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The pine caterpillar, Dendrolimus punctatus (Walker), is a notorious forest pest. An efficient and convenient synthesis of the sex pheromones of this pest has been achieved. In our synthetic approach, a Wittig coupling of an aldehyde with an ester-bearing phosphonium salt was used to construct the Z-alkene, whereas the E-alkene was prepared via a stereoselective reduction of an alkyne with LiAlH₄. The synthetic sex pheromones would be useful for integrated pest management of the pine caterpillar. Full article

This paper discusses significant advancements in using lignocellulosic biomass for the sustainable production of biofuels and chemicals. As fossil-based resources decline and environmental concerns rise, the paper emphasizes the role of integrated biorefineries in producing renewable liquid fuels and high-value chemicals from biomass. It highlights exploring various green pathways for biomass conversion, with a particular focus on nanocatalysis. Due to their large surface area-to-volume ratio, nanocatalysts provide enhanced catalytic activity and efficiency in biomass transformation processes. The review delves into the synthesis of value-added and furfural platform chemicals alongside the hydrogenolysis of 5-hydroxymethylfurfural (5-HMF) into biofuels like 2,5-dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF). The paper ultimately underscores the importance of nanotechnology in achieving high yield and selectivity in the biomass conversion process, positioning it as a promising approach for future sustainable energy and chemical production. Full article

The objective of this study was to examine the catalytic pyrolysis process of three distinct types of biomasses: baru endocarp (ENB), macaúba endocarp (ENM), and macaúba epicarp (EPM). This was performed with the aim of optimizing the production of hydrocarbons and other volatile compounds of interest through the use of different catalysts. The catalysts utilized in this study were calcium oxide (CaO), phosphate mining waste (PO), niobium pentoxide (Nb₂O₅), and Ni/Nb₂O₅. The methodology entailed pyrolyzing the biomass at temperatures spanning from 508 °C to 791 °C, utilizing a micropyrolyzer in conjunction with a gas chromatograph with mass spectrometry (GC/MS) for product analysis. An experimental design was implemented to assess the impact of catalyst concentration and temperature on the yield and composition of the volatile products. The findings demonstrated that CaO was efficacious in deoxygenating the compounds, particularly at elevated temperatures, thereby promoting the generation of saturated and unsaturated hydrocarbons. In contrast, Nb₂O₅ was effective in the formation of oxygenated compounds, particularly carboxylic acids and phenols. Ni/Nb₂O₅ has been shown to be effective in the production of cyclic, aromatic, alkadienes, and alkenes hydrocarbons. Phosphate mining waste exhibited moderate performance, with potential for specific applications at high temperatures, with important production of cyclic, aromatic, and alkane hydrocarbons. Among the biomasses, EPM demonstrated the greatest potential for hydrocarbon production, indicating its suitability for the development of advanced biofuels. This study advances our understanding of the catalytic pyrolysis of alternative biomasses and underscores the pivotal role of catalysts in optimizing the process, offering invaluable insights for the sustainable production of biofuels and interest in renewable chemicals. Full article

Flow chemistry has shown significant versatility over the last two decades, offering advantages in efficiency, scalability, and sustainability. In this study, the continuous stirred tank reactor (CSTR) was used to optimise the synthesis of α-hydroxyphosphonates via the Pudovik reaction and their subsequent conversion to phosphates through the phospha-Brook rearrangement. The study highlights that using CSTRs allows for better control over reaction parameters, leading to reduced reaction times and improved yields compared to traditional batch methods. The optimised conditions successfully facilitated a range of organophosphates, including electron-rich and electron-poor derivatives, with high efficiency. Additionally, a one-pot tandem process combining the Pudovik reaction and the phospha-Brook rearrangement was developed, reducing reaction times to two hours while maintaining comparable yields. This work demonstrates the potential of CSTRs in flow chemistry for synthesising complex organophosphorus compounds, achieving higher reaction yields and shorter reaction times, highlighting the effectiveness of continuous flow methodologies. Full article

A new topological material, the [c2]daisy-chain rotaxane network, was successfully synthesized via a thiol-ene reaction between a [c2]daisy-chain rotaxane, which consists of a host–guest compound (H–G compound) where a crown ether and a secondary ammonium salt are linked, and a multi-branched thiol compound. The resulting network polymer exhibited higher compressive strength compared to one without the [c2]daisy-chain rotaxane. Additionally, the neutralized [c2]daisy-chain rotaxane network, in which the ammonium salt was neutralized and there was no interaction with the crown ether, showed increased rigidity compared to its state before neutralization. Furthermore, a gel electrolyte was prepared by impregnating the [c2]daisy-chain rotaxane network with an organic electrolyte containing dissolved lithium salts, and its ionic conductivity was investigated. As a result, high ionic conductivity was achieved despite the high polymer content. Full article

The high cost of equipment is a significant entry barrier to research for smaller organisations in developing solutions to air pollution problems. Low-cost electrochemical sensors have shown sensitivity at parts-per-billion by volume (ppbV) mixing ratios but are subject to variations due to changing environmental conditions, particularly temperature. We have previously demonstrated that under isothermal/isohume conditions such as those found in kinetic studies, very stable electrochemical responses occur. In this paper, we demonstrate the utility of a low-cost IoT-based sensor system that employs four-electrode electrochemical sensors under isothermal/isohume conditions for studying the kinetics of the atmospheric oxidation of nitrogen oxides. The results suggest that reproducible results for NO and NO₂ kinetics can be achieved. The method produced oxidation rates of 7.95 × 10³ L² mol⁻² s⁻¹ (±1.3%), for NO and 7.99 × 10⁻⁴ s⁻¹ (±2.1%) for NO₂. This study suggests that the oxidation kinetics of nitrogen oxides can be assessed with low-cost sensors, which can support a wide range of industrial applications, such as designing biocatalytic coatings for air pollution remediation. Full article

The enzymes Cytochrome P450 and Superoxide Reductase, which have a similar coordination center [FeN4S], begin their biochemical cycles similarly. They absorb an oxygen molecule, add two electrons, and link a hydrogen atom to the distal oxygen atom of the product obtained, creating the so-called Compound 0 in the case of the first enzyme. However, the bio-catalytic processes of these two enzymes continue in different ways. In the bio-catalytic cycle of Cytochrome P450, the enzyme binds another proton to the distal oxygen atom, producing a water molecule and Compound 1. In contrast, in the bio-catalytic cycle of the Superoxide Reductase, the enzyme binds a proton to the proximal oxygen atom, producing a hydrogen peroxide molecule, which later decomposes into oxygen and water. The MCSCF method in the CASSCF form was used to study the difference in Cytochrome P450 and Superoxide Reductase’s bio-catalytic cycles. The results of these enzymes’ hydroperoxo adduct models’ geometric optimization showed that, in fact, all their properties, including their spin states, the wave functions in their active zones, and the Fe-N, Fe-S, and Fe-O bond lengths, are different. The Fe-N, Fe-S, and Fe-O chemical bond lengths are much longer in the case of the second enzyme compared to the chemical bond lengths in the case of the first enzyme, reflecting a spin value equal to 5/2 in the second case and a spin value equal to 1/2 in the first. A decisive role in the difference in their bio-catalytic cycles is played by the fact that the first bonded hydrogen atom is linked to the distal oxygen atom in the side position in the case of Compound 0 and the up position in the case of the hydroperoxo adduct of the enzyme Superoxide Reductase, protecting the distal oxygen atom from possible interaction with the substrate. The second protonation to Compound 0 at the distal oxygen atom in the case of Cytochrome P450’s bio-catalytic cycle and the second protonation at the proximal oxygen atom in the case of the hydroperoxo adduct of Superoxide Reductase’s bio-catalytic cycle depend on the proton transfer through the Asp251 channel in the first case and on the transferal of H⁺ from the substrate to the water molecule and the proximal oxygen in the second case. Full article

Drylands in Brazil have been exploring sisal (Agave sisalana) as an essential source of income. However, the solid residues generated because of this activity still need suitable destinations; therefore, research has been carried out to transform them into added-value products. Therefore, the present study evaluated the potential of sisal or agave solid residue as a precursor feedstock for second-generation ethanol production. Acid and acid–alkaline pretreatments were carried out on sisal residues to enrich the biomass with cellulose and maximize enzymatic digestibility. Second-generation ethanol production was carried out using Semi-simultaneous saccharification and fermentation (SSSF). Regardless of catalyst dosage and incubation time, oxalic acid pretreatments generated samples with a similar chemical composition to those pretreated with sulfuric acid. However, samples pretreated with oxalic acid showed lower enzymatic digestibility. Samples pretreated with oxalic acid and sodium hydroxide obtained 14.28 g/L of glucose and cellulose conversion of 79.1% (at 5% solids), while 21.49 g/L glucose and 91.2% of cellulose conversion were obtained in the hydrolysis of pretreated samples with sulfuric acid and sodium hydroxide combined pretreatments. The pretreatment sequence efficiently reduced cellulase dosage from 20 to 10 FPU/g without compromising sugar release. SSSF achieved maximum production of 40 g/L ethanol and 43% ethanol conversion using 30% solids and gradually adding biomass and cellulases. Full article

In this work, an attempt is made to theoretically substantiate the experimentally known facts of the influence of halogen concentration on the catalytic properties of the neodymium-based Ziegler–Natta system. Based on the structural and thermochemical data obtained using modern methods of quantum chemistry, the process of the 1,3-butadiene cis-1,4-polymerization under the model active centers of the neodymium Ziegler–Natta catalysts with different contents of chloride ions was studied. Results are presented that explain the increase in the cis-stereospecificity and activity of the polymerization system with an increase in the content of the chloride ions in the neodymium catalytic system. Reasons were established for the decrease in the concentration of active centers relative to the introduced Nd(III) with an excess of chloride ions and the occurrence of the anti-syn isomerization as a source of the formation of the trans-1,4-structures in the cis-1,4-polybutadiene. Full article

Waste plastics were successfully decomposed with a solid acid catalyst to make oil. Spent FCC (Fluid Catalytic Cracking) catalyst was used for this process. The operation of this process was conducted in a horizontal agitated laboratory reactor with an inner volume of 1 L with 0.1 kg/h to the capacity of 80 kg/h of the demonstrate plant conducted by continuously feeding a plastic flake or molded cube to the heated powder catalyst bed at around 400–450 °C. The yield of oil was as high as 70 to 85%, depending on the type of plastic. The processing of a variety of waste plastics from home waste, industrial waste and even marine plastics could be processed to obtain oil with a low freezing point and a high heating value. The product was mainly composed of iso-paraffins, olefins and aromatics. The effective in situ dichlorination was attained from the waste plastic containing PVC. A small amount of PET in the plastic was converted to methyl benzene during the cracking operation. Full article

Zinc oxide and titanium dioxide are materials with strong photocatalytic and antimicrobial activity. This activity is greater when the material is in nanocrystalline form. It has been seen that these properties are also present in the ZnO-TiO₂ nanocomposite material, and the extent depends on multiple factors, such as crystallinity, structural composition, crystallite size, and morphology. These structural properties can be varied by acting on the synthesis of the material, obtaining a wide variety of composites: random nanoparticles, nanorods, nanowires, nanotubes, nanofibers, tetrapods, core–shell, hollow spheres, inverse opal structures (IOSs), hierarchical structures, and films. When an interface between nanocrystallites of the two oxides is created, the composite system manages to have photocatalytic activity greater than that of the two separate oxides, and in certain circumstances, even greater than P25. The antimicrobial activity results also improved for the composite system compared to the two separate oxides. These two aspects make these materials interesting in various fields, such as wastewater and air treatment, energy devices, solar filters, and pharmaceutical products and in the context of the restoration of monumental cultural assets, in which their use has a preventive purpose in the formation of biofilms. In this review we analyse the synthesis techniques of ZnO-TiO₂ nanocomposites, correlating them to the shape obtained, as well as the photocatalytic and antimicrobial activity. It is also illustrated how ZnO-TiO₂ nanocomposites can have a less negative impact on toxicity for humans and the environment compared to the more toxic ZnO nanoparticles or ZnO. Full article

Acetoin biosynthesis by two Bacillus subtilis strains valorising crude glycerol was thoroughly explored within a pre-defined range of culture conditions and systems. B. subtilis ACA-DC 1176 stood out for its higher efficiency in acetoin production, prompting an investigation into the potential for enhanced productivity through the evaluation of diverse culture conditions and media compositions. The primary by-products of the biodiesel and corn industries, namely crude glycerol and corn steep liquor, respectively, were successfully employed as the principal carbon and nitrogen sources of the newly developed low-cost culture medium. Furthermore, the results of the various feeding strategies that were tested indicated that the conversion of 2,3-butanediol (BDO) to acetoin occurred exclusively when the concentration of glycerol was below approximately 5 g/L. This seemed to be necessary for the production of NADH, which is essential for maintaining cellular processes. Following the complete depletion of glycerol, acetic acid increased and became the predominant metabolite, while both acetoin and BDO decreased, presumably resulting in ATP generation. This is likely a mechanism employed by the cell to generate energy in the absence of a carbon source. In the fed-batch bioreactor culture, the kinetics of metabolites differed, as there was no conversion of BDO to acetoin at the final depletion of glycerol. At volumetric mass transfer coefficient (k_La) levels exceeding approximately 70 1/h, the production of acetoin was favoured over that of BDO, with the highest observed acetoin/BDO ratio reaching 4.29 g/g. Conversely, at k_La values below approximately 60 1/h, the titres of acetoin and BDO were found to be nearly equal. The final concentrations of acetoin and BDO reached 36.0 g/L and 25.5 g/L, respectively, resulting in a total yield of both (acetoin + BDO) per glycerol consumption of 0.40 g/g. To the best of our knowledge, this is the first study to focus on acetoin production from crude glycerol fermentative valorisation. The study presents new findings regarding the parameters influencing the level of BDO conversion to acetoin. However, further research is required in order to gain a comprehensive understanding of the underlying phenomena and metabolic pathways involved. Full article

Mg₂Ni is a highly promising candidate for solid-state hydrogen storage due to its high storage capacity. However, its synthesis is challenging due to the high melting point of Ni (1455 °C) and the boiling point of Mg (1090 °C). In this study, elemental powder mixtures of Mg and 30 at% Ni were processed by high-pressure torsion (HPT) to synthesize the Mg₂Ni intermetallic compound through mechanical methods. The formation of 11 wt% of Mg₂Ni after 50 turns of HPT was confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS), reaching a maximum of 59 wt% after 100 turns. Rietveld refinement confirmed a nanocrystalline size for the Mg₂Ni phase synthesized via HPT. Hydrogenation tests showed that the Mg-Ni synthesized by HPT can absorb hydrogen at 350 °C even after several weeks of air exposure. Furthermore, a maximum absorption capacity of 3.8 wt% was reached after 20 h of hydrogen exposure for the sample with 100 turns. This capacity is close to the theoretical capacity of 3.9 wt% for this composition. The results confirm that combining HPT with subsequent heat treatment is an efficient strategy to increase the Mg₂Ni fraction after HPT processing. Full article

Trametes hirsuta GMA-01 was cultivated in a culture medium supplemented with orange waste, starch, wheat bran, yeast extract, and salts. The fungus produced several holoenzymes, but the laccase levels were surprisingly high. Given the highlighted applicability of laccases in various biotechnological areas with minimal environmental impact, we provided a strategy to increase its production using response surface methodology. The immobilization of laccase into ionic supports (CM-cellulose, DEAE-agarose, DEAE-cellulose, DEAE-Sephacel, MANAE-agarose, MANAE-cellulose, and PEI-agarose) was found to be efficient and recuperative, showcasing the technical prowess of research. The crude extract laccase (CE) and CM-cellulose-immobilized crude extract (ICE) showed optimum activity in acidic conditions (pH 3.0) and at 70 °C for the CE and 60 °C for the ICE. The ICE significantly increased thermostability at 60 °C for the crude extract, which retained 21.6% residual activity after 240 min. The CE and ICE were successfully applied to sugarcane bagasse hydrolysis, showing 13.83 ± 0.02 µmol mL⁻¹ reducing sugars after 48 h. Furthermore, the CE was tested for dye decolorization, achieving 96.6%, 71.9%, and 70.8% decolorization for bromocresol green, bromophenol blue, and orcein, respectively (0.05% (w/v) concentration). The properties and versatility of T. hirsuta GMA-01 laccase in different biotechnological purposes are interesting and notable, opening several potential applications and providing valuable insights into the future of biotechnological development. Full article

The decomposition efficiency of C₂HCl₃ and CHCl₃ in a barrier discharge is very different, even though these compounds differ little in chemical composition. In both compounds, there are three chlorine atoms and one hydrogen atom. The difference between them is the presence of one carbon atom in CHCl₃ and two carbon atoms connected by a double bond in C₂HCl₃ and the higher polarizability of C₂HCl₃. The polarizability of C₂HCl₃ is 10.21 ų and that of CHCl₃ is 8.39 ų. As a result of these differences, the C₂HCl₃ conversion was two to three times higher than the CHCl₃ conversion. The main product of CHCl₃ decomposition containing chlorine was ClO₂, while Cl₂, COCl₂, HCl, CCl₄, and Cl⁻ were formed in smaller amounts. The main products of C₂HCl₃ decomposition, which contain chlorine, were COCl₂, HCl, and Cl⁻. CCl₄ was not formed. Cl₂ and ClO₂ were formed in smaller amounts. Pathways of C₂HCl₃ and CHCl₃ decomposition are shown in this paper. The process was carried out at low power (0.2–0.8 W) in air. The gas flow was 10 L/h, and the concentration of the decomposed compound was 0.4%. The volume of the gas space of the reactor (plasma zone) was 27 cm³. Full article

One of the challenges in Fischer–Tropsch synthesis (FTS) is the high reduction temperatures, which cause sintering and the formation of silicates. These lead to pore blockages and the coverage of active metals, particularly in conventional catalyst promotion. To address the challenge, this article investigates the effects of the preparation method, specifically the inverse promotion of SiO₂-supported Co catalysts with manganese (Mn), and their reduction in H₂ for FTS. The catalysts were prepared using stepwise incipient wetness impregnation of a cobalt nitrate precursor into a promoted silica support. The properties of the catalysts were characterized using XRD, XPS, TPR, and BET techniques. The structure–performance relationship of the inversely promoted catalysts in FTS was studied using a fixed-bed reactor to obtain the best performing catalysts for heavy hydrocarbons (C₅₊). XRD and XPS results indicated that Co₃O₄ is the dominant cobalt phase in oxidized catalysts. It was found that with increase in Mn loading, the reduction temperature increased in the following sequence 10%Co/SiO₂ < 10%Co/0.25%Mn-SiO₂ < 10%Co/0.5%Mn-SiO₂ < 10%Co/3.0%Mn-SiO₂. The catalyst with the lowest Mn loading, 10%Co/0.25%Mn-SiO₂, exhibited higher C₅₊ selectivity, which can be attributed to less MSI and higher reducibility. This catalyst showed the lowest CH₄ selectivity possibly due to lower H₂ uptake and higher CO chemisorption. Full article

In this study, methyl/^tbutyl salicylate-bearing zirconium complexes (C1–C8) were prepared by the reaction of zirconium (IV) propoxide/butoxide with salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, and 3,5-di-tert-butylsalicylic acid in alcohols, respectively. All these complexes (C1–C8) were characterized by ¹H NMR, ¹³C NMR, FTIR, mass spectroscopy (MS), elemental, and thermogravimetric analyses (TGA). These complexes were utilized as catalysts in the ring-opening polymerization (ROP) of Ɛ-caprolactone and were very effective. Polycaprolactone (PCL) was characterized by ¹H-NMR, ¹³C NMR, and gel permeation chromatography (GPC). In this study, perhaps for the first time, the effects of electron-donating substituents (Me and ^tBu) on Ɛ-caprolactone polymerization reactions on salicylate ligands linked to zirconium atoms were investigated. Full article

Edible oils are one of the renewable sources that enable the possibility of producing biodiesel sustainably. The transesterification of canola oil with methanol using cesium-modified phosphotungstic acid (Cs_2.5H_0.5PW₁₂O₄₀) as a heterogeneous catalyst was studied. Reaction conditions, specifically reaction time, catalyst loading, and the ratio of methanol to canola oil, were systematically explored. The canola oil conversion reached 55% at room temperature after 24 h. The reusability tests showed that the conversion of canola oil to biodiesel was maintained. Full article

N-alkylated C₂-symmetric amino acid amide derivatives were shown to catalyse the Michael addition of 2-hydroxy-1,4-napthoquinone to β-nitrostyrene, achieving a maximum ee of 44%. The corresponding trifluoroacetic acid salts also catalysed the aldol reaction between 4-nitrobenzaldehyde and hydroxyacetone, leading to the formation of predominantly syn-aldol products in up to 55% ee. Aspects of the solvent dependence of the aldol reaction and the H-bonding of the catalyst were investigated. Full article