The computational analysis revealed strong interactions between nadolol, organic acids, and the TiO₂ surface, leading to competitive adsorption and partial blocking of photocatalytically active sites. These results provide mechanistic insight into the role of natural organic acids in TiO₂-based photocatalytic systems and highlight the importance of considering real-water matrix components when designing efficient and sustainable photocatalytic water treatment processes. Full article

In this work, the kinetics of the redistribution of oils, resins, and asphaltenes in high-viscosity oil from the Karazhanbas field (Republic of Kazakhstan) were investigated. This was achieved with an ultrasonic treatment (22 kHz, 50 W) in the presence of a zeolite catalyst (1.0 wt%). The parameters of the technological process were established as a temperature range from 30 to 70 °C and an exposure time of 3 to 11 min. This allowed us to increase the oil content by 14.8% and decrease the concentration of resins by 12.2% and asphaltenes by 2.6%. Conversion schemes (“oils ↔ resins” and “resins ↔ asphaltenes”) were developed, which made it possible to determine the main direction of the reaction processes. The most rapid process is the conversion of resins to oils (k₂ = 0.1148–0.1860 min⁻¹). The process of the cracking of asphaltenes with the formation of resins (k₄ = 0.1023–0.1413 min⁻¹) ranks second in rates. Condensation reactions, including the transition of oils to resins (k₁ = 0.0175–0.0252 min⁻¹) and resins to asphaltenes (k₃ = 0.0139–0.0194 min⁻¹), occur significantly more slowly. The calculated activation energies (7.0–10.4 kJ/mol) show that the cavitation treatment of high-viscosity oil in the presence of a catalyst effectuates the processing of heavy oil with minimal energy consumption. A group composition analysis of the light and middle oil fractions demonstrated an increase in paraffinic, naphthenic, benzenic, and olefinic hydrocarbons, with a simultaneous decrease in naphthalenes and heteroatomic compounds. The results obtained confirm the effectiveness of ultrasonic–catalytic treatment for the structural cracking of high-viscosity oil and the formation of lighter hydrocarbon fractions. Full article

The trade-off between the ionic conductivity and the stability of the proton exchange membrane (PEM) is a major concern in the development of PEM water electrolysis (PEMWE). This review focuses on the design and fabrication of homogeneous and composite PEMs for water electrolysis and establishes the structure–performance relationships between the membrane chemical/physical structures and their efficiency metrics—specifically, proton conductivity, hydrogen permeability, and chemical and mechanical stability. A special focus is placed on the fundamental connection between the microstructure and performance of membrane materials. At the molecular level, we systematically illustrate the design principles for main chains, side chains, and sulfonate groups, covering both fluorinated PEMs (encompassing perfluorinated and partially fluorinated membranes) and non-fluorinated PEMs (including aromatic polymers with heteroatom backbones and all-carbon backbones). At the macroscopic level, the review provides an in-depth exploration of two primary modification strategies: creating composites with organic polymers and with inorganic nanofillers. In summary, this review elucidates how these composite approaches leverage material synergies to improve the membrane’s mechanical integrity, proton conduction efficiency, and chemical resistance and offers a theoretical framework for the rational design of next-generation, high-performance PEMs to advance the commercialization of PEMWE technology. Full article

A total of 250 known and novel compounds—ketamine and serotonergic psychedelics or their analogues—designed to target depression, addictions and/or other mental or neurological disorders and developed as “recreational” (illegal) drugs from three chemical families, ergolines, tryptamines and phenylethylamines, were investigated in the context of their ability to cross the human placenta. Using a novel multivariate model involving compounds’ drug-likeness (according to Lipinski’s Ro5), caco-2 membrane permeability, fraction unbound to plasma proteins, steady-state volume of distribution and the total count of heteroatoms (non-carbon atoms with hydrogens included), it was established that the majority of studied compounds are likely to cross the placenta easily, most probably by the passive diffusion mechanism. Atomic contributions of structural elements of studied compounds were investigated using the Morgan fingerprinting algorithm and it was postulated that the fragments promoting transport of compounds across the placenta are carbonyl, hydroxyl, nitro- and phosphoryloxy groups—rigid polycyclic structures, bulky alkyl/aryl groups and halogen atoms restrict the trans-placental passage. All studied compounds are expected to be relatively easily obtained by synthetic routes, which makes them an interesting target for manufacturers of illegal drugs and warrants the need to pursue pharmacological studies of these compounds in silico. Full article

Environmental pollution caused by industrialization and population growth has intensified the demand for sustainable materials capable of mitigating contaminants effectively. In this context, the green synthesis of carbon-based nanomaterials derived from biomass has gained significant attention as an eco-friendly and renewable approach that reduces dependence on fossil resources. These nanomaterials exhibit outstanding physicochemical characteristics, including high surface area, tunable porosity, abundant functional groups, and excellent stability, which enhance their performance in environmental remediation. Specifically, biomass-derived carbon nanomaterials have demonstrated remarkable efficiency as adsorbents for the removal of heavy metals and organic pollutants, as well as photocatalysts for the degradation of toxic compounds under visible light irradiation. The physicochemical properties of the resulting materials are strongly influenced by the type and pretreatment of the biomass, along with synthesis parameters such as pyrolysis temperature, activation process, and heteroatom doping. This review highlights recent advances in the synthesis, characterization, and environmental applications of biomass-derived carbon nanomaterials, emphasizing their potential as cost-effective, scalable, and sustainable solutions for wastewater treatment and pollutant degradation in both aquatic and atmospheric systems. Full article

This study investigates coke formation, structure, and combustion behaviors in paraffin-based Menggulin and naphthenic-based Xinjiang heavy oils under simulated in-situ combustion (ISC) conditions (350 °C, 450 °C), utilizing GC-MS, SEM, ¹³C ss-NMR, and TG-DSC. The results indicate that the crude oil composition determines the coking mechanisms: Xinjiang oil, rich in cyclic hydrocarbons and O/N/S heteroatoms, forms high-yield, compact, sheet- or block-like coke at 350 °C via π–π stacking. In contrast, Menggulin oil, composed primarily of long-chain alkanes, yields loose coke at 350 °C but produces dense, highly aromatized coke at 450 °C, which corresponds to the critical alkane cracking temperature, through intense cracking–polymerization. Temperature differentially regulates oxidative processes, thereby shaping the divergent functional group distributions. Correlations between coke structure and combustion properties reveal that oxygenated/aliphatic-rich cokes exhibit high reactivity, whereas aromatized cokes release more heat. These findings provide guidance for ISC optimization, suggesting that sufficient high-temperature energy is required for paraffinic oils while medium-temperature oxidation regulation is suitable for naphthenic oils. This work advances the theory of ISC coke formation and supports enhanced recovery of heavy oils. Full article

A comparative study on the adsorption of ciprofloxacin (CIP) and sulfamethoxazole (SMX) onto CO₂-activated biochars derived from leather tannery waste (ABT) and Sargassum brown macroalgae (ABS) is presented. N₂ physisorption revealed that ABS possesses a higher Langmuir surface area (1305 m²/g) and a hierarchical micro–mesoporous structure, whereas ABT exhibits a lower surface area (412 m²/g) and a predominantly microporous texture. CHNS and FTIR analyses confirmed the presence of N-, O-, and S-containing heteroatoms and functional groups on both adsorbents, enhancing surface reactivity. Adsorption isotherms fitted well to the Langmuir model, with ABS showing superior maximum capacities of 256.41 mg/g (CIP) and 256.46 mg/g (SMX) compared to ABT (210.13 and 213.00 mg/g, respectively). Kinetic data followed a pseudo-second-order model (R² > 0.998), with ABS exhibiting faster uptake due to its mesoporosity. Over eight reuse cycles, ABS retained >75% removal efficiency for both antibiotics, while ABT declined to 60–70%. pH-dependent adsorption behavior was governed by the point of zero charge (pH_PZC≈ 9.0 for ABT; ≈7.2 for ABS), influencing electrostatic and non-electrostatic interactions. These findings demonstrate that ABS is a highly effective, sustainable adsorbent for antibiotic removal in water treatment applications. Full article

This work reports on the synthesis and ring-opening metathesis polymerization (ROMP) of two novel homologous sulfonyl-containing norbornene dicarboximide monomers, specifically, N-4-(trifluoromethylsulfonyl)phenyl-norbornene-5,6-dicarboximide (1a) and N-4-(trifluoromethylsulfonyl)phenyl-7-oxanorbornene-5,6-dicarboximide (1b) using the Grubbs 2nd generation catalyst (I). The polymers are thoroughly characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermomechanical analysis (TMA), thermogravimetric analysis (TGA), atomic force microscopy (AFM), and X-ray diffraction (XRD), among other techniques. A comparative study of gas transport in membranes based on these ROMP-prepared polymers is performed and the gases studied are hydrogen, oxygen, nitrogen, carbon dioxide, methane, ethylene and propylene. It is found that the presence of sulfonyl pendant groups in the polymer backbone increases the gas permselectivity in slight detriment of the gas permeability compared to a polynorbornene dicarboximide lacking sulfonyl groups. The membrane of the sulfonyl-containing polymer with an oxygen heteroatom in the cyclopentane ring, 2b, is also found to have one of the largest permselectivity coefficients reported to date for the separation of H₂/C₃H₆ in glassy polynorbornene dicarboximides. Full article

In this paper, three quinoline-based quaternary ammonium salts were successfully synthesized, with quinoline, 8-hydroxyquinoline, and 8-methoxyquinoline used as raw materials, and benzyl chloride as a quaternization reagent. The as-synthesized quaternary ammonium salts showed excellent corrosion inhibition performance in the acidic environment based on the derivative’s cationic activity, heteroatom electron effect, and conjugated aromatic system. Specifically, the methoxy-containing product exhibited the highest corrosion inhibition efficiency of 96.92%. The quantitative calculation analysis demonstrated that the addition of methoxy and hydroxyl groups facilitated the quaternization reaction and enhanced the adsorption of the quaternary ammonium salts on the metal surface. The molecular dynamics study indicated that the three corrosion inhibitors adsorbed on the metal surface in a parallel orientation. This study has a certain reference significance for the research and development of quaternary ammonium salt as corrosion inhibitors in an acidic environment. Full article

Carbon dots (CDs) have recently emerged as a novel class of eco-friendly and multifunctional corrosion inhibitors owing to their nanoscale dimensions, tunable surface functionalities, and sustainable synthesis pathways. This review summarizes the latest progress in CD-based inhibitors, focusing on synthesis methods, applications, and inhibition mechanisms. Various strategies—including hydrothermal/solvothermal treatment, microwave irradiation, pyrolysis, electrochemical synthesis, and chemical oxidation—have been employed to obtain CDs with tailored size, heteroatom doping, and surface groups, thereby enhancing their inhibition efficiency. CDs have demonstrated remarkable applicability across diverse corrosive environments, including acidic, neutral chloride, CO₂-saturated, microbiologically influenced, and alkaline systems, often achieving inhibition efficiencies exceeding 90%. Mechanistically, their performance arises from strong adsorption and compact film formation, heteroatom-induced electronic modulation, suppression of anodic and cathodic reactions, and synergistic effects of particle size and structural configuration. Compared with conventional inhibitors, CDs offer higher efficiency, environmental compatibility, and multifunctionality. Despite significant progress, challenges remain regarding precise structural control, scalability of synthesis, and deeper mechanistic understanding. The effectiveness of CDs inhibitors is highly dependent on factors such as pH, temperature, inhibitor concentration, and exposure time, which should be tailored for specific applications to maximize performance. Future research should focus on integrating sustainable synthesis with rational heteroatom engineering and advanced characterization to achieve long-term, cost-effective, and environmentally benign corrosion protection solutions. Compared to earlier reviews, this review discusses the emerging trends in the field of CDs as corrosion inhibitors. Full article

Effective prediction of blood–brain barrier (BBB) permeability remains essential for central nervous system drug development. This study evaluates multiple supervised machine learning models using a public dataset of permeable and non-permeable compounds. Random Forest models demonstrate optimal balance between accuracy and generalizability, outperforming more complex gradient boosting methods that were prone to overfitting. Feature analysis identifies NH/OH and NO group counts as key determinants of passive diffusion, with reduced hydrogen bond donor and heteroatom counts enhancing permeability. Additionally, model performance deteriorates at NH/OH count = 3, establishing this as a decision boundary where hydrogen bonding complexity disrupts reliable prediction. This study shows the non-linear structure-permeability relationships that challenge traditional descriptor-based approaches, while demonstrating that machine learning can simultaneously provide both accurate prediction and applicable insights for drug discovery applications. Full article

Metal–organic frameworks (MOFs) are materials with extremely valuable properties. The latter depend largely on the ligand used; therefore, the design of new organic linkers is a priority task today. A series of s-triazines possessing variable heteroatom-bridged identical substituents, useful ligands for the synthesis of MOFs, is obtained in good to excellent yields. The problem of obtaining free carboxyl groups without forming salts with nitrogen atoms is solved. The products are characterized by NMR spectra and single crystal XRD of selected samples. Unexpected O-triazine bond cleavage under basic hydrolysis conditions is observed. Full article

Element doping and functional group modification engineering serve as efficient approaches that contribute to the improvement of the functional efficiency in graphitic carbon nitride (CN) materials. A CN photocatalyst co-modified with sulfur (S) and cyano moieties was prepared through thermal condensation polymerization. The introduced S species modulated the band structure, increased charge carrier mobility, and significantly promoted charge separation and transport. Additionally, the introduction of cyano groups extended light absorption range and improved the material’s selective adsorption of reactant molecules. The as-prepared sulfur-modified CN photocatalyst obtained after a 6 h thermal treatment, which was capable of degrading organic pollutants and producing hydrogen (H₂) efficiently and stably, exhibited excellent catalytic performance. The photocatalyst’s photocatalyst exhibited a significantly enhanced photocatalytic activity, with a Rhodamine B (RhB) removal efficiency reaching 97.3%. Meanwhile, the H₂ production level reached 1221.47 μmol h⁻¹g⁻¹. Based on four-cycle experiments, the photocatalyst exhibited excellent recyclability and stability in both H₂ production processes and photocatalytic organic pollutant degradation. In addition, mechanistic studies confirmed the dominant role of ·OH and ·O₂⁻ as active species responsible for the reaction system’s performance. This study highlights that the co-decoration of heteroatoms and functional groups can markedly enhance the photocatalytic performance of CN-based materials, offering considerable potential for future applications in energy conversion and environmental remediation. Full article

Terminal alkynes, characterized by sp-hybridized carbon atoms at the molecular termini, possess high electron density and exceptional chemical reactivity. These properties make them ideal candidates for the synthesis of one-dimensional molecular wires and two-dimensional networks. Advances in nanoscale characterization techniques, such as scanning tunneling microscopy and atomic force microscopy, have enabled the real-space visualization of molecular assembly and chemical reactions of terminal alkynes and in situ atomic-level manipulations under surface-confined conditions. In addition, through the combination of spectroscopic measurements, physicochemical properties of and information about resulting nanostructures have been achieved. Moreover, density functional theory calculations provide deeper insights into the underlying reaction pathways and mechanisms. From this perspective, this review summarizes recent progress in the assembly and chemical transformations of terminal alkynes on noble metal surfaces. It discusses strategies for structural modulation and reaction selectivity control, including direct incorporation of heteroatoms or functional groups into precursors, the selection of metal surfaces, the introduction of extrinsic components into molecular systems, and atomic-scale manipulations using scanning probes. Full article