Reactions

1,3-Dipolar cycloadditions on nitrone dipoles are key reactions to access five-membered heterocycles, which are useful intermediates in the synthesis of biologically relevant glycomimetics. The good atomic balance and high stereoselectivity characteristic of such reactions make them good candidates for the development of green protocols. In the present work, these features were maximized by avoiding the use of organic solvents and considering starting materials derived from biomass. Reactions involving (acyclic and cyclic) carbohydrate-derived nitrones as dipoles and levoglucosenone as dipolarophile were considered. Performing selected 1,3-dipolar cycloadditions in neat conditions showed reduced reaction times, maintaining similar selectivity and yields with respect to the classical protocols. The use of microwave irradiation and orbital shaking were also exploited to increase the sustainability of the synthetic protocols. The collected results highlight the potential of solvent-free 1,3-dipolar cycloadditions in the design of efficient synthetic routes according to green chemistry principles, such as prevention, atom economy, safer solvents and auxiliaries, and use of renewable feedstocks. Full article

In this study, we develop a concise and efficient synthetic strategy for the construction of eight-membered cyclic diaryl sulfides by undertaking [3+2] cycloaddition, 1,2-hydrogen shift, and C(sp²)-S bond cleavage steps on 2-methylenebenzothiophene-3-ones with aryne, using TBAT as the fluorine source. This transformation proceeds well under mild conditions and affords the target products in high to excellent yields (up to 93% yields). The process provides a practical route to achieving sulfur-containing medium-sized heterocycles. Full article

We describe the design and synthesis of a series of N-[arylsulfonyl]-1H-pyrrole-2-carboxamides as hybrid analogs of the DCAF15 binders E7820 and tasisulam, two representative SPLAMs (sulfonamide-containing molecular glues). These hybrid molecules were designed to combine the key interactions of both parent ligands within the DCAF15 binding site, as supported by docking studies. Binding affinity was evaluated using fluorescence polarization assays, and structure–activity relationships were established, highlighting the importance of dichlorinated pyrrole moieties. Selected compounds were also tested in HCT116 cells to assess in vitro activity. Full article

Mixed oxides were obtained via calcination at 550 °C from layered double hydroxides (LDHs), which were synthesized in a previous study via co-precipitation and co-precipitation followed by hydrothermal treatment using aluminum residues as the source of this element. After characterization, these oxides (Mg-Al-_LDH-CP and Mg-Al-_LDH-H, named according to the synthesis methods of the precursor LDHs) were applied as heterogeneous catalysts in the methyl transesterification of ethyl acetate (EA). The formation of mixed oxides was confirmed by the absence of basal peaks associated with the layered LDH structure in the XRD analysis, due to calcination. Further characterization revealed that Mg-Al-_LDH-CP exhibited the highest number of acidic sites, while Mg-Al-_LDH-H had the highest number of basic sites. The transesterification activity was evaluated in the reaction between ethyl acetate (EA) and methanol (MeOH). The best result, obtained under a molar ratio of 1:5:0.005 (EA:MeOH:catalyst) at 120 °C, was a 63% conversion after 360 min of reaction for the Mg-Al-_LDH-CP catalyst, which had a higher number of acidic sites and fewer basic sites. Additionally, the catalysts demonstrated robustness, maintaining catalytic activity over four cycles without a significant decrease in performance. These results indicate the feasibility of using mixed oxides derived from LDH, synthesized from aluminum residues, as heterogeneous catalysts in transesterification reactions, highlighting their potential for advancing more sustainable catalyst development. Full article

The unique properties of lanthanum oxide nanoparticles (La₂O₃NPs) make them highly suitable for various environmental applications. This study explores the plant-based synthesis of La₂O₃NPs using Drypetes sepiaria as a reducing agent. The synthesized La₂O₃NPs were characterized through a range of spectroscopic and microscopic techniques. Scanning electron microscopy (SEM) revealed that the La₂O₃NPs have an uneven surface and a stony appearance. A morphological analysis indicated that the nanoparticles range in size from 20 to 50 nm. The appreciable band gap energy values were concluded as 5.5 eV. The crystal structure and elemental composition were determined using X-ray diffraction (XRD) and energy-dispersive spectroscopy (EDS). The results from the microplate assay method demonstrated enhanced anti-biofilm properties, and photocatalytic tests showed significant dye-degradation capabilities. The degradation efficiency and zone inhibition values of the La₂O₃NPs were found to be 90.12% and 39.18%, respectively. Full article

Unlike on Fe and Co catalysts, the CO conversion effect on Ru catalyst performance is little reported. This study is undertaken to explore the issue using a series of Ru/NaY catalysts under 200–230 °C, 2.0 MPa, H₂/CO = 2, and 10–60% CO conversion in a 1 L continuous stirred tank reactor (CSTR). The results are comparatively studied with those of Fe and Co catalysts reported previously. The NaY support and four 1.0%, 2.5%, 5.0%, and 7.5% Ru/NaY catalysts were characterized by BET, H₂ chemisorption, H₂O-TPD, XRD, HRTEM, and XANES/EXAFS techniques. The BET and XRD results suggest a high surface area (730 m²/g), high degree of crystallinity of the NaY support, and high dispersion of Ru, while an hcp Ru structure and well-reduced Ru were reflected in the HR-TEM FFT and XANES/EXAFS results. The reaction results indicate that the CO conversion effect on CH₄ and C₅₊ selectivities on the Ru is the same as that on the Fe and Co catalysts, with CH₄ selectivity decreasing and C₅₊ selectivity increasing with increasing CO conversion. However, the CO conversion effect on olefin formation for the Ru catalyst was found to be opposite to that of the Fe and Co; increasing CO conversion enhanced olefin formation but suppressed secondary reactions of 1-olefins. The H₂O cofeeding experiments showed that H₂O impacted olefin formation by suppressing hydrogen adsorption and hydrogenation. The H₂O-TPD experiment evidenced a much stronger H₂O adsorption capacity (6.8 mmol/g-cat) on Ru followed by Co (1 mmol/g-cat), and then Fe (0.2 mmol/g-cat)., which showed only a very low H₂O adsorption capacity.This finding may explain the opposite CO conversion effect on olefin formation observed on the Ru catalyst, and may also explain why low CH₄ selectivity (i.e., 3%) occurred on the Ru catalyst and high CH₄ selectivity (i.e., 6–8%) occurred on the Co catalyst, both of which possess low water gas shift (WGS) activity. Full article

Polypropylene carbonate (PPC) is a biodegradable material derived from propylene oxide (PO) with the renewable resource CO₂. In this study, PPC was prepared by the catalytic polymerization of CO₂ with PO using a zinc glutarate/zinc cobalt double metal cyanide (ZnGA/DMC) composite catalyst prepared from two heterogeneous catalysts, zinc glutarate (ZnGA) and zinc cobalt double metal cyanide (Zn-Co DMC). High selectivity of PPC was achieved among the polymer and propylene carbonate. The prepared PPC had high molecular weight. The thermal stability of the PPC product was obviously improved by the optimization of the reaction conditions. The catalytic effect of the composite catalyst was superior to that of individual ZnGA and Zn-Co DMC, overcoming the shortcomings of those two catalysts. And the composite catalyst also stimulated some synergistic effects between the two composites, which significantly improved the catalytic effect. Full article

The development of efficient and stable photocatalysts is critical for addressing water pollution challenges caused by persistent organic contaminants. However, single-component photocatalysts often suffer from rapid photogenerated carrier recombination and limited visible-light absorption. In this study, a two-dimensional lamellar stacked Bi₂O₃/CeO₂ type-II heterojunction photocatalyst (BC) was successfully synthesized in situ by a topological transformation strategy induced by high-temperature oxidation of monolithic Bi. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) analyses confirmed the uniform distribution of Bi₂O₃ nanosheets on CeO₂ surfaces, forming an intimate interfacial contact that enhances charge separation and transfer efficiency. Photoluminescence (PL) spectroscopy, UV–visible diffuse reflectance spectroscopy (DRS), and electrochemical characterization revealed extended visible-light absorption (up to 550 nm) and accelerated electron migration in the heterojunction. Under simulated sunlight, the optimized BOC (3:1) composite exhibited a ciprofloxacin (CIP) degradation rate constant 2.30 and 5.63 times higher than pure Bi₂O₃ and CeO₂, respectively. Theoretical calculations validated the type-II band alignment with conduction and valence band offsets of 0.07 eV and 0.17 eV, which facilitated efficient spatial separation of photogenerated carriers. This work provides a rational strategy for designing heterojunction photocatalysts and advancing their application in water purification. Full article

Achieving net-zero carbon emissions, this study introduces a sustainable pathway for reducing strontium sulfate (SrSO₄) and celestite ore to strontium sulfide (SrS) using biofuels (biomethane, bioethanol) derived from agro-industrial waste and green hydrogen. Traditional SrSO₄ reduction methods, which rely on fossil-derived reductants like coal and operate at energy-intensive temperatures (1100–1200 °C), generate significant greenhouse gases and toxic byproducts, highlighting the need for eco-friendly alternatives. Experimental results demonstrate that bioethanol outperformed other reductants, achieving 97% conversion of synthetic SrSO₄ at 950 °C within 24 min and 74% conversion of natural celestite ore over 6 h. Remarkably, this bioethanol-driven process matches the energy efficiency of the conventional black ash method while enabling carbon neutrality through renewable feedstock utilization, reducing CO₂ emissions by 30–50%. By valorizing agro-industrial waste streams, this strategy advances circular economy principles and aligns with Mexico’s national agenda for sustainable industrial practices, including its commitment to decarbonizing heavy industries. This study contributes to sustainable development goals and offers a scalable solution for decarbonizing strontium compound production in the chemical industry. Full article

This study shows how important the coordination of Al³⁺ ions in the silver support is for the overall activity in soot combustion. Five silver catalysts with a silver content of 14.7 wt.% were prepared using the following supports: α-Al₂O₃, which has only octahedrally coordinated Al³⁺, θ-Al₂O₃, which has both octahedrally and tetrahedrally coordinated Al³⁺, and zeolites, which contain only tetrahedrally coordinated Al³⁺: 10X, 13X, and 5A. The analysis of the diffraction patterns showed that silver on the surface of catalysts made with the first four supports was mainly in the metallic form, except for Ag/5A in which there was a lack of reflections from Ag⁰ in the XRD pattern. Nevertheless, the difference in the activity of the support and the catalyst as well as the EDX results indicate the presence of silver on the catalyst. The SEM-EDX analysis showed that the silver dispersion strongly depends on the support and that even the zeolites with large silver particles on the surface have silver evenly distributed across the surface. The activity of the catalysts decreased in the following series: Ag/Al 1200 > Ag/5A ≈ Ag/13X > Ag/10X ≈ Ag/Al 550. Time-of-Flight Secondary Ion Mass Spectrometry was used to delve into the reason why the catalyst with the low-surface area α-Al₂O₃ support yielded a better catalyst than that obtained using the high-surface area alumina support and showed that different ratios of secondary ions were emitted from the two surfaces. Full article

Glucose is the most abundant monosaccharide as it is the primary unit of cellulose and starch, which are the more relevant feedstocks for biorefineries. Dehydration of glucose can lead to anhydroglucoses, whose interest has been increasing due to its potential industrial use. Commercial sulfonic polymer resins and a synthesized organic–inorganic mesoporous material were taken as Brønsted acid catalysts. High hexose conversion (up to 98%) and selectivity to anhydroglucoses (~80%) could be reached, turning this process into an alternative route to carbohydrate pyrolysis that presents an energy-intensive downstream. Hexose conversion to anhydroglucoses was related to the amount of acid sites, and the removal of one molecule of water from hexoses to produce anhydroglucoses was found as the preferential dehydration route over a bare Brønsted acid catalyst in anhydrous polar aprotic solvent (DMF) at mild conditions. Product distribution changed dramatically upon catalyst deactivation with HMF and fructose emerging as relevant products. It was suggested that an additional Lewis surface is produced during the deactivation process, probably arising from the formation of insoluble high molecular weight compounds in acidic media. Full article

This review analyzes TiO₂-based coatings formed by the plasma electrolytic oxidation (PEO) process of titanium for the photocatalytic degradation of methyl orange (MO) under simulated solar irradiation conditions. PEO is recognized as a useful technique for creating oxide coatings on various metals, particularly titanium, to assist in the degradation of organic pollutants. TiO₂-based photocatalysts in the form of coatings are more practical than TiO₂-based photocatalysts in the form of powder because the photocatalyst does not need to be recycled and reused after wastewater degradation treatment, which is an expensive and time-consuming process. In addition, the main advantage of PEO in the synthesis of TiO₂-based photocatalysts is its short processing time (a few minutes), as it excludes the annealing step needed to convert the amorphous TiO₂ into a crystalline phase, a prerequisite for a possible photocatalytic application. Pure TiO₂ coatings formed by PEO have a low photocatalytic efficiency in the degradation of MO, which is due to the rapid recombination of the photo-generated electron/hole pairs. In this review, recent advances in the sensitization of TiO₂ with narrow band gap semiconductors (WO₃, SnO₂, CdS, Sb₂O₃, Bi₂O₃, and Al₂TiO₅), doping with rare earth ions (example Eu³⁺) and transition metals (Mn, Ni, Co, Fe) are summarized as an effective strategy to reduce the recombination of photo-generated electron/hole pairs and to improve the photocatalytic efficiency of TiO₂ coatings. Full article

Cu₂O, a narrow-bandgap semiconductor with visible light absorption capabilities, faces limitations in photocatalytic applications due to photocorrosion from hole self-oxidation and insufficient light absorption. In this work, a series of novel spherical Cu₂O/FePO₄ Z-scheme heterojunctions were successfully synthesized via self-assembly to overcome these challenges. The photocurrent, electrical impedance spectroscopy (EIS), and photoluminescence (PL) tests showed that Cu₂O/1.5FePO₄ (CF1.5) had excellent electron hole separation efficiency. Subsequently, photocatalytic degradation was utilized as a probing technique to further confirm the above conclusions, with the kinetic reaction constants of CF1.5 being 2.46 and 11.23 times higher than those of Cu₂O and FePO₄, respectively. After five cycles of experiments and XPS analysis, it was found that the content of Cu(I) in CF1.5 did not significantly decrease after the reaction, indicating that it has superior anti-photocorrosion performance compared to single Cu₂O, which is also due to the establishment of a Z-scheme heterojunction. Systematic studies using radical scavenging experiments and ESR tests identified ·OH and ·O₂⁻ as the main active species involved in photocatalysis. The formation of a Z-scheme heterojunction not only enhances the photocatalytic activity of the CF1.5 composite but also effectively suppresses the photocorrosion of Cu₂O, thereby offering a promising approach for enhancing anti-photocorrosion of Cu₂O. Full article

The development of heterostructures incorporating photocatalysts optimized for visible-light activity represents a major breakthrough in the field of environmental remediation research, offering innovative and sustainable solutions for environmental purification. This study explores the photocatalytic capabilities of a SnFe₂O₄/g-C₃N₄ heterojunction nanocomposite, successfully synthesized from graphitic carbon nitride (g-C₃N₄) and tin ferrate (SnFe₂O₄) and applied to the degradation of the cationic dye brilliant cresyl blue (BCB) in an aqueous solution. These two components are particularly attractive due to their low cost and ease of fabrication. Various characterization techniques, including XRD, FTIR, SEM, and TEM, were used to confirm the successful integration of SnFe₂O₄ and g-C₃N₄ phases in the synthesized catalysts. The photocatalytic and photo-Fenton-like activity of the heterojunction composites was evaluated by the degradation of brilliant cresyl blue under visible LED illumination. Compared to the pure components SnFe₂O₄ and g-C₃N₄, the SnFe₂O₄/g-C₃N₄ nanocomposite demonstrated a superior photocatalytic performance. Furthermore, the photo-Fenton-like performance of the composites is much higher than the photocatalytic performances. The significant improvement in photo-Fenton activity is attributed to the synergistic effect between SnFe₂O₄ and g-C₃N₄, as well as the efficient separation of photoexcited electron/hole pairs. The recyclability of the SnFe₂O₄/g-C₃N₄ composite toward BCB photo-Fenton like degradation was also shown. This study aimed to assess the modeling and optimization of photo-Fenton-like removal BCB using the SnFe₂O₄/g-C₃N₄ nanomaterial. The main parameters (photocatalyst dose, initial dye concentration, H₂O₂ volume, and reaction time) affecting this system were modeled by two approaches: a response surface methodology (RSM) based on a Box–Behnken design and artificial neural network (ANN). A comparison was made between the predictive accuracy of RSM for brilliant cresyl blue (BCB) removal and that of the artificial neural network (ANN) approach. Both methodologies provided satisfactory and comparable predictions, achieving R² values of 0.97 for RSM and 0.99 for ANN. Full article

A heterogeneous polybenzimidazole-supported Mo(VI) catalyst and tert-butyl hydroperoxide (TBHP) as an oxidising reagent have been utilised to establish a more environmentally friendly and greener alkene epoxidation process. A polybenzimidazole-supported Mo(VI) complex (PBI.Mo) has been prepared, characterised and evaluated successfully. The stability and catalytic activity of the produced catalyst have been evaluated for the epoxidation of 1,7-octadiene and 1,5-hexadiene in a jacketed stirred batch reactor to assess its performance towards these alkenes. The suitability and efficiency of the catalyst have been compared by studying the effect of reaction temperature, feed mole ratio of alkene to TBHP, catalyst loading, and reaction time on the yield of 1,2-epoxy-5-hexene and 1,2-epoxy-7-octene. Response surface methodology (RSM) using Box–Behnken Design (BBD) has been employed to design experimental runs and study the catalytic performance of the PBI.Mo catalyst for all batch experimental results. A quadratic regression model has been developed representing an empirical relationship between reaction variables and response, which is the yield of epoxides. The numerical optimisation technique concluded that the maximum yield that can be reached is 66.22% for 1,7-octadiene and 64.2% for 1,5-hexadiene. The reactivity of alkenes was observed to follow the sequence 1,5-hexadiene > 1,7-octadiene. The findings of this study confirm that the optimal reaction conditions vary between the two reactions, indicating differences in catalytic performance for each alkene. Full article

In this work, we studied the main decomposition reactions on the ground state of nitromethane (CH₃NO₂) with the CASPT2 approach. The energetics of the main elementary reactions of the title molecule have been analyzed on the basis of Gibbs free energies obtained from standard expressions of statistical thermodynamics. In addition, we describe a mapping method (orthogonalized 3D representation) for the potential energy surfaces (PESs) by defining an orthonormal basis consisting of two $R^n$ orthonormal vectors (n, internal degrees of freedom) that allows us to obtain a set of ordered points in the plane (vector subspace) spanned by such a basis. Geometries and harmonic frequencies of all species and orthogonalized 3D representations of the PESs have been computed with the CASPT2 approach. It is found that all of the analyzed kinetically controlled reactions of nitromethane are endergonic. For such a class of reactions, the dissociation of nitromethane into CH₃ and NO₂ is the process with the lower activation energy barrier (ΔG); that is, the C-N bond cleavage is the most favorable process. In contrast, there exists a dynamically controlled process that evolves through a roaming reaction mechanism and is an exergonic reaction at high temperatures: CH₃NO₂ → [CH₃^…NO₂]* → [CH₃ONO]* → CH₃O + NO. The above assertions are supported by CASPT2 mappings of the potential energy surfaces (PESs) and classical trajectories obtained by “on-the fly” CASSCF molecular dynamics calculations. Full article

We describe the design and synthesis of a series of 7-(N-aryl pyrrolidinyl) indoles and oxo-analogs as isosteric mimics of the DCAF15 binder E7820, a well-known member of aryl sulfonamides known as SPLAMs. The functionalization of C-7 in indoles was achieved by metal-catalyzed CH-activation with unexpected results. Binding assays revealed the pyrrolidine N-aryl carboxylic acid analog to be as equally active as E7820. Full article

In this work, tin and zinc salts of silicotungstic and phosphotungstic acids were synthesized, characterized, and tested as catalysts for esterification reactions of glycerol with acetic acid (HOAc) to produce glycerol esters such as monoacetyl glycerol (MAG), which are used as additives in the pharmaceutical and food industries and in the manufacturing of explosives, or, in the case of di- or triacetyl glycerol (DAG and TAG), green bioadditives for diesel or gasoline. The activity of metal-exchanged salts (Zn, Sn) in H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀ heteropolyacids was evaluated in esterification reactions at room temperature. Among the catalysts tested, Sn_2/3PW₁₂O₄₀ was the most active and selective toward the glycerol esters. The process’s selectivity can be controlled by changes to reaction conditions. The maximum selectivitiesy of DAG and TAG were 60% and 30%, respectively, using a 1:3 molar ratio of glycerol/HOAc and a Sn_3/2PW₁₂O₄₀/673 K catalyst load of 0.4 mol%. Under these conditions, a glycerol conversion rate of 95% was observed and selectivity towards DAG and TAG was observed at 60% and 30%, respectively. The results were achieved after an 8 h reaction at a temperature of 333 K. The Sn_3/2PW₁₂O₄₀/673 K catalyst demonstrated the highest efficiency, which was attributed to its higher degree of acidity. Full article

This study combines experimental and density functional theory (DFT) to evaluate the influence of alkaline cation characteristics on the electronic structure and photodegradation efficacy of organic dyes in MNbO₃ (M = Na, K) perovskites. The X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Near Edge Spectroscopy (XANES) spectra at the Nb edge of the Perovskites were employed to characterize its chemical and structural properties. The DFT calculations were carried out to simulate XANES spectra as well as the structural and electrical properties of KNbO₃ and NaNbO₃. Our results show that the simulated and experimental XANES spectra are similar, indicating that the computational simulations were able to capture the local structure of the niobate samples. In addition, a photocatalytic experiment was conducted to benchmark the methylene blue consumption efficiency between different niobates. The findings demonstrated that KNbO₃ is more efficient than NaNbO₃ for methylene blue UV photocatalytic degradation, which is associated with their electronic properties. This arises as a direct result of the variably deformed NbO₆ octahedra resulting from the different alkali used. Our findings facilitate the advancement of stable and abundantly available photocatalysts, which may be employed for energy-intensive processes such as the mineralization of organic water pollutants and hydrogen production by water splitting. Full article