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Herein, gold nanoparticle-decorated amorphous carbon (Au/AC) was prepared by reducing chloroauric acid and layering it on amorphous carbon. The characteristics of Au/AC were examined using FT-IR, XRD, TGA, SEM, EDS, and XPS. To assess its catalytic activity, Au/AC was tested in a reaction involving anthranilamide and benzyl alcohol at 110 °C for 24 hours. This reaction yielded various 2-phenylquinazolin-4(3H)-one derivatives in moderate to good yields (44–80%). Furthermore, control experiments were conducted to demonstrate the oxidation and cyclization functions of Au/AC. Noteworthy aspects of this approach included the ease of isolating Au/AC (via recrystallization) and the ability to recycle it. [ABSTRACT FROM AUTHOR]

We present an intramolecular [3+2] cycloaddition of innovative (E)-α-aryl enal derivatives with 4-aminopyrazolone hydrochlorides/3-aminooxindole hydrochlorides to afford an array of atropisomeric benzoxepinone-based styrenes fused to spiro[pyrrolidine–pyrazolone/oxindole] scaffolds, and kinetic resolutions of the racemic adducts were implemented by reacting with benzyl alcohols, giving the corresponding two types of axially chiral styrenes in enantioenriched form with high s-factor. In addition, product transformations such as oxidative dehydrogenation and cross-coupling reactions have been demonstrated. [ABSTRACT FROM AUTHOR]

Three new hybrid polyoxometalates (POMs) based on transition metals, namely, copper metal with γ-[Mo8O26]4− polyoxometalates [Cu(DMF)4(Mo8O26)·2C3H8NO]·1.8 DMF (1), cobalt metal with hexamolybdate [Co(DMSO)6][Mo6O19] (2), and nickel metal with hexamolybdate [Ni(DMSO)6][Mo6O19] (3), were developed. These materials were characterised by applying both analytical and spectroscopic techniques (IR, TGA, and CHNO elemental analysis), and structural elucidation was performed using single-crystal X-ray diffraction studies. Among these hybrid POMs, octamolybdate with copper was used for the catalytic production of benzimidazoles. The incorporation of [Cu(DMF)4] between two octamolybdates results in the transformation of POMs into a useful catalyst, which effectively catalyses the oxidative cross-coupling of anilines, benzyl alcohol, and sodium azide to produce benzimidazole. This catalytic reaction occurs in the presence of tert-butyl hydroperoxide (TBHP) at a moderate temperature. Benzimidazole and its derivatives are highly preferred owing to their wide-ranging biological activities and clinical applications. These compounds are exceptionally effective in terms of their selectivity ratio and inhibitory activity. The catalytic reaction presented herein is a one-pot procedure that includes a series of reactions, such as C–H functionalization, condensation, ortho selective amination, and cyclization. [ABSTRACT FROM AUTHOR]

Modification of polyester (poly(ethylene terephthalate)) fabric by grafting with poly(methacrylic acid) was studied. The objective was to improve the hydrophilicity of polyester and, hence, its water uptake. The modified polyester fabrics were characterized by gravimetric method, Fourier transform infrared, dynamic mechanical analysis, and scanning electron microscopy. It was found that grafting of methacrylic acid onto polyester fabrics could be effected by radical reaction using benzoyl peroxide as radical initiator. Swelling of polyester fabric with benzyl alcohol was also found to be necessary for grafting to occur. The parameters which affected the modification reaction were initiator concentration, monomer to fabric ratio, reaction temperature, and reaction time. In addition, it was shown that the percentage uptake of moisture of the modified fabric (1–4.6%) increased with increase in the extent of grafting (5–32%). The modified fabric tended to be stiffer than the unmodified fabric, but they could be softened by controlled treatment with aqueous solution of sodium hydroxide. The stability of the modified polyester fabric, however, was found to decrease with increase in the extent of modification (high monomer to fabric ratio) and increasing concentration of sodium hydroxide solution. Thus, careful control of sodium hydroxide treatment process was necessary to prevent deterioration of the modified polyester fabric. [ABSTRACT FROM AUTHOR]

Tandem processes are valuable tools that allow to build molecular complexity while reducing waste production and the number of steps of synthetic routes. In this work, the in situ photooxidation of benzyl alcohols to the corresponding benzaldehydes is coupled with a Knoevenagel condensation for the preparation of benzylidenemalononitrile derivatives. In this rapid one‐pot tandem process, sodium anthraquinone‐1,5‐disulfonate (SAS) and β‐alanine are employed as safe and inexpensive catalysts, while air is used as a terminal oxidant. Moreover, using water as reaction medium results in most cases in the precipitation of the target products, thus facilitating their isolation. [ABSTRACT FROM AUTHOR]

An electroreductive deoxygenative carboxylation of alkyl oxalates with CO2 is demonstrated for the first time, which offers a general and scalable method for obtaining various carboxylic acids. This electrochemical method features a broad substrate scope and mild reaction conditions; various secondary benzyl alcohols and non-benzylic alcohols, primary benzyl alcohols and non-benzylic alcohols, and tertiary benzyl alcohols and non-benzylic alcohols can be converted into the corresponding carboxylic acids in good to excellent yields. Importantly, this electroreductive deoxygenative carboxylation reaction also offers a mild and straightforward route to access drug molecules, such as ibuprofen, (±) naproxen, fenoprofen, hexaprofen, and biprofen. [ABSTRACT FROM AUTHOR]

An electroreductive deoxygenative carboxylation of alkyl oxalates with CO2 is demonstrated for the first time, which offers a general and scalable method for obtaining various carboxylic acids. This electrochemical method features a broad substrate scope and mild reaction conditions; various secondary benzyl alcohols and non-benzylic alcohols, primary benzyl alcohols and non-benzylic alcohols, and tertiary benzyl alcohols and non-benzylic alcohols can be converted into the corresponding carboxylic acids in good to excellent yields. Importantly, this electroreductive deoxygenative carboxylation reaction also offers a mild and straightforward route to access drug molecules, such as ibuprofen, (±) naproxen, fenoprofen, hexaprofen, and biprofen. [ABSTRACT FROM AUTHOR]

Two‐dimensional covalent organic frameworks (2D‐COFs) have recently emerged as fascinating scaffolds for solar‐to‐chemical energy conversion because of their customizable structures and functionalities. Herein, two tris(triazolo)triazine‐based COF materials (namely COF‐JLU51 and COF‐JLU52) featuring large surface area, high crystallinity, excellent stability and photoelectric properties were designed and constructed for the first time. Remarkably, COF‐JLU51 gave an outstanding H2O2 production rate of over 4200 μmol g−1 h−1 with excellent reusability in pure water and O2 under one standard sun light, that higher than its isomorphic COF‐JLU52 and most of the reported metal‐free materials, owing to its superior generation, separation and transport of photogenerated carriers. Experimental and theoretical researches prove that the photocatalytic process undergoes a combination of indirect 2e− O2 reduction reaction (ORR) and 4e− H2O oxidation reaction (WOR). Specifically, an ultrahigh yield of 7624.7 μmol g−1 h−1 with apparent quantum yield of 18.2 % for COF‐JLU52 was achieved in a 1 : 1 ratio of benzyl alcohol and water system. This finding contributes novel, nitrogen‐rich and high‐quality tris(triazolo)triazine‐based COF materials, and also designate their bright future in photocatalytic solar transformations. [ABSTRACT FROM AUTHOR]

Our novel binuclear complex-anchored Ru(III) catalyst, designed and assembled by sonicating 2,2′-(4,6-dihydroxy-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid), Ru(DMSO)4Cl2 and 4-methylpyridine, demonstrates remarkable efficiency and selectivity. It promotes one-pot reactions, including active methylenes and benzyl alcohols in water, via a tandem aerobic oxidation/Knoevenagel condensation process, yielding benzylidene malononitrile in excellent yields. The catalyst's ability to oxidize benzyl alcohols to aldehydes, which then undergo Knoevenagel condensation with active methylenes, makes it a multifunctional catalyst. Notably, the catalyst can be successfully retrieved and recycled for five successive rounds with no significant decrease in catalytic efficiency. The ICP study showed that no catalyst leaching was observed, indicating that the designed catalyst is indeed heterogeneous. The Ru catalyst outperformed other documented catalysts in terms of lower dose, shorter duration, decreased working temperature, and the absence of dangerous additives. This demonstrates the catalyst's robustness and sustainability, making it a promising candidate for future organic conversions and industrial uses. [ABSTRACT FROM AUTHOR]

[Display omitted] The highly efficient photo-oxidation of alcohols has sparked significant potential to cope with environmental pollution and the ever-increasing energy crisis. This study reports a unique Ti 3 C 2 /BiOBr (TB) heterojunction with a rich inter-face based on in situ exfoliation of MXene and subsequently anchored onto BiOBr sheets. The TB nano-composites exhibited substantially improved photo-catalytic activity towards the photo-oxidation of benzyl alcohol (BA) to benzaldehyde and achieved a formation rate of 1.73 mmol g−1 h−1, greater than pristine BiOBr. The ultra-thin inter-facial contact boosted the oxygen vacancies (O v) and Ti3+ and possessed the most negative adsorption energy, which boosted the transfer and separation of inter-facial charge carriers and the adsorption and dissociation of BA. Overall, the successful synthesis of TB composite, along with its exceptional photo-catalytic performance, offers valuable insights for applications in green chemistry and environmental remediation. [ABSTRACT FROM AUTHOR]

Shiikuwasha, a citrus fruit native to Okinawa, Japan, has various cultivation lines with distinct free volatile and non-volatile components. However, the glycosylated volatiles, which are sources of hidden aromas, remain unknown. This study aimed to characterize the chemical profiles of free and glycosidically bound volatile as well as non-volatile components in the mature fruits of six Shiikuwasha cultivation lines: Ishikunibu, Izumi kugani-like, Kaachi, Kohama, Nakamoto seedless, and Ogimi kugani. Free volatiles were analyzed using solid-phase microextraction–gas chromatography–mass spectrometry. Glycosides were collected via solid-phase extraction and hydrolyzed with β-glucosidase, and the released volatiles were measured. Additionally, the non-volatile components were determined using non-targeted proton nuclear magnetic resonance analysis. Total free and bound volatiles ranged from 457 to 8401 µg/L and from 104 to 548 µg/L, respectively, and the predominant free volatiles found were limonene, γ-terpinene, and p-cymene. Twenty volatiles were released from glycosides, including predominant 1-hexanol and benzyl alcohol, with Kaachi and Ogimi kugani showing higher concentrations. Principal component analysis (PCA) revealed that taste-related compounds like sucrose, citrate, and malate influenced line differentiation. The PCA of the combined data of free and bound volatile and non-volatile components showed flavor component variances across all lines. These findings provide valuable insights into the chemical profiles of Shiikuwasha fruits for fresh consumption and food and beverage processing. [ABSTRACT FROM AUTHOR]

ABSTRACT CuI–Zn(OAc)2 catalyzed a new, fast, solvent‐free strategy for the synthesis of quinazolin‐4(3H)‐ones via selective scission of CC bond of the 1,3‐diketone (both cyclic and acyclic) and β‐ketoester was achieved under microwave irradiation. In contrast to the frequently applied synthetic strategy that involves cyclization‐oxidation sequence of anthranilamides (2‐aminobenzamides) with various aldehydes or benzyl alcohols, here, anthranilamide reacts with β‐ketoester/1,3‐diketo compounds in presence of CuI‐Zn(OAc)2 catalyst to form quinazolin‐4(3H)‐ones scaffold through an uncommon CC bond cleavage under solvent‐free mild conditions with excellent yields. Besides, this method displays its capacity for gram‐scale reactions. [ABSTRACT FROM AUTHOR]

Photocatalytic carbon‐carbon (C─C) coupling of benzyl alcohol is a promising means to coproduce the value‐added chemicals with H2 but is generally subject to low efficiency in terms of photon utilization. Here, efficient benzyl alcohol C─C coupling is achieved over Zn2In2S5 containing a tunable content of Zn vacancies (VZn). The VZn tends to form shallow defect states below the conduction band that can expedite photocarrier separation by collecting the photo‐generated electrons. The VZn‐collected electrons are essential for a high selectivity of the C─C coupling reactions because they enable a fast elimination of the byproduct benzaldehyde by catalyzing its reduction back to the ketyl radicals. Under simulated sunlight, the VZn‐containing Zn2In2S5 accomplishes ≈100% conversion of benzyl alcohol for merely 1 h and attains ≈100% selectivity for the C─C coupling compounds for 2 h, delivering an apparent quantum yield as high as 7.7% at 420 ± 20 nm. The benefits of VZn have also been verified by the theoretical calculations that indicate reduced energy barriers for various surface reactions in the presence of VZn. This work brings fresh mechanistic insights into the role of VZn and can serve as a useful guideline in the design of efficient photocatalysts. [ABSTRACT FROM AUTHOR]

Molecularly‐modified electrode materials that maintain stability over a broad pH range are rare. Typically, each electrochemical transformation necessitates a specifically tuned system to achieve strong binding and high activity of the catalyst. Here, we report the functionalisation of mesoporous indium tin oxide (mITO) electrodes with the macrocyclic host molecule pillar[6]arene (PA[6]). These electrodes are stable within the pH range of 2.4–10.8 and can be equipped with electrochemically active ruthenium complexes through host–guest interactions to perform various oxidation reactions. Benzyl alcohol oxidation serves as a model reaction in acidic media, while ammonia oxidation is conducted to assess the systems performance under basic conditions. PA[6]‐modified electrodes demonstrate catalytic activity for both reactions when complexed to different guest molecules and can be reused by reabsorption of the catalyst after its degradation. Furthermore, the system can be employed to perform subsequent reactions in electrolyte with varying pH, enabling the same electrode to be utilised in multiple different electrocatalytic reactions. [ABSTRACT FROM AUTHOR]

Even distribution of core–shell heterojunction on porous catalyst supports is promising to get the super‐catalysts, yet laborious preparation hinders the wide application. A novel strategy of urea enzymolysis‐induced ions replacement is proposed for one‐pot loading of Bi12O17Cl2@Bi48Al2O75 core–shell heterojunction onto porous Al2O3 nanorod (named as Al2O3‐Bi12O17Cl2@Bi48Al2O75). The clever combination of urea enzymolysis and precipitation reactions that consume the ions generated in urea enzymolysis can switch the “on‐off” of urease, and thus allow the precise controlling of the concentration and existence time of the ions, as well as ions replacement. It is the urea enzymolysis‐induced ions replacing strategy that can generate the unique structure of Al2O3‐Bi12O17Cl2@Bi48Al2O75, and it is the distinctive structure that can get the selectivity of 96% benzaldehyde with 90% benzyl alcohol (BA) conversion in the photocatalytic oxidation of BA. The ions replacement, the growth of Al2O3‐Bi12O17Cl2@Bi48Al2O75, and the photocatalytic mechanism are investigated in detail. This work highlights a novel and convenient strategy for one‐pot loading core–shell heterojunction onto porous nanorod support, unveils a fresh biosynthesis of nanomaterials with elaborate structure, and thus paves the way for wide application of elaborate nanomaterials. [ABSTRACT FROM AUTHOR]

Aminoarenes are important molecules for broad applications in nearly all modern industries that involve chemicals. Direct and site‐selective C−H bond amination of arenes provides the most efficient and convenient method to prepare aminoarenes. A main challenge is to selectively install the amino group (or other functional groups) to the distal para‐carbon of arenes (especially multi‐substituted arenes) during the C−H bond functionalization events. Herein, we address this problem by designing a new strategy via a sequential radical dearomatization/radical amination/rearomatization process for para‐selective amination of benzyl alcohols. The para‐selectivity of our reaction is completely independent of the electronic and steric properties of the other substituents of the arene substrates. Aminoarenes with many substituents (up to full substitution) and diverse substitution patterns, including those difficult to synthesize previously, could be readily prepared using our protocols. Further exploration of the current strategy shall lead to other challenging C−H functionalization of arenes. [ABSTRACT FROM AUTHOR]

Following our recent strategy of using suitably substituted ligand precursors for the synthesis of Ru(II)–CNC pincer complexes [Ru(CHNCMe)(PPh3)2Cl]Cl (1 and 2) with mixed protic- and classical-NHCs in the same molecule, synthesis of new phosphine-free complexes [Ru(CHNCMe)(CNMe)I]PF6 (3), [Ru(CHNCMe)(CNi-Pr)I]PF6 (4), [Ru(CHNCAd)(CNMe)I]PF6 (5), and [Ru(CHNCAd)(CNi-Pr)I]PF6 (6) has been achieved starting from our in-house made Ru(III)–NHC complexes [Ru(CNR′)(H2O)(Cl)3] (R′ = Me (P1), i-Pr (P2)) as precursors. This is the first report of phosphine-free Ru-complexes having mixed, protic- and classical-NHC within the same pincer ligand platform. We also note that this synthetic strategy gives racemic mixtures of chiral-at-the-metal complexes from nonchiral precursors. All new complexes have been characterized as racemic mixtures using multinuclear NMR (1H, 31P{1H}, 13C{1H} NMR) and high-resolution mass spectrometry (HRMS). The molecular structure of the racemic complex 6 has been determined by single-crystal X-ray diffraction and was found to contain both enantiomers in the same lattice. The catalytic activity of these complexes for oxidant-free, acceptorless dehydrogenation of benzyl alcohols to benzoic acids has been explored, revealing superior activity of complex 4 among the new complexes. Catalyst 4 was then screened for a wide range of substrates, including aliphatic, aromatic, and heteroaromatic benzyl alcohols, to give their corresponding carboxylic acids. Mechanistic investigations help identify some crucial intermediates during the catalytic reaction, and a plausible mechanism has been proposed. A maximum TON of 20 000 has been observed, greater than several previously reported ruthenium catalysts. [ABSTRACT FROM AUTHOR]

Benzyl alcohol (E1519) is an aromatic alcohol used in the pharmaceutical and food industry. It is used to protect food products against microorganisms during storage, as a flavoring in the production of chocolate and confectionery products, as an important ingredient in fragrance, and as a preservative in medical products. However, little is known of its effect on insects. The main aim of this study was to determine the influence of benzyl alcohol on the defense systems of the wax moth Galleria mellonella, i.e., its cuticular lipid composition and critical elements of its immune system. A gas chromatography/mass spectrometry (GC/MS) analysis found benzyl alcohol treatment to elicit significant quantitative and qualitative differences in cuticular free fatty acid (FFA) profiles. Our findings indicate that benzyl alcohol treatment increased the levels of HSP70 and HSP90 and decreased those of HSF1, histamine, and cysteinyl leukotriene. Benzyl alcohol application also increased dismutase level in the hemolymph and lowered those of catalase and 8-OHdG. The treatment also had negative effects on G. mellonella hemocytes and a Sf9 cell line in vitro: 48-h treatment resulted in morphological changes, with the remaining cells being clearly spindle-shaped with numerous granules. The high insecticidal activity of compound and its lack of toxicity towards vertebrates suggest it could be an effective insecticide. [ABSTRACT FROM AUTHOR]

As one of the most important synthetic fine chemicals and pharmaceuticals, benzaldehyde is widely used in pharmaceuticals, dyestuffs, fragrances and pesticides. It is still a difficult challenge to promote the conversion of benzyl alcohol to benzaldehyde by photocatalysis with high selectivity and high conversion. In this paper, the content of the reactive substance ·O2− is regulated by constructing suitable oxygen vacancies in TiO2 nanotubes, thus improving the photocatalytic conversion and selectivity. Herein, we have prepared TiO2-X 1D nanotubes enriched with different concentrations of oxygen vacancies by template method, hydrolysis of tetrabutyl titanate and vacuum annealing. By constructing suitable concentrations of oxygen vacancies in the TiO2 material, we can increase its ability to adsorb oxygen to produce more ·O2− on the one hand, and help to construct defective energy levels to prevent the compounding of photogenerated charge carriers to enhance photocatalytic activity on the other. As a result, the best photocatalytic activity of TiO2-X nanotubes obtained by vacuum annealing at 300 °C was 78% for benzyl alcohol conversion and 88% for benzaldehyde production selectivity, which is 2.6 and 1.8 folds higher than that of pristine TiO2 nanoparticles. Our work may provide insights for designing efficient photocatalysts for selective oxidation of benzyl alcohols. [ABSTRACT FROM AUTHOR]

[Display omitted] Solar-light driven oxidation of benzylic alcohols over photocatalysts endows significant prospects in value-added organics evolution owing to its facile, inexpensive and sustainable process. However, the unsatisfactory performance of actual photocatalysts due to the inefficient charge separation, low photoredox potential and sluggish surface reaction impedes the practical application of this process. Herein, we developed an innovative Z-Scheme Cs 3 BiBr 9 nanoparticles@porous C 3 N 4 tubes (CBB-NP@P-tube-CN) heterojunction photocatalyst for highly selective benzyl alcohol oxidation. Such composite combining increased photo-oxidation potential, Z-Scheme charge migration route as well as the structural advantages of porous tubular C 3 N 4 ensures the accelerated mass and ions diffusion kinetics, the fast photoinduced carriers dissociation and sufficient photoredox potentials. The CBB-NP@P-tube-CN photocatalyst demonstrates an exceptional performance for selective photo-oxidation of benzylic alcohol into benzaldehyde with 19, 14 and 3 times higher benzylic alcohols conversion rate than those of C 3 N 4 nanotubes, Cs 3 Bi 2 Br 9 and Cs 3 Bi 2 Br 9 @bulk C 3 N 4 photocatalysts, respectively. This work offers a sustainable photocatalytic system based on lead-free halide perovskite toward large scale solar-light driven value-added chemicals production. [ABSTRACT FROM AUTHOR]

Fluoride ion batteries (FIBs) are regarded as one of the most promising candidates for next‐generation energy storage systems to achieve lower cost and higher energy density. However, the appropriate electrolyte design strategy is still lacking for FIBs to simultaneously settle the issues of fluoride salt dissolution and metal cation shuttle. Herein, a novel fluoride ion shuttle electrolyte with the synergistic high‐donor solvent (N, N‐dimethylacetamide, DMA) and alcohol anion acceptor (benzyl alcohol, BA) is developed. BA enables the promotion of solubility of inorganic fluoride salt (CsF). Meanwhile, benefiting from the re‐configuration of hydrogen bonding network by DMA, the solvation structures of anions and cations are regulated with reduced hindrance to F− shuttle and mitigated dissolution of active material. This electrolyte formation achieves superior interfacial stability with cathode, high F− conductivity (2.05 mS cm−1), and transference number (0.53). After matching CuF2 cathode and Pb anode, the full cell exhibits the highly reversible conversion reaction process with an initial discharge capacity of 300.8 mAh g−1 and a reversible capacity of 245.5 mAh g−1 after 43 cycles. This study proposes a solution to high‐performance rechargeable FIBs at room temperature by synergistically manipulating the anionic and cationic solvation chemistry. [ABSTRACT FROM AUTHOR]

As fluorine atoms significantly strengthen the metabolic stability and bioavailability of organic molecules, benzyl fluoride is found as an essential skeleton in pharmaceuticals or biologically active molecules. Here, we employ sulfur hexafluoride (SF6) as an efficient fluorinating reagent, achieving nucleophilic fluorination of widely available benzyl alcohols under visible LED light irradiation with a low dosage of photocatalyst 4CzIPN. The reaction is compatible with several substrate backbones and is not air- or moisture-sensitive, realizing the degradation and utilization of SF6, a potent greenhouse gas resource. [ABSTRACT FROM AUTHOR]

An effective, facile, trivial, and one‐pot procedure for the synthesis of chromenopyrroles from benzyl alcohols, 2‐hydroxyacetophenones, and methyl/ethyl isocyanoacetate at room temperature in the presence of visible light has been developed. The Ag salt plays an important role in the activation of isocyanoacetate and the cyclization step. Air‐stable and low‐cost Knölker iron complex has been utilized for the dehydrogenation of primary alcohols that would typically require a higher temperature. The established protocol is scalable and has an extensive functional group tolerance, generating good to excellent yields of the chromenopyrroles at room temperature. [ABSTRACT FROM AUTHOR]

Replacing the sluggish oxygen evolution reaction with the oxidation of benzyl alcohol to construct the hybrid water electrolysis system has been attractive for its merits of environmentally friendly and economically efficient. However, the activity of the catalyst to oxidize alcohols needs to be further improved. Tailoring the d-band center (E d) has been proven as an effective method to promote the hydrogen evolution reaction (HER). How feasible is this strategy in the oxidation of benzyl alcohol? Here, using Co 2 C as a research platform, the doping nonmetal heteroatom (P, S, N) engineering is adopted to promote its electrocatalytic BA oxidation and HER performance. The results of electrochemical tests show that the P-doped Co 2 C (P–Co 2 C) only requires a low potential of 1.33 and 1.38 V vs. RHE to achieve current densities of 20 and 100 mA cm−2 for BA oxidation, which is superior to that of S–Co 2 C, N–Co 2 C, and pristine Co 2 C. The conversation and faradaic efficiency for BA is up to 98.1% and 93.8% during ten consecutive cycle tests. The P–Co 2 C also exhibited outstanding activity and stability toward HER. The density functional theory (DFT) calculation revealed that specified P doping could modify the d-band center of Co 2 C approaching the peak of the volcano map (electrochemical overpotentials ∼ E d). The Gibbs free energy of the BA oxidation was also reduced, thus optimizing the adsorption and desorption process of intermediates. On the other hand, the catalyst surface physical properties of Co 2 C such as hydrophilicity was promoted by the doped heteroatoms which was favorable for the gas-liquid-solid triphase electrocatalytic reaction. This work offers a facial perception of regulating the d-band to design advanced bifunctional electrocatalysts for organic matter oxidation and HER. The d-band center engineering was employed to boost the bifunctional electrocatalytic performance of X–Co 2 C (X = P, S, N). [Display omitted] • The X-doped Co 2 C (X = P, S, N) electrocatalysts were designed for BA oxidation and HER. • Among the prepared samples, the P–Co 2 C exhibited superior hydrophilicity and catalytic performance. • The P doping could change the d-band center of Co 2 C and optimize the adsorption/desorption process of intermediates. • The Gibbs free energy derived from the DFT was consistent with the order of electrochemical activity. [ABSTRACT FROM AUTHOR]

Simultaneous utilization of photogenerated electrons and holes to achieve overall redox reactions is attractive but still far from practical application. The emerging step (S)‐scheme mechanism has proven to be an ideal approach to inhibit charge recombination and supply photoinduced charges with highest redox potentials. Herein, a hierarchical phosphotungstic acid (H3PW12O40, HPW)@Znln2S4 (ZISW) heterojunction was prepared through one‐pot hydrothermal method for simultaneous hydrogen (H2) evolution and benzyl alcohol upgrading. The fabricated HPW‐based heterojunctions indicated much enhanced visible‐light absorption, promoted photogenerated charge transfer and inhibited charge recombination, owing to hierarchical architecture based on visible‐light responsive Znln2S4 microspheres, and S‐scheme charge transfer pathway. The S‐scheme mechanism was further verified by free‐radical trapping electron spin resonance (ESR) spectra. Moreover, the wettability of composite heterojunction was improved by the modification of hydrophilic HPW, contributing to gaining active hydrogen (H+) from water sustainably. The optimal ZISW‐30 heterojunction photocatalyst indicated an enhanced hydrogen evolution rate of 27.59 mmol g−1 h−1 in benzyl alcohol (10 vol. %) solution under full‐spectrum irradiation, along with highest benzaldehyde production rate is 8.32 mmol g−1 h−1. This work provides a promising guideline for incorporating HPW into S‐scheme heterojunctions to achieve efficient overall redox reactions. [ABSTRACT FROM AUTHOR]

Multifunctional carbon materials have revealed distinctive features and excellent performance in the field of catalysis. However, the facile fabrication of bifunctional carbon materials with special wettability and catalytic activity remains a grand challenge in Pickering emulsion catalysis. Herein, we reported one‐step construction of bifunctional biochar with superamphiphilicity and catalytic activity directly from the thermolysis of sawdust and 1‐butyl‐3‐methylimidazolium tetrafluoroborate for enhancing the oxidation of benzyl alcohol in Pickering emulsion. Co‐doping of B and F enhanced the hydrophilicity of biochar, and the oleophilicity of biochar was kept simultaneously. Conversion became 4 times using bifunctional biochar compared with blank results during the oxidation of benzyl alcohol. More interestingly, the turnover frequency (TOF) value using bifunctional biochar enhanced 61 % than that employing N‐doped superamphiphilic carbon without catalytic activity. Catalytic activities of bifunctional biochar could be ascribed to the existence of different chemical bonds containing the element B. This work paves a path toward rational design of bifunctional biochar materials with special wettability and catalytic activity for greatly enhancing the liquid‐liquid biphasic reaction efficiencies. [ABSTRACT FROM AUTHOR]

The binary vapor–liquid equilibria (VLE) of (methyl benzoate + benzyl alcohol) and (methyl benzoate + benzaldehyde) were measured and correlated using activity coefficient models. The measurements were performed using a modified Othmer still at constant pressures of 101.3, 51.3, and 21.3 kPa. The measured data were tested for consistency and correlated using the non-random two-liquid (NRTL), Wilson, and universal quasi-chemical (UNIQUAC) models. The data were also compared with predictive models, such as UNIFAC and the machine learning version of COSMO-SAC. Temperature dependence of the interaction parameters was required to accurately represent the data, covering the pressure range of the experiments. These results can be used to design a purification process for methyl benzoate production. [ABSTRACT FROM AUTHOR]

Summary: Congou black tea is mainly processed from single variety leaves, with obvious variety characteristics. This study investigated the effects of mixed processing withered leaves varieties on sensory quality, the volatile and non‐volatile compounds of seven Congou black tea samples. Sensory quality evaluation revealed that the Congou black tea with three leaves varieties were fresher, more floral and had coordinate taste. The total quality score was in the order: MPH > H > M&H > M > M&P > H&P > P. However, samples MPH and M&H have a higher content of theaflavins and amino acids, especially theanine. Furthermore, 130 volatile substances were identified in seven black teas by using HS‐SPME/GC–MS. M&H and MPH have more aroma types and total amount than that of M, P and H. The mixed processing of withered leaves may fully use the catalysis of endogenous enzymes to increase the 19 kinds of black tea key aromas including Benzyl alcohol, trans‐2‐hexenyl hexanoate, Hexyl hexanoate and Methyl jasmonate. Thus, blended processing can enhance the taste, aroma and LC quality of black tea. [ABSTRACT FROM AUTHOR]

Herein, we have reported a new series of NNS‐donor ligands coordinated Ni(II) complexes and utilized them as catalytic activator to synthesize N‐alkylated amines and 1,2‐disubstituted benzimidazoles. The reaction of thiophenol/4‐chlorothiophenol/4‐methylthiophenol/4‐methoxythiophenol with 2‐bromo‐N‐quinolin‐8‐yl‐acetamide in presence of sodium hydroxide in ethanol at 80 °C gave [C9H6N‐NH−C(O)−CH2‐S−Ar] [Ar=C6H5 (L1); C6H4Cl‐4 (L2); C6H4Me‐4 (L3) and C6H4‐OMe‐4 (L4)], respectively. The corresponding reaction of L1‐L4 with Ni(OAc)2 in methanol at 80 °C for 3 hours resulted in octahedral nickel complexes [(L1‐H)2Ni] (C1), [(L2‐H)2Ni] (C2), [(L3‐H)2Ni] (C3), and [(L4‐H)2Ni] (C4), respectively. All compounds have been characterized by micro and spectroscopic analysis. The molecular structure of complexes C1–C3 has also been determined by single crystal X‐ray diffraction data. The utility of complexes C1–C4 were evaluated for the N‐alkylation of aniline with benzyl alcohols, and for 1,2‐disubstituted benzimidazoles synthesis. The obtained results indicate that complex C1 showed better catalytic activity in both N‐alkylation of amines with benzyl alcohols [catalyst loading: 2.0 mol %; Yield up to 92 %], and for 1,2‐disubstituted benzimidazoles derivatives [catalyst loading: 2.0 mol %; Yield up to 94 %)]. The mechanistic studies suggested that the reaction works through hydrogen borrowing from benzyl alcohol and its subsequent utilization for in situ reduction of imine. The experimentally observed catalytic reactivity patterns of complexes C1–C4 have found in good agreement with the HOMO‐LUMO energy gaps obtained by DFT analysis of corresponding complexes. [ABSTRACT FROM AUTHOR]

In this study, a Mn-Cr catalysts supported on self-synthesized SBA-15 for the oxidation of substituted benzyl alcohols using oxygen as the oxidant had been investigated. The mesoporous nature of SBA-15, characterized by its high specific surface area and regular pore structure, makes it an ideal carrier for catalysts with catalytic properties. Through careful optimization, an efficient Mn-Cr/SBA-15 catalyst had been developed, achieving a benzyl alcohol conversion rate of nearly 90% with a selectivity exceeding 98% towards benzaldehyde and its derivatives. Furthermore, the supported Mn-Cr catalysts exhibited remarkable stability, allowing for their reuse for at least five cycles without significant loss of activity or selectivity. These findings highlight the potential of Mn-Cr/SBA-15 catalysts as sustainable and effective options for the oxidation of substituted benzyl alcohols. The study contributes to the development of greener and more efficient oxidation processes in organic synthesis. A Mn-Cr/SBA-15 catalyst achieved an impressive conversion rate of nearly 90% for benzyl alcohol, with a selectivity exceeding 98% towards benzaldehyde. [ABSTRACT FROM AUTHOR]

Chemometric evaluation of potentially harmful volatile compound and toxic metal(loid) distribution patterns in fruit spirits relating to distinct fruit classes most commonly used in spirit production highlighted the potential of several volatiles as candidates for differentiation markers while dismissing toxic metal(loid)s. Pome fruit and grape pomace spirits were mostly characterized by a lower abundance of n-propanol, methanol, ethyl acetate and acetaldehyde, while stone fruit spirits contained lower amounts of isoamyl alcohol and isobutanol. Chemometric analysis of the fruit spirit composition of aromatics identified additional potential markers characteristic for certain fruits—benzoic acid ethyl ester, benzyl alcohol, benzaldehyde, butanoic acid 3-methyl-ethyl ester, butanoic acid 2-methyl-ethyl ester and furfural. This study explored the variability in the risk potential of the investigated spirits, considering that some chemicals known to be detected in spirits are potent health hazards. Ethyl carbamate in combination with acetaldehyde showed a higher potential risk in stone fruit spirits, methanol in stone and pome fruit spirits and acetaldehyde in grape pomace spirits. It is of great interest to evaluate to what extent consumers' preference for spirits of distinct fruit types affects health risks. Consumers of stone fruit spirits are potentially at higher risk than those consuming pome fruit or grape pomace spirits. [ABSTRACT FROM AUTHOR]

Two novel synthetic routes to 4‐(N‐Boc‐N‐methylaminomethyl)benzaldehyde, an important pharmaceutical starting material, were developed using terephthaloyl chloride and terephthalaldehyde. In the first approach, terephthaloyl chloride was converted to an ester amide. The treatment of the ester amide with LiAlH4 followed by protection of the resulting amine with tert‐butoxycarbonyl anhydride yielded the corresponding benzyl alcohol. The benzyl alcohol was oxidized to the aldehyde completing the first‐generation synthesis. The second approach utilized a one‐step protocol mono‐selective reductive amination of terephthalaldehyde with N‐Boc‐methylamine using chlorodimethylsilane. Both methods were scalable to 50 mmol and provided the desired aldehyde in a synthetically useful yield, demonstrating their practicality. [ABSTRACT FROM AUTHOR]

ZIF-67 has garnered much attention in the field of photocatalytic water splitting due to the advantages of MOFs and zeolite sieves. However, post-modification and composite strategies have emerged as effective approaches to enhance its photocatalytic performance, particularly in enabling bi-functionality for oxidation-coupled reduction reactions. In this study, 2-mercaptobenzimidazole (MBI) modified ZIF-67 and cadmium sulfide (CdS) composites were prepared to investigate their application in photocatalytic oxidation-coupled hydrogen evolution reactions. The results demonstrated an enhancement in hydrogen production performance over CdS@ZIF-67-MBI, with an increase from 2.39 mmol g−1 h−1 to 4.49 mmol g−1 h−1 upon the introduction of MBI. Moreover, the conversion efficiency of benzyl alcohol reached an improved value of 58.5%. The study findings revealed that the heterogeneous coupling between ZIF-67 and CdS, along with the effective charge transfer facilitated by the anion S, played a decisive role in promoting charge–hole separation of composite materials and improving carrier transport efficiency. This demonstrates the viability of utilizing ZIF-67 in a bifunctional photocatalytic reaction system, thereby paving the way for broader applications of ZIF-67. [ABSTRACT FROM AUTHOR]

A straightforward asymmetric transfer hydrogenation for accessing enantiomerically enriched secondary benzyl alcohols involving free phenolic hydroxyl group(s) under mild conditions was developed. Various of optical pure aryl alcohols with a remarkable functional group compatibility were achieved with 78 %–97 % yields, 84 %–>99 % ee's and up to 10 000 TON. This rhodium‐catalyzed reaction could be performed in a gram‐scale without loss of the efficiency. Furthermore, the synthetic utility has also been demonstrated in the asymmetric synthesis of (S)‐adrenaline and (S)‐phenylephrine. [ABSTRACT FROM AUTHOR]

Unspecific Peroxygenases (UPOs) have emerged as robust biocatalysts for selective oxygenation reactions, as they are easily produced at scale and require only hydrogen peroxide as the external oxidant. UPOs can catalyze the oxygenation of the primary benzylic carbons of toluenes to give alcohol, aldehyde and carboxylic acid products. They can also catalyze hydroxylation at the benzylic position of ethylbenzenes, and the subsequent oxidation of the secondary alcohols to ketones. In this study, we have investigated factors that affect the balance of products in UPO‐catalyzed benzylic oxygenations using a range of functionalised toluenes and ethyl benzenes, and a UPO from Agrocybe aegerita (rAaeUPO‐PaDa‐I‐H variant). The product distribution is dependent upon a mixture of steric and electronic effects and, in selected cases, controlling the reaction conditions permits products from each product series to be generated chemoselectively. In this way, electron poor toluenes were converted directly into carboxylic acids in isolated yields of 36–99 % on preparative scale. [ABSTRACT FROM AUTHOR]

The syntheses of novel spirobenzazepinoindole derivatives has been achieved through a highly efficient and synthetic route. The approach involves a two‐step reaction, utilizing indole derivatives, 2‐amino benzyl alcohol, and ninhydrin as key starting materials under mild reaction conditions. The reaction proceeds via a sequential cascade process involving cyclization, condensation and spiro‐annulation, leading to the formation of the spirobenzazepinoindole core structure in good to excellent yields. The method offers broad substrate scope, high atom economy, and operational simplicity. The synthesized spirobenzazepinoindoles were fully characterized by spectroscopic techniques, including NMR (1H & 13C), IR and mass spectrometry. The methodology provides a valuable tool for the rapid generation of structurally complex spirobenzazepinoindoles, which could serve as scaffolds for the development of new therapeutic agents. [ABSTRACT FROM AUTHOR]

The hydrogenation of nitrogen‐containing heterocyclic precursors in aqueous medium is challenging, especially at ambient temperature and pressure. Electrochemical hydrogenation (ECH) of quinoline to 1,2,3,4‐tetrahydroquinoline (THQ) at mild conditions using water as the hydrogen source is demonstrated with splendid activity on a Cu‐based nonprecicous catalyst. The yield of THQ is up to ≈100% with ≈100% selectivity at −1.275 V vs Hg/HgO. The real active sites and key intermediates are deciphered, where the Lewis acid‐base sites on the heterointerface of Cu/Cu2O are beneficial to the quinoline adsorption in a dual‐site coordination configuration and water dissociation to afford H*. The presence of Cu0 plays a vital role in inhibiting the binding of H*, which ensures good Faradaic efficiency. In addition, a novel co‐production system by coupling benzyl alcohol oxidation at the anode is established, achieving dual benefits in both energy utilization efficiency and economic benefits. [ABSTRACT FROM AUTHOR]

We report an efficient protocol for oxidation of primary/secondary benzyl alcohols and benzylamines to produce corresponding aldehydes or ketones. Our unified method involves the use of commercially available (diethylamino)sulfur trifluoride (DAST) as a reagent combined with DMSO as solvent and oxidant. The reaction provided corresponding carbonyl compounds in good to excellent yields with high purity and in short reaction times. [ABSTRACT FROM AUTHOR]

Scenting is an important process for the formation of aroma quality in floral Longjing tea. There are differences in the aroma quality of osmanthus Longjing teas processed by different scenting processes. The efficient isolated scenting method was employed to process a new product of osmanthus Longjing tea in this study, and this was compared with the traditional scenting method. The volatile compounds of osmanthus Longjing tea were analyzed by a GC-MS instrument. In addition, the effects of scenting time and osmanthus consumption on the aroma quality of Longjing tea were studied. The results indicated that there were 67 kinds of volatile compounds in the osmanthus Longjing tea produced by the isolated scenting process (O-ISP), osmanthus Longjing tea produced by the traditional scenting process (O-TSP), and raw Longjing tea embryo (R), including alcohols, ketones, esters, aldehydes, olefins, acids, furans, and other aroma compounds. The proportions of alcohol compounds, ester compounds, aldehyde compounds, and ketone compounds in O-ISP were higher than in O-TSP and R. When the osmanthus consumption was increased, the relative contents of volatile aroma compounds gradually increased, which included the contents of trans-3,7-linalool oxide II, dehydrolinalool, linalool oxide III (furan type), linalool oxide IV (furan type), 2,6-Dimethyl cyclohexanol, isophytol, geraniol, 1-octene-3-alcohol, cis-2-pentenol, trans-3-hexenol, β-violet alcohol, 1-pentanol, benzyl alcohol, trans-p-2-menthene-1-alcohol, nerol, hexanol, terpineol, 6-epoxy-β-ionone, 4,2-butanone, 2,3-octanedione, methyl stearate, cis-3-hexenyl wasobutyrate, and dihydroanemone lactone. When the scenting time was increased, the relative contents of aroma compounds gradually increased, which included the contents of 2-phenylethanol, trans-3,7-linalool oxide I, trans-3,7-linalool oxide II, dehydrolinalool, isophytol, geraniol, trans-3-hexenol, β-ionol, benzyl alcohol, trans-p-2-menthene-1-ol, nerol, hexanol, terpineol, dihydroβ-ionone, α-ionone, and β-ionone,6,10. The isolated scenting process could achieve better aroma quality in terms of the floral fragrance, refreshing fragrance, and tender fragrance than the traditional scenting process. The isolated scenting process was suitable for processing osmanthus Longjing tea with high aroma quality. This study was hoped to provide a theoretical base for the formation mechanism and control of quality of osmanthus Longjing tea. [ABSTRACT FROM AUTHOR]

Two mononuclear complexes, [Cu(L1)2] (complex 1) and [Cu(HL2)2](NO3)2 (complex 2) where HL1 is 1-((cyclohexylmethylimino)methyl)-naphthalen-2-ol and HL2 is 4-bromo-2-((2-morpholinoethylimino)methyl)phenol, have been synthesized under mild conditions and characterized by different standard analytical methods. Single crystal X-ray diffraction analysis shows that the copper atoms in both copper(II) complexes are in a square planar geometry. These complexes have been used as catalysts in the oxidation of benzyl alcohol and benzyl alcohol with various substituents in the presence of NaOCl as the terminal oxidant. The results show that complex 1 acts as a better catalyst than the other with the highest yield of 91% in the case of 4-methoxy benzyl alcohol oxidation. The copper complex transfers the oxygen of sodium hypochlorite to the alcohol to produce the aldehyde. The use of NaOCl as an oxidant in alcohol oxidation is rare although it is cheap and nonexplosive. [ABSTRACT FROM AUTHOR]

Achieving positionally selective distal C–H functionalization remains a fundamental and longstanding challenge in the field of C–H activation. The directing template strategy has emerged as a promising solution to this problem. Herein, we disclose the development of a novel non-aromatic meta-selective directing template, which showed eminent reactivity and site-selectivity in palladium-catalyzed remote meta-C–H olefination, deuteration and acetoxylation of benzyl alcohols. [ABSTRACT FROM AUTHOR]

The enantioselective benzylic oxidation to synthesize chiral benzyl alcohols from alkylarenes poses a challenge. This study introduces a one-pot, two-step C–H bond hydroxylation process that integrates HRP-catalyzed oxidation and carbonyl reductase-catalyzed reduction for the enantiocomplementary synthesis of benzyl alcohols (up to 77% yield and 99% ee). This mild and operationally simple process provides an alternative approach to enantioselective benzylic hydroxylation. [ABSTRACT FROM AUTHOR]

A bifunctional thiourea‐amine‐based organocatalyst (Takemoto's catalyst), employing a metal‐free approach, is presented for the regioselective ring‐opening polymerization (ROP) of optically active (D and L) methyl glycolide (MG). In this study, a chiral version of Takemoto's catalyst efficiently promotes the ROP of MG at room temperature, yielding poly(lactic‐co‐glycolic acids) (PLGAs) with predicted molecular weights and narrow polydispersity indices (PDI≤1.2). These PLGAs exhibit highly alternating structures without transesterification, as confirmed by 1H NMR, SEC, and MALDI‐TOF analyses. Additionally, various macromolecular architectures, including linear and star‐shaped PLGAs, were successfully synthesized using the corresponding multi‐functional alcohol initiators while maintaining the same alternating structures and regioselectivity with PLGA obtained from benzyl alcohol as initiator. Computational studies were conducted to elucidate the mechanism of alternating PLGA formation, revealing two key transition states (TSs): TS‐1, which implicates the nucleophilic attack of the hydroxyl group of the initiator or propagating chain on the carbonyl carbon of MG, and TS‐2, which involves the subsequent ring‐opening of the cyclic ester. The results indicate that ring‐opening occurs at both the glycolyl and lactyl sites, with a preference for the glycolyl site, as supported by experimental results. The resulting atactic PLGAs are amorphous, rendering them suitable for drug delivery applications. [ABSTRACT FROM AUTHOR]

Herein, we present an efficient, one‐pot reaction for accessing 3‐benzylated indoles via the coupling of benzyl alcohols with indoles under heterogeneous catalysis by manganese ferrite (MnFe2O4) nanoparticles. Notably, this reaction, for the first time, employs MnFe2O4 nanoparticles prepared using a simple grinding method. The high compatibility of MnFe2O4 nanoparticles enables a broad substrate scope and high regioselectivity. Moreover, this approach offers several attractive highlights including the use of a recyclable oxide catalyst and green and cost‐effective alkylating reagents under solvent‐free conditions. [ABSTRACT FROM AUTHOR]

The photocatalytic oxidation of biomass‐derived benzyl alcohol provides a promising way for the synthesis of benzoic acid, which is an important intermediate with wide applications. To improve the efficiency of photocatalytic benzyl alcohol oxidation to benzoic acid is of great interest. In this work, we propose the utilization of NH2‐UiO‐66‐ID‐Fe catalyst for photocatalytic oxidation of benzyl alcohol to benzoic acid, where NH2‐UiO‐66 is a typically used metal‐organic framework, ID is indole‐2,3‐dione (ID) that has biocompatibility, light absorption property and can be covalently combined with amino‐functionalized substances. The NH2‐UiO‐66‐ID‐Fe catalyst exhibits improved light absorption and photo‐generated electron‐hole separation ability compared with NH2‐UiO‐66. The photocatalytic performance of NH2‐UiO‐66‐ID‐Fe was examined for the oxidation of bio‐based benzyl alcohol under mild conditions of air atmosphere, room temperature and no additive or additional oxidant involved. The results show that the conversion of benzyl alcohol and the selectivity to benzoic acid could both reach over 99 % in 6 h, and the generation rate of benzoic acid per gram of catalyst is 3.36 mmol g−1 h−1. The reaction mechanism was detected by radical trapping method and in situ electron paramagnetic resonance. This study presents an efficient and environmentally benign avenue for the synthesis of carboxylic acid compounds. [ABSTRACT FROM AUTHOR]

Background: Benzyl acetate is an aromatic ester with a jasmine scent. It was discovered in plants and has broad applications in food, cosmetic, and pharmaceutical industries. Its current production predominantly relies on chemical synthesis. In this study, Escherichia coli was engineered to produce benzyl acetate. Results: Two biosynthetic routes based on the CoA-dependent β-oxidation pathway were constructed in E. coli for benzyl acetate production. In route I, benzoic acid pathway was extended to produce benzyl alcohol by combining carboxylic acid reductase and endogenous dehydrogenases and/or aldo-keto reductases in E. coli. Benzyl alcohol was then condensed with acetyl-CoA by the alcohol acetyltransferase ATF1 from yeast to form benzyl acetate. In route II, a plant CoA-dependent β-oxidation pathway via benzoyl-CoA was assessed for benzyl alcohol and benzyl acetate production in E. coli. The overexpression of the phosphotransacetylase from Clostridium kluyveri (CkPta) further improved benzyl acetate production in E. coli. Two-phase extractive fermentation in situ was adopted and optimized for benzyl acetate production in a shake flask. The most optimal strain produced 3.0 ± 0.2 g/L benzyl acetate in 48 h by shake-flask fermentation. Conclusions: We were able to establish the whole pathway for benzyl acetate based on the CoA-dependent β-oxidation in single strain for the first time. The highest titer for benzyl acetate produced from glucose by E. coli is reported. Moreover, cinnamyl acetate production as an unwanted by-product was very low. Results provided novel information regarding the engineering benzyl acetate production in microorganisms. [ABSTRACT FROM AUTHOR]

In this study, amine-functionalized and Ni(II)-immobilized mesoporous silica materials were synthesized. This research aimed to synthesize mesoporous silica based on rice husk ash functionalized with amine and immobilized with Ni(II). The activity of amine-functionalized and Ni(II)-immobilized mesoporous silica materials was studied for the acetylation of benzyl alcohol with acetic anhydride as the acetylating agent. First, mesoporous silica was synthesized using rice husk ash using the sol-gel method, followed by amine functionalization using (3-aminopropyl)triethoxysilane (APTES) and Ni(II) immobilization through ultrasonic treatment. The results obtained showed that amine-functionalized and Ni(II)- immobilized mesoporous silica (SiO2/APTES/Ni(II)) were successfully synthesized, confirmed by Fourier transform infrared and Energy-dispersive X-ray spectrometry data. In addition, the synthesized materials had an average pore diameter of 12.83 nm. Afterward, the catalytic activity test showed that SiO2/APTES/Ni(II) was able to convert 98.34% of benzyl alcohol in the acetylation reaction at 45 °C for 5 h. The use of the SiO2/APTES/Ni(II) catalyst for three cycles obtained percent conversion values with a slight decreases (98.34%, 95.20%, and 90.61%). [ABSTRACT FROM AUTHOR]

The versatility and significance of imines (Schiff bases) make them highly attractive for many industrial applications. This study investigates photocatalytic routes for the one-pot synthesis of Schiff bases using alcohol and an aromatic nitro compound as reagents, rather than the more conventional amine and aldehyde or ketone. Utilizing photoirradiation at 370 nm with TiO2 loaded with various metals, we demonstrate the exceptional efficiency of the one-pot synthesis of Schiff bases under an inert atmosphere. Notably, the Fe3O4@TiO2 magnetic catalyst offers an excellent option for synthesizing the corresponding imine, achieving a remarkable production rate of 6.8 mmol h−1 during the first 6 h of irradiation with UVA light and reaching over 99% yield after 20 h. This success is attributed to a series of reactions involving the photocatalytic oxidation of benzyl alcohol to benzaldehyde and the simultaneous in situ reduction of nitrobenzene to aniline. The subsequent catalytic condensation of these products, facilitated by the active sites at the TiO2-metal interface, ultimately yields the desired imine. Additionally, while irradiation in the UVA region alone can photocatalyze the process, incorporating blue light (450 nm) accelerates it significantly. Dual-wavelength irradiation increased the production of the benzaldehyde to 77.9 mmol and more than doubled the Schiff base yield, from 7.5 mmol (with UVA light) to 17 mmol in 3 h of irradiation. Additionally, the reusability of the catalyst under simultaneous 450 nm and 370 nm light exposure significantly enhanced Schiff base production, which rose from 16.9 mmol to 48.9 mmol after adding fresh 0.1 M nitrobenzene for the second use. This highlights the effectiveness of color-coordinated catalysis in advancing sustainable chemistry through two-color photochemistry. The magnetic catalytic system not only demonstrates remarkable performance but also shows excellent reusability, representing a promising alternative for sustainable and efficient chemical transformations. [ABSTRACT FROM AUTHOR]