Since the beginning of the 20th century, numerous research efforts made elegant use of barbituric acid derivatives as building blocks for the elaboration of more complex and useful molecules in the field of pharmaceutical chemistry and material sciences. However, the construction of chiral scaffolds by the catalytic enantioselective transformation of barbituric acid and derivatives has only emerged recently. The specific properties of these rather planar scaffolds, which also encompass either a high Brønsted acidity concerning the native barbituric acid or the marked electrophilic character of alkylidene barbituric acids, required specific developments to achieve efficient asymmetric processes. This review covers the enantioselective catalytic reactions developed for barbituric acid platforms using an organocatalytic and metal-based enantioselective sequences. These achievements currently allow several unique addition and annulation reactions towards the construction of high valued chiral heterocycles from barbituric acid derivatives along with innovative enantioselective developments. Full article

Utilizing plant-based materials as a biofuel source is an increasingly popular attempt to redesign the global energy cycle. This endeavour underlines the potential of cellulase enzymes for green energy production and requires the structural and functional engineering of natural enzymes to enhance their utilization. In this work, we aimed to engineer enzymatic and functional properties of Endoglucanase I (EGI) by swapping the Ala43-Gly83 region of Cellobiohydrolase I (CBHI) from Trichoderma reesei. Herein, we report the enhanced enzymatic activity and improved thermal stability of the engineered enzyme, called EGI_swapped, compared to EGI. The difference in the enzymatic activity profile of EGI_swapped and the EGI enzymes became more pronounced upon increasing metal-ion concentrations in the reaction media. Notably, the engineered enzyme retained a considerable level of enzymatic activity after thermal incubation for 90 min at 70 °C while EGI completely lost its enzymatic activity. Circular Dichroism spectroscopy studies revealed distinctive conformational and thermal susceptibility differences between EGI_swapped and EGI enzymes, confirming the improved structural integrity of the swapped enzyme. This study highlights the importance of swapping the metal-ion coordination region in the engineering of EGI enzyme for enhanced structural and thermal stability. Full article

We report a general, highly selective method for Suzuki–Miyaura cross-coupling of N-acylphthalimides via N–C(O) acyl cleavage catalyzed by Pd–PEPPSI-type precatalysts. Of broad synthetic interest, the method introduces N-acylphthalimides as new, bench-stable, highly reactive, twist-controlled, amide-based precursors to acyl-metal intermediates. The reaction delivers functionalized biaryl ketones by acylative Suzuki–Miyaura cross-coupling with readily available boronic acids. Studies demonstrate that cheap, easily prepared, and broadly applicable Pd–PEPPSI-type precatalysts supported by a sterically demanding IPr (1,3-Bis-(2,6-diisopropylphenyl)imidazol-2-ylidene) ancillary ligand provide high yields in this reaction. Preliminary selectivity studies and the effect of Pd–N-heterocyclic carbenes (NHC) complexes with allyl-type throw-away ligands are described. We expect that N-acylphthalimides will find significant use as amide-based acyl coupling reagents and cross-coupling precursors to acyl-metal intermediates. Full article

The unique morphological characteristics of carbon nanotubes (CNTs) present the intriguing opportunity of exploiting the inner cavity for carrying out chemical reactions. Such reactions are catalysed either by the individual tubes that function both as catalysts and nanoreactors or by additional catalytic species that are confined within the channel. Such confinement creates what is called “confinement effect”, which can result in different catalytic features affecting activity, stability and selectivity. The review highlights the recent major advancements of catalysis conducted within the CNTs, starting from the synthesis of the catalytic composite, and discussing the most notable catalytic processes that have been reported in the last decade. Full article

Zeolites are promising catalysts that are widely used in petrochemical, oil, and gas industries due to their unique characteristics, such as ordered microporous networks, good hydrothermal stability, large surface area, tunable acidity, and shape-selectivity. Nevertheless, the sole presence of microporous channels in zeolites inevitably restricts the diffusion of bulky reactants and products into and out of the microporous networks, leading to retarded reaction rates or catalyst deactivation. This problem can be overcome by developing hierarchical zeolites which involve mesoporous and macroporous networks. The meso- and macro-porosities can enhance the mass transport of molecules and simultaneously maintain the intrinsic shape selectivity of zeolite microporosity. Hierarchical zeolites are mainly developed through post-synthesis and pre-synthesis or in situ modification of zeolites. In this review, we evaluated both pre-synthesis and post-synthesis modification strategies with more focus on post-synthesis modification strategies. The role of various synthesis strategies on the intrinsic properties of hierarchical zeolites is discussed. The catalytic performance of hierarchical zeolites in important biomass reactions, such as catalytic pyrolysis of biomass feedstock and upgradation of bio-oil, has been summarized. The utilization of hierarchical zeolites tends to give a higher aromatic yield than conventional zeolites with microporosity solely. Full article

A TiO₂-Carbon (TiO₂C) composite was prepared using the microwave-assisted method and sulfonated using fuming sulfuric acid to produce a TiO₂C solid acid catalyst. The prepared solid acid catalyst was characterised using scanning electron microscopy, Brunauer-Emmett-Teller analysis, Fourier transform infrared spectroscopy, and X-ray diffraction. Crystallinity analysis confirmed that TiO₂C has an anatase structure, while analysis of its morphology showed a combination of spheres and particles with a diameter of 50 nm. The TiO₂C solid acid catalyst was tested for use in the catalytic dehydration of fructose to 5-hydroxymethylfurfural (5-HMF). The effect of reaction time, reaction temperature, catalyst dosage, and solvent were investigated against the 5-HMF yield. The 5-HMF yield was found to be 90% under optimum conditions. The solid acid catalyst is very stable and can be reused for four catalytic cycles. Hence, the material has great potential for use in industrial applications and can be used for the direct conversion of fructose to 5-HMF because of its high activity and high reusability. Full article

The influence of the protecting agent’s nature on gold particle size and dispersion was studied in this work over a series of gold-based catalysts. CO and glucose oxidation were chosen as catalytic reactions to determine the catalyst’s structure–activity relationship. The nature of the support appeared to be the predominant factor for the increase in activity, as the oxygen mobility was decisive for the CO oxidation in the same way that the Lewis acidity was decisive for the glucose oxidation. For the same catalyst composition, the use of montmorillonite as the stabilizing agent resulted in better catalytic performance. Full article

Palladium catalysts supported by a mesoporous form of sulfonated poly-divinylbenzene, Pd/µS-pDVB10 (1%, w/w) and Pd/µS-pDVB35 (3.6% w/w), were applied to the direct synthesis of hydrogen peroxide from dihydrogen and dioxygen. The reaction was carried for 4 h out in a semibatch reactor with continuous feed of the gas mixture (H₂/O₂ = 1/24, v/v; total flow rate 25 mL·min⁻¹), at 25 °C and 101 kPa. The catalytic performances were compared with those of a commercial egg-shell Pd/C catalyst (1%, w/w) and of a palladium catalyst supported by a macroreticular sulfonated ion-exchange resin, Pd/mS-pSDVB10 (1%, w/w). Pd/µS-pDVB10 and Pd/C showed the highest specific activity (H₂ consumption rate of about 75–80 h⁻¹), but the resin supported catalyst was much more selective (ca 50% with no promoters). The nanoparticles (NP) size was somewhat larger in Pd/µS-pDVB10, showing that either the reaction was structure insensitive or diffusion limited to some extent over Pd/C, in which the support is microporous. The open pore structure of Pd/µS-pDVB10, possibly ensuring the fast removal of H₂O₂ from the catalyst, could also be the cause of the relatively high selectivity of this catalyst. In summary, Pd/µS-pDVB10 was the most productive catalyst, forming ca 375 mol_H2O2·kg_Pd⁻¹·h⁻¹, also because it retained a constant selectivity, while the other ones underwent a more or less pronounced loss of selectivity after 80–90 min. Ageing experiments showed that for a palladium catalyst supported on sulfonated mesoporous poly-divinylbenzene storage under oxidative conditions implied some deactivation, but a lower drop in the selectivity; regeneration upon a reductive treatment or storage under strictly anaerobic conditions (dry-box) lead to an increase of the activity but to both a lower initial selectivity and a higher drop of selectivity with time. Full article

While commercial hydrodeoxygenation (HDO) processes convert fats, oils, and grease (FOG) to fuel-like hydrocarbons, alternative processes based on decarboxylation/decarbonylation (deCO_x) continue to attract interest. In this contribution, the activity of 20% Ni-5% Cu/Al₂O₃ in the deCO_x of waste free fatty acid (FFA)-based feeds—including brown grease (BG) and an FFA feed obtained by steam stripping a biodiesel feedstock—was investigated, along with the structure-activity relationships responsible for Ni promotion by Cu and the structural evolution of catalysts during use and regeneration. In eight-hour experiments, near quantitative conversion of the aforementioned feeds to diesel-like hydrocarbons was achieved. Moreover, yields of diesel-like hydrocarbons in excess of 80% were obtained at all reaction times during a BG upgrading experiment lasting 100 h, after which the catalyst was successfully regenerated in situ and found to display improved performance during a second 100 h cycle. Insights into this improved performance were obtained through characterization of the fresh and spent catalyst, which indicated that metal particle sintering, alloying of Ni with Cu, and particle enrichment with Cu occur during reaction and/or catalyst regeneration. Full article

Serious water pollution and the exhausting of fossil resources have become worldwide urgent issues yet to be solved. Solar energy driving photocatalysis processes based on semiconductor catalysts is considered to be the most promising technique for the remediation of wastewater. However, the relatively low photocatalytic efficiency remains a critical limitation for the practical use of the photocatalysts. To solve this problem, numerous strategies have been developed for the preparation of advanced photocatalysts. Particularly, incorporating a semiconductor with various functional components from atoms to individual semiconductors or metals to form a composite catalyst have become a facile approach for the design of high-efficiency catalysts. Herein, the recent progress in the development of novel photocatalysts for wastewater treatment via various methods in the sight of composite techniques are systematically discussed. Moreover, a brief summary of the current challenges and an outlook for the development of composite photocatalysts in the area of wastewater treatment are provided. Full article

To overcome the rapid deactivation of conventional ZSM-5, novel nanosheet MFI zeolites, with different Si/Al molar ratios were well fabricated. It was found that Si/Al molar ratios, do not just affect acid properties, but also determine the morphologies of nanosheet MFI zeolites by changing a-c plane areas of zeolite nanosheets. In reaction of gas phase glycerol dehydration to acrolein, the nanosheet MFI zeolites were much more active and stable than conventional ZSM-5 catalysts, owing to their suitable acidity and unique nanosheet structure. For nanosheet MFI zeolite, with Si/Al = 50 (NMZ-50), the conversion of glycerol is higher than 99% in the initial 12 h, with an acrolein selectivity of 86.6%, better than most previous reports. This superior stability of NMZ-50 can be ascribed to its low coke deposition rate and improved coke tolerance capacity. Additionally, it is interesting to find that Al contents do not just simply affect acid properties, but also determine morphologies of nanosheet MFI zeolites, and thus influence catalytic performance. Full article

Crosslinked enzyme aggregates (CLEAs) of a thermostable cyclodextrin glucosyltransferase (CGTase) from Thermoanaerobacter sp. have been prepared for the production of cyclodextrins (CDs). Different parameters in the precipitation (nature and concentration of precipitant) and crosslinking steps (time of reaction with cross-linker, nature and concentration of the crosslinker) were evaluated on the production of CLEAs of CGTase. Among the seven studied precipitants, acetone with a 75% (v/v) concentration produced the aggregates of CGTase with higher activity, which retained 97% of the initial activity. Concerning the cross-linker (glutaraldehyde, starch–aldehyde, and pectin–aldehyde), starch–aldehyde produced the most active CLEAs. The use of bovine serum albumin as co-feeder decreased the expressed activity. Addition of polyethylenimine at the end of cross-linking step prevented the leakage of the enzyme and the subsequent Schiff’s bases reduction with sodium borohydride permitted to maintain 24% of the initial activity even with the large dextrin as substrate. The optimal conditions for the immobilization process required were defined as 75% (v/v) acetone as precipitation reagent for 1 h at 20 °C, 20 mM starch–aldehyde as crosslinking reagent for 2 h at 20 °C, treatment with 1 mg/mL of polyethylenimine for 5 min, reduction with 1 mg/mL of sodium borohydride. The CLEAs of CGTase were active catalyst (similarly to the free enzyme) in the production of cyclodextrins at 50 °C and pH 6.0 for 6 h reaction, maintaining intact their structures. Besides this, after five cycles of 3 h the total cyclodextrin yield was 80% of the initial value (first batch, with around 45% CD yield). Full article

Dehydrogenation of ethane to ethylene was investigated in the presence of CO₂ over Au catalyst supported on an Mn-doped ceria nanorod. The activity can be greatly enhanced by proper Mn doping. Mn was found to preferentially occupy defect sites or surface sites of ceria, resulting in the formation of extra oxide ions. Characterization results indicated that the reducible oxygen species related to ceria might play a vital role in the dehydrogenation. The addition of CO₂ improved the stability of the catalysts remarkably, since CO₂ can sustainably replenish the reducible oxygen species and eliminate the coke on the surface of the catalysts, which was proved by the H₂-TPR and Raman analysis of spent catalysts. An ethane conversion of 17.4% with an ethylene selectivity of 97.5% can be obtained after 44 h of reaction. Full article

Establishing a heterojunction for two kinds of semiconductor catalysts is a promising way to enhance photocatalytic activity. In this study, nanodiamond (ND) and CuFe-layered double hydroxide (LDH) were hybridized by a simple coprecipitation method as a novel heterojunction to photoactivate H₂O₂. The ND/LDH possessed a hydrotalcite-like structure, large specific surface area (S_BET = 99.16 m²/g), strong absorption of visible-light and low band gap (E_g = 0.94 eV). Under the conditions of ND/LDH dosage 0.0667 g/L, H₂O₂ concentration 19.6 mmol/L, and without initial pH adjustment, 93.5% of 10 mg/L methylene blue (MB) was degraded within 120 min, while only 78.3% of MB was degraded in the presence of LDH instead of ND/LDH. The ND/LDH exhibited excellent stability and maintained relatively high activity, sufficient to photoactivate H₂O₂ even after five recycles. The mechanism study revealed that in the heterojunction of ND/LDH, the photoelectrons transferred from the valence band of LDH (Cu/Fe 3d t_2g) to the conduction band of LDH (Cu/Fe 3d e_g) could spontaneously migrate onto the conduction band of ND, promoting the separation of photo-induced charges. Thus, the photoelectrons had sufficient time to accelerate the redox cycles of Cu³⁺/Cu²⁺ and Fe³⁺/Fe²⁺ to photoactivate H₂O₂ to produce hydroxyl radicals, resulting in excellent photo-Fenton efficiency on MB degradation. Full article

Two novel chiral verbenone-derived triazolium salts have been synthesized from readily available (−)-verbenone and found to be efficient for the enantioselective intramolecular Stetter reaction. The approach, based on the intramolecular annulation between acyl anion equivalents and Michael acceptors, benefits from broad substrate scope, high chemical and stereochemical efficiency, and operational simplicity. Mono-, and disubstituded chromanone derivatives have been obtained in excellent yields and in a highly stereochemical manner. Full article

Cobalt nanoparticles modified with N-doped hierarchical porous carbon derived from biomass are found to be a highly efficient, reusable heterogeneous catalyst for the coupling of nitroarenes with alcohols, selectively affording imines and amines via the borrowing hydrogen strategy for the first time. The product selectivity between imine and amine may be precisely tuned by simple alteration of the reaction conditions without changing the catalyst in one reaction system. In this study, a broad set of complex imines and amines was successfully synthesized in good to high yields with various functional groups tolerated for both nitroarenes and alcohols, highlighting the potentially practical utility of the protocol. This heterogeneous catalyst can be easily removed from the reaction medium by external magnet and can be reused at least four times without significant loss in activity and selectivity. Full article