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In this paper, we reported the preparation, characterization, and catalytic performance of TiO2 doped with Mn for the selective oxidation of toluene to benzyl alcohol and benzaldehyde without any solvent. The structure of the catalyst was determined by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), nitrogen adsorption–desorption analysis (Brunauer–Emmet–Teller [BET]), scanning electron microscope (SEM), transmission electron microscope (TEM), and mapping. The results demonstrated that the catalytic properties of Mn‐TiO2 were higher than those of pure Mn3O4 and TiO2. The effects of reaction temperature, reaction time, oxygen pressure, and the amount of catalyst were studied. Under the optimal conditions, Mn‐TiO2 could afford 6.4% toluene conversion at a combined benzyl alcohol/benzaldehyde selectivity of 58.6%. Moreover, the catalyst can be repeated in the experiment for five times without significant loss of activity. [ABSTRACT FROM AUTHOR]

This paper presents a study on the effects of oxygen functionalities on a mesoporous and graphitized carbon support (GNP, Graphene Nanoplatelets), on the catalytic activity of Pd/GNP catalysts in hydrogenation reactions. A functionalization method in liquid phase has been employed, using different oxidants (HNO3, H2O2, KMnO4), with the aim to tune the amount and the type of introduced oxygen functionalities. Preformed Pd nanoparticles have been used as Pd‐precursor to limit differences in metal particle size and dispersion on differently functionalized carbon. The catalytic behaviour in benzaldehyde hydrogenation/hydrogenolysis to benzyl alcohol and toluene revealed that the introduction of oxygen functionalities has a generally detrimental effect. NMR relaxometry studies highlighted the weaker interaction between the carbonyl group and the functionalized Pd/GNP surface than the non–functionalized Pd/GNP demonstrating that the origin of the different catalytic activity lies on the first step of the reaction. O‐functionalities also impacted on the Pd0/Pd2+ ratio at the surface which is an established parameter correlated to the reaction rate. [ABSTRACT FROM AUTHOR]

BACKGROUND: Photothermal catalytic oxidation technology for synthesis of high value‐added chemicals has become a hot topic of research at home and abroad. As a special structure, titania (TiO2) nanotubes (Ti‐NTs) possess larger specific surface area and adsorption capacity, which have shown great application prospects in photothermal catalytic oxidation. RESULTS: In this work, high‐performance palladium (Pd‐Ti‐NTs catalyst were prepared and applied to the photothermal catalytic oxidation of 5‐hydroxymethyl (HMF) and benzyl alcohol. The photothermal dependence on catalytic activity and selectivity of HMF and benzyl alcohol oxidation was studied in detail. The results revealed that compared with thermal catalytic oxidation, the catalysts showed significantly higher conversions of both benzyl alcohol and HMF under light. in particular, HMF conversion increase from 55.6% to 99.7%. Aldehyde oxidation is inhibited by alcohol and can be dramatically promoted by light radiation. This is probably because alcohol can inhibit the adsorption of aldehyde, and this inhibiting effect is weakened through light radiation, thus promoting the oxidation of aldehydes. Therefore, the selectivity of the final products 2,5‐furandicarboxylic acid (FDCA) and benzoic acid were dramatically increased in both systems under light radiation, and the selectivity for FDCA was obviously increased from 5.8% to 61.3%, and the yield reached 61.0%, which is higher than that of most of the reported Pd‐TiO2‐based catalysts for FDCA. CONCLUSIONS: In this paper, we verify that Pd‐Ti‐NTs could preferentially promote the conversion of aldehydes to acids in the presence of light, and obtained catalysts with high catalytic performance and high stability for benzyl alcohol and HMF oxidation. © 2024 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

In this paper the density functional theory (DFT) method was employed to investigate the cross‐coupling of methanol with benzyl alcohol to afford methyl benzoate, catalysed by Mn‐PNN pincer complex. The whole reaction process mainly includes three stages: the dehydrogenation of benzyl alcohol to benzaldehyde, the coupling of benzaldehyde with methanol to hemiacetal and the dehydrogenation of hemiacetal to methyl benzoate. The calculated results indicated that two dehydrogenation processes are influenced by two competitive mechanisms of inner and outer spheres. Dehydrogenation of benzyl alcohol to benzaldehyde is the rate‐determining step of the whole reaction, with the energy barrier of 22.1 kcal/mol. In addition, the regeneration of catalyst is also extremely important. Compared with direct dehydrogenation, the dehydrogenation mode assisted by formic acid is more advantageous. This work might provide theoretical insights and shed light on the design of cheap transition‐metal catalysts for the dehydrogenation reaction. [ABSTRACT FROM AUTHOR]

This paper reports a heterogeneous magnetic impressive nickel catalyst in which Fe3O4 nanoparticles have been coated with chitosan and decorated with nickel nanoparticles (Fe3O4@CS‐Ni). This catalyst has been used for direct α‐alkylation of aryl ketones with substituted benzyl alcohols through borrowing hydrogen and dehydrogenation mechanism that affords the corresponding α‐benzyl ketones, with good to excellent yield. The core‐shell morphology has been confirmed with different analysis techniques such as Fourier‐transform infrared (FT‐IR), X‐ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), SEM mapping, energy‐dispersive X‐ray (EDX), inductively coupled plasma (ICP), and thermogravimetric analysis (TGA). Moreover, the catalyst could be recovered from the reaction mixture by using an external magnetic field and reused for six successive cycles without a considerable decrease in catalytic activity. [ABSTRACT FROM AUTHOR]

Recent progress of the catalytic promiscuity of enzymes have invigorated the use of biocatalysis in organic chemistry. Explorations of biocatalysis for the synthesis of esters are critical since up to now, existing traditional methods are complicated, which usually require long reaction times, microwaves or even toxic reagents. This paper presents a versatile biocatalytic methodology to obtain benzyl esters through a transesterification reaction of methyl esters with Candida antarctica lipase B (CaLB) and benzyl alcohol in the absence of solvent. In addition, the effect of the nucleophile size and the substituent directly attached to the carbonyl group was studied. The results show that, in some cases, using a vacuum shifts the equilibrium of the reaction towards the products. Based on these results, molecular docking studies were carried out, where specific regions in the CaLB catalytic cavity were analyzed. [ABSTRACT FROM AUTHOR]

The morphologies of the internal organs of echinoderm larvae and juveniles are difficult to study using conventional optical microscopes because of their structural complexity and opaqueness. This paper describes an easy and rapid protocol involving Nile blue staining followed by benzyl alcohol/benzyl benzoate (BABB) clearing to overcome this limitation. This method was developed for a three‐dimensional (3D) analysis of the internal structures of advanced larvae and juveniles of echinoderms (the sea lily Metacrinus rotundus, the sea urchin Hemicentrotus pulcherrimus, and the sand dollar Scaphechinus mirabilis) and is suitable for obtaining serial optical images by confocal microscopy without the use of specific antibodies or special reagents for labeling. Nile blue is an easy‐to‐use stain that offers several advantages for confocal microscopy such as it can stain various tissues with strong fluorescent signals without substantial bleaching during observation. We found that the strong fluorescence signal of Nile blue quickly yielded clear high‐resolution optical section images for 3D reconstruction. BABB clearing rendered opaque larvae highly transparent. The clearing procedure was also easy and quick. During the process, agarose embedding prior to staining and clearing was found to be critical for handling the samples of less than 500‐μm length and stabilizing their orientations. To conclude, the protocol described is useful for performing a rapid and accurate 3D morphological analysis of echinoderm larvae and juveniles. [ABSTRACT FROM AUTHOR]

This paper describes the novel method of Ag deposition on the surface of TiO2, additionally investigates the photocatalytic properties of the new photocatalyst in the oxidation of benzyl alcohol under visible‐light as well as sunlight. Silver nanoparticles were deposited on surface of titanium dioxide through the Tollens test method. Ag(0) has been prepared in situ by reduction of [Ag (NH3)2]+ by glucose as a moderate and green reducing agent for the first time. The properties of n‐TiO2‐P25/Ag were investigated through X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐Ray (EDX), inductively coupled plasma optical emission spectrometry (ICP‐OES), BET analysis, UV–visible/DRS techniques, and photoluminescence (PL) analysis. [ABSTRACT FROM AUTHOR]

This paper describes a new mutual transformation mode occurred between two aluminium complexes, L1(AlMe2)2·AlMe3 and (L1AlMe)2, which were generated upon different solvents and bearing the oxazoline‐amido‐phenolate ligand. Density functional theory (DFT) studies support plausible mechanisms. Their catalytic studies were investigated towards ring opening polymerization of ε‐caprolactone and l‐lactide with the benzyl alcohol as the initiating reagent. [ABSTRACT FROM AUTHOR]

The development of efficient and eco‐friendly methods for the synthesis of elaborate amines is highly desired as they are valuable chemicals. The catalytic alkylation of amines using alcohols as alkylating agents, through the so‐called borrowing hydrogen process, satisfies several of the principles of green chemistry. In this paper, four neutral half‐sandwich complexes of Ru(II), Rh(III), and Ir(III) have been synthesized and tested as catalysts in the N‐benzylation of amines with benzyl alcohol. The new derivatives contain a N^N′ anionic ligand derived from 5‐(pyridin‐2‐ylmethylene)hydantoin (Hpyhy) that has never been tested in metal complexes with catalytic applications. In particular, the Ir derivatives, [(Cp*)IrX(pyhy)] (X = Cl or H), exhibit high activity along with good selectivity in the process. Indeed, the scope of the optimized protocol has been proved in the benzylation of several primary and secondary amines. The selectivity towards monoalkylated or dialkylated amines has been tuned by adjusting the amine:alcohol ratio and the reaction time. Experimental results support a mechanism consisting of three consecutive steps, two of which are Ir catalyzed, and a favorable condensation step without the assistance of the catalyst. Moreover, an unproductive competitive pathway can operate when the reaction is performed in open‐air vessels, due to the irreversible release of H2. This route is hampered when the reaction is carried out in close vessels, likely because the release of H2 is reversed through metal‐based heterolytic cleavage. From our viewpoint, these results show the potential of the new catalysts in a very attractive and promising methodology for the synthesis of amines. [ABSTRACT FROM AUTHOR]

A highly efficient copper‐catalyzed three component, one‐pot reaction has been described for the synthesis of imidazo[1,2‐c]quinazolines and benzimidozo[1,2‐c]quinazolines from 2‐(2‐bromophenyl)‐1H‐imidazoles/benzimidazoles using benzyl alcohol or benzylamine as benzaldehyde surrogate and sodium azide as nitrogen source. Various functional groups were well tolerated and desired products were obtained in moderate to good yields. The reaction involves copper‐catalyzed sequential azidation of 2‐(2‐bromophenyl)‐1H‐imidazoles/benzimidazoles through SNAr reaction and reductive amination followed by oxidative condensation with benzyl alcohols or benzylamines. The significant practical advantages of the protocol are utilization of the readily accessible simple substrates, broad substrate scope, and ligand‐free reaction conditions. [ABSTRACT FROM AUTHOR]

Using a type of tetra‐substituted metal phthalocyanine carbon nanotubes composite material [4 a (OPh‐p‐CF3)CuPc]‐MWCNTs as a catalyst, a method to synthesize benzamides through the oxidative amidation of benzyl alcohol was developed. Synthesize copper phthalocyanine by simple DBU liquid phase catalytic method, and then load phthalocyanine on carbon nanotubes by ultrasound to form four‐substituted metal phthalocyanine carbon nanotubes composite material [4 a (OPh‐p‐CF3)CuPc]‐MWCNTs. The composite materials were detected by ultraviolet visible spectroscopy (UV‐Vis), Fourier transforms infrared spectroscopy (FT‐IR), X‐ray diffraction spectroscopy (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). To achieve high‐efficiency and optional catalyze, studied solvent type, oxidant type and dosage, catalyst dosage, time and temperature. In the screening experiment, [4 a (OPh‐p‐CF3)CuPc]‐MWCNTs composite material has high catalytic ability in the oxidation of benzyl alcohol. At the greatest of times, the highest conversion ratio of benzyl alcohol (100 %), selectivity of benzamide (89 %) was obtained. The oxidant was TBHP and the amount was 3 mL, 60 °C for 24 h in DMF. Different kinds of amides were set up by various substituted benzyl alcohols, and good results were obtained. [ABSTRACT FROM AUTHOR]

The synthesis of secondary amine by the photoalkylation of nitrobenzene with benzyl alcohol using a simple light source and sunlight is a challenging task. Herein, a one‐pot cascade protocol is employed to synthesize secondary amine by the reaction between nitrobenzene and benzyl alcohol. The one‐pot cascade protocol involves four reactions: (a) photocatalytic reduction of nitrobenzene to aniline, (b) photocatalytic oxidation of benzyl alcohol to benzaldehyde, (c) reaction between aniline and benzaldehyde to form imine, and (d) photocatalytic reduction of imine to a secondary amine. The cascade protocol to synthesize secondary amine is accomplished using Bi2MoO6 and Pd nanoparticles decorated Bi2MoO6 catalysts. The surface characteristics, oxidation states, and elemental compositions of the materials are characterized by several physicochemical characterization techniques. Optoelectronic and photoelectrochemical measurements are carried out to determine the bandgap, band edge potentials, photocurrents, charge carrier's separation, etc. An excellent yield of secondary amine is achieved with simple household white LED bulbs. The catalyst also exhibits similar or even better activity in sunlight. The structure‐activity relationship is established using catalytic activity data, control reactions, physicochemical, optoelectronic characteristics, and scavenging studies. Bi2MoO6 and Pd nanoparticles decorated Bi2MoO6 exhibit excellent photostability and recyclability. The simple catalyst design with a sustainable and economical light source for the synthesis of useful secondary amine from the nitrobenzene and benzyl alcohol would attract the researchers to develop similar catalytic protocols for other industrially important chemicals. [ABSTRACT FROM AUTHOR]

The mesoporous silica SAB‐15 material and a series of nano‐composite bimetal oxides‐SBA‐15 materials are synthesized. The oxidation of various benzyl alcohols to aromatic aldehydes has been studied using nano‐composite bimetal oxides‐SBA‐15 materials as catalysts in air. The results indicate that the CrMnOx‐SBA‐15 material can promote the oxidation of benzyl alcohols to aromatic aldehydes with excellent yields smoothly. The microstructure and morphology of SBA‐15 and CrMnOx‐SBA‐15 materials are characterized by SEM, TEM, XRD and nitrogen adsorption/desorption isotherms, respectively. In addition, the UHRTEM images, EDS image mapping, and the X‐ray photoelectron spectroscopy (XPS) of CrMnOx‐SBA‐15 material also are characterized, which indicate the structure of the catalyst is advantageous to improve its catalytic activity. [ABSTRACT FROM AUTHOR]

Copper‐based metal‐organic framework (Cu3(BTC)2(H2O)3]n⋅nH2OMeOH (HKUST‐1) has been subjected to thermolysis under air atmosphere at different temperatures ranging from 100 to 300 °C. This treatment produces the partial removal of ligands, the generation of structural defects and additional porosity in a controlled way. The resulting defective materials denoted according to the literature as quasi‐MOFs, were subsequently employed as heterogeneous catalysts in the one pot synthesis of N‐benzylideneaniline from aniline and benzyl alcohol in open air as terminal oxidant at 70 °C under base‐ and dehydrating agent‐free conditions. The Q‐HKUST catalysts calcined at 240 °C (QH‐240) was the most efficient in the series, promoting imine synthesis. Data from Knoevenagel condensation of malononitrile shows that in QH‐240 the distances of Cu ions in HKUST‐1 cavities are preserved, increasing the Knoevenagel activity, but a strong rearrangement takes place at 300 °C or above. The unsaturated copper active sites with simultaneous presence of micro‐ and mesopores in QH‐240 are responsible for this excellent catalytic performance. The effective parameters on catalytic activity of QH‐240 including deligandation temperature, the amount of catalyst, the ratio of reactants, and reaction temperature as well as the stability and recyclability of the catalyst were also investigated. The possible mechanism used by QH‐240 follows alcohol aerobic oxidation and subsequent anaerobic condensation of aldehyde intermediate with aniline. [ABSTRACT FROM AUTHOR]

Polyimide fabric, as a high-performance fabric, possesses advantageous properties, such as outstanding thermal stability and chemical resistance, but has poor dyeability. In this paper, polyimide fabric was dyed successfully with disperse dyes by high-temperature and high-pressure dyeing in the presence of a swelling agent and auxiliaries. Under optimal dyeing conditions, it is pretreated with Na OH 6 g l−1 and dyed with disperse dyes 5% o.w.f., NaCl 1 m, benzyl alcohol 60 ml l−1 at 135 °C for 45 min to obtain a satisfactory colour yield with good washing fastness and dry rubbing fastness with 93.3% strength retention. The experimental results demonstrate that the Nernst adsorption isotherm is a favourable model for polyimide fabric dyeing with disperse dyes. [ABSTRACT FROM AUTHOR]

In this study, we prepared a series of dinuclear aluminium complexes {Bis{2-OAlMe2-3-CH=N[CH2CH2N(CH3)2]-5-CH3C6H2} CH2, Bis[2-OAlMe2-3-CH=N(2-PyCH2)-5-CH3C6H2]CH2, and Bis{2- OAlMe2-3-CH=N[2-N(CH3)2C6H4]-5-CH3C6H2}CH2} as well as their corresponding mononuclear aluminium compounds derived from NNO-tridentate Schiff-base ligands. The compounds were characterised by ¹H and 13C spectroscopy and elemental analyses. Complexes 4 and 7 were additionally characterised by single-crystal X-ray diffraction. Their activities toward the ringopening polymerisation (ROP) of ε-caprolactone (ε-CL) were investigated. In the presence of benzyl alcohol (BnOH), these complexes are catalytically active for the ROP of ε-CL. The kinetic studies for the polymerisation catalysed by these complexes indicated that the polymerisation was well controlled and produced polymers within a narrow molecular weight distribution. At low monomer concentrations, the catalytic activity of binuclear complexes is considerably greater than that of mononuclear complexes. [ABSTRACT FROM AUTHOR]

The Cover shows a micro‐kinetic model being applied to benzylic alcohol oxidation over metal nanoparticles. In their new Full Paper, A. Savara et al. report the first micro‐kinetic modeling of liquid phase benzylic alcohol oxidation over transition metal nanoparticles. The micro‐kinetic model was applied to palladium nanoparticles and enabled applying the concept of a sticking coefficient in solution. The kinetic simulations were able to reproduce the 18 trends observed in the responses of the six products when varying the alcohol concentration, oxygen pressure, and temperature. The mechanism used was based on surface science knowledge and an earlier study published in ChemCatChem. More information can be found in the Full Paper by A. Savara et al. et al. on page 2482 in Issue 15, 2016 (DOI: 10.1002/cctc.201600368). [ABSTRACT FROM AUTHOR]

In the published paper, there is a mistake in the assignment of the fragments to the mass spectra in Figure. GLO:OLD/02dec19:chem201905072-fig-0005.jpg PHOTO (COLOR): GC-MS spectrum from the TG-GC-MS measurement. Injection at 320 °C: the peaks at 3.57, 8.6 and 9.72 min are associated to Boc, Cbz and Pht, respectively. gl. [Extracted from the article]

In this work, the catalytic efficiency of a novel biorelevant triazine (TA)-based pantothenate (vitamin B5) copper(II) complex [Cu(II)-TA/B5] in the aerobic oxidation of benzyl alcohols and tandem synthesis of bis(indolyl)methanes was exploited. The star-shaped catalyst was characterized by different techniques such as FT-IR, EDX, ICP, TEM, and TGA. TEM images revealed a honeycomb structure resulting from the accumulation of nanoparticles with size ranging between 2–6 nm. The high yields and excellent selectivity were obtained for the production of various benzaldehydes and bis(indolyl)methanes under aerobic conditions. Recycling tests, spectroscopic data, and leaching experiments testified that the title heterogeneous biorelevant catalyst preserved its activity and structural integrity during oxidation and coupling reactions. The presented catalytic systems qualify all requirements for efficient catalytic systems for applied goals. [ABSTRACT FROM AUTHOR]

The Cover shows an industrial landscape, where Au nanoparticles are used as catalysts for oxidation reactions.In their Full Paper, L. M. D. R. de Sousa Martins et al. demonstrate an efficient single‐pot oxidative functionalization of cyclohexane and benzyl and methylbenzyl alcohols under mild conditions with high selectivity, catalyzed by reusable Au nanoparticles on Al2O3, Fe2O3, ZnO, and TiO2. Au nanoparticles on Fe2O3 led to an unusual almost exclusive formation of cyclohexanol by control of reaction time, but Au nanoparticles on TiO2 had a remarkable catalytic effect on acetophenone yield. [ABSTRACT FROM AUTHOR]

Benzyl nitrite (PhCH2ONO) was previously identified as the pivotal intermediate in the HNO3-mediated oxidation of benzyl alcohol. Its acid-catalyzed decomposition yields benzaldehyde and HNO, the precursor of undesirable N2O. Most likely, an analogous mechanism is responsible for the formation of N2O during the oxidation of cyclohexanol and cyclohexanone to adipic acid, the largest industrial source of this important greenhouse gas. In this paper, the decomposition of benzyl nitrite is studied in more detail, allowing the kinetic isotope effect and the influence of substituents to be determined. A linear Evans-Polanyi correlation between the measured Arrhenius activation energies and the computed reaction energies was established. Furthermore, the differences in the reactivities of the substituted benzyl nitrites are reflected in the oxidation of the corresponding alcohols, and also affect the rate-determining step in the overall mechanism. The results of this study corroborate the importance of the nitrite intermediate in HNO3-based oxidation technology. [ABSTRACT FROM AUTHOR]

In flowering plants that produce concealed rewards, pollinator foraging preferences may select for floral advertisement traits that are correlated with rewards. To date, studies have not focused on the potential for honest signals to vary across populations, which could occur due to differences in pollinator communities or plant mating system.We tested for variation in honest signals across and within populations and mating systems in Arabis alpina, a broadly distributed arctic‐alpine perennial herb that is visited by a variable community of insects. In a greenhouse common garden, we tested for correlations between corolla area, floral scent and nectar volume in 29 populations. In 12 field populations, we examined variation in pollen limitation and corolla area.Across and within populations and mating systems, larger flowers generally produced more nectar. Total scent emission was not correlated with nectar production, but two compounds—phenylacetaldehyde and benzyl alcohol—may be honest signals in some populations. Corolla area was correlated with pollen limitation only across populations.Our results suggest that honest signals may be similar across populations but may not result from contemporary direct selection on floral advertisements. Read the free Plain Language Summary for this article on the Journal blog. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Alcohols as among the most widely occurring organic compounds known, deoxygenative transformations of free alcohols as partners in radical addition reactions remain formidable challenges with great opportunities to achieve new and useful transformations. Herein, we report a protocol via C—O bond cleavage and C—C bond‐forming reaction of trifluoromethyl alkenes with free alcohols assisted by titanium reagents via a deoxygenative radical strategy, enabling the divergent synthesis for functional‐group‐rich organofluorinated compounds in high efficiencies. In this transformation, tertiary alcohols by Ti‐catalysis could be converted to trifluoromethyl alkanes without defluorination in acidic conditions, while benzyl alcohols are employed by Ti‐mediated activation to supply the gem‐difluoroalkenes with defluorination in the presence of a base. This protocol is applicable for a broad range of trifluoromethyl alkenes with good functional group tolerance and a variety of tertiary alcohols and benzyl alcohols (including primary, secondary, and tertiary alcohols), and is scalable to the gram level. Remarkably, the utility of this protocol is demonstrated by several derivatizations and late‐stage functionalization of drug molecules. The successful applications in scale up reactions and late‐stage functionalization of several drug molecules demonstrate its potential synthetic value in drug discovery settings. [ABSTRACT FROM AUTHOR]

The performance of six newly synthesized benzo[h]quinoline‐derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5‐bis‐trifluoromethylphenyl)borate salts bearing different substituents −X (−OMe, −H, −Cl, −Br, −NO2 and −(NO2)2) on the heterochelating ligand were evaluated in the dehydro‐O‐silylation of benzyl alcohol and the monohydrosilylation of 4‐methoxybenzonitrile by Et3SiH, two reactions involving the electrophilic activation of the Si−H bond. The benchmark shows a direct dependence of the catalytic efficiency with the electronic effect of −X, which is confirmed by theoretical assessment of the intrinsic silylicities Π of hydridoiridium(III)‐silylium adducts and by the theoretical evaluation of the propensity of hydridospecies to transfer the hydrido ligand to the activated substrate. The revisited analysis of the Ir−Si−H interactions shows that the most cohesive bond in hydridoiridium(III)‐silylium adducts is the Ir−H one, while the Ir−Si is a weak donor‐acceptor dative bond. The Si...H interaction in all the cases is noncovalent in nature and dominated by electrostatics confirming the heterolytic cleavage of the hydrosilane's Si−H bond in this key catalytically relevant species. [ABSTRACT FROM AUTHOR]

A chemically stable 2D microporous COF (PMCR‐1) was synthesized via the multicomponent Povarov reaction. PMCR‐1 exhibits a remarkable and long‐term stable photocatalytic H2O2 production rate (60 h) from pure and sea water under visible light. The H2O2 production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π–π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H2O2 formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well‐defined micropores of PMCR‐1 enable size‐selective photocatalytic oxidation. [ABSTRACT FROM AUTHOR]

Empowered by reticular chemistry, an ocu‐metal‐organic framework (MOF) catalyst has been created for the first time. The catalyst, SYD‐1, was rationally designed and successfully synthesised by assembling 8‐c prismatic zirconium oxo‐clusters and 6‐c octahedral Ru(bpy)32+‐based metalloligands into a three‐dimensional structure. Catalytically active metal sites were then attached to the coordinatively unsaturated sites on the Zr oxo‐clusters postsynthetically via a sequential practice of solvent‐assisted ligand exchange and metalation processes, giving rise to SYD‐1‐CuNi. SYD‐1‐CuNi was thoroughly characterised via an array of X‐ray diffraction, 77 K N2 sorption experiments, nuclear magnetic resonance measurements, microscopic analysis, optical absorption spectra analysis and electrochemical measurements to demonstrate the successful synthesis of the targeted SYD‐1‐CuNi and its potential in photocatalysis. The photocatalytic performance of SYD‐1‐CuNi was illustrated by driving a model reaction, namely photocatalytic CO2 reduction reaction (yield of CH4 19.2 μmol g−1 h−1)/hydrogen evolution reaction (yield of H2 200.4 μmol g−1 h−1) concomitantly with oxidation of benzyl alcohol to benzaldehyde (286.6 μmol g−1 h−1). The present work highlights the power and potential of reticular chemistry in the at‐will synthesis of MOF materials for a specific application. [ABSTRACT FROM AUTHOR]

Selective oxidation of alcohols to the carboxylic acid plays an important role in the production of valuable chemicals. Herein, NiCo hydroxide (NiCo(OOH)x) nanosheets with a thickness of ~4 nm were controllably fabricated in a facile way efficient for the electrooxidation of benzyl alcohol (BAL) to benzoic acid (BAD). Mechanistic studies confirmed the hydroxyl active intermediate (OH*) generated on the surface of NiCo(OOH)x nanosheets through operando electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy analysis during the electrooxidation process. Importantly, we discovered that the OH* was crucial to boost the selective oxidation of BAL by attacking the hydroxyl end group to achieve carboxylic acid. The early onset potential of 1.16 VRHE in the presence of BAL was below 1.23 VRHE for oxygen evolution reaction. The rotating ring‐disk electrode further revealed that the electrocatalytic BAL oxidation reaction occurred earlier in the oxygen evolution reaction. In 150 mM BAL, NiCo(OOH)x nanosheets generated a high BAD selectivity of >99% and full conversion of BAL in 3 h. The experimental and theoretical calculation revealed that the dominant pathway of BAL oxidation was the interaction between nucleophilic BAL with OH* to form BAL‐OH* directly by dehydrogenates, thereby producing BAD with high efficiency. This research sheds mechanism insights on the electrocatalytic alcohols oxidation reaction. [ABSTRACT FROM AUTHOR]

In this paper, a series of novel N‐(substituted phenyl/benzyl)‐2‐methylthio‐4‐((pyridin‐3‐ylmethyl)amino)pyrimidine‐5‐carboxamides were synthesized by multistep reactions. Their in vitro antifungal activity against two kinds of plant pathogenic funguese was evaluated, and the result showed that most target compounds possessed excellent activities against rape S. sclerotiorum. More details will be discussed by Dr. Lin Jiang and his co‐workers on page 445–451 in this issue. [ABSTRACT FROM AUTHOR]

Vat polymerization allows for the accurate and fast fabrication of personalized implants and devices. While the technology advances rapidly and more materials become available, the fabrication of flexible yet tough resorbable materials for biomedical applications remains a challenge. Here, a formulation that can be 3D printed with high accuracy using vat polymerization, yielding materials that are tough, degradable, and non‐toxic is presented. This unique combination of properties is obtained by combining a long‐chain polycaprolactone macromonomer with a small molecule cross‐linker. A wide range of properties is achieved by tuning the ratio of these components. The use of benzyl alcohol as a non‐volatile, benign solvent enables fabrication on a low‐cost desktop 3D printer, with an exposure time of 8 s per 50‐micron layer. The 3D‐printed networks are tough and elastic with a tensile strength of 11 MPa at 116% elongation at break. Cells attach and proliferate on the networks with a viability of >91%. The networks are fully degradable to soluble products. This new 3D printable material opens up a range of opportunities in biomedical engineering and personalized medicine. [ABSTRACT FROM AUTHOR]

The best activity of bimetallic AuPd nanoparticles for alcohol oxidation reaction is usually achieved by adjusting the Au/Pd molar ratio. Herein, alloy AuPd nanoparticles of ∼2.5–3.5 nm, ranging from Au‐rich to Pd‐rich compositions, were synthesized through a sol‐immobilization method. A calcination step under air conditions caused an increase in size up to 5.5 nm, but also driven the segregation of Pd to the surface, which generated an Au rich core with Pd on the shell. At high Pd content, the shell structure is formed by PdO. The catalytic activity of Pd‐rich samples (1 : 1, 1 : 2 and 1 : 4 Au : Pd) for benzyl alcohol oxidation increased ∼4‐fold after calcination. Upon reduction with H2, surface PdO motifs are reduced to Pd that did not dissolve back into the AuPd alloy core, maintaining the metallic Pd shell. The catalytic activity decreased. Therefore, restructuring alloyed AuPd nanoparticles into core‐shell like structures with PdO in the shell is beneficial to the catalytic activity, but reduction of PdO layer was detrimental. These results provide new insights on the optimization of AuPd catalysts, considering not only the Au/Pd molar ratio, but also the importance of PdO, which was not anticipated in the previous literature. [ABSTRACT FROM AUTHOR]

The synthesis of imines denotes a cornerstone in organic chemistry. The use of alcohols as renewable substituents for carbonyl-functionality represents an attractive opportunity. Consequently, carbonyl moieties can be in situ generated from alcohols upon transition-metal catalysis under inert atmosphere. Alternatively, bases can be utilized under aerobic conditions. In this context, we report the synthesis of imines from benzyl alcohols and anilines, promoted by KOtBu under aerobic conditions at room temperature, in the absence of any transition-metal catalyst. A detailed investigation of the radical mechanism of the underlying reaction is presented. This reveals a complex reaction network fully supporting the experimental findings. [ABSTRACT FROM AUTHOR]

A series of benzoylacetone‐imine ligands, PhCOCHCMeNHR (L1H, R = CH2Ph; L2H, R = CH2Ph‐4‐Me; and L3H, R = CH2Ph‐4‐OMe), are first synthesized following the condensation of benzoylacetone and 4‐substituted benzylamine. Later, reacting L1H–L3H with one equivalent of AlMe3 in toluene, the monomeric Al derivatives are generated, (PhCOCHCMeNR)AlMe2 (1, R = CH2Ph; 2, R = CH2Ph‐4‐Me; 3, R = CH2Ph‐4‐OMe). All the ligands and metal derivatives are characterized by 1H and 13C NMR spectroscopy. Single crystal X‐ray diffraction analysis reveals the geometry of all ligands and complex 2. As supporting catalysts, the Al derivatives, 1–3, are effective to initiate the coupling of CO2 and styrene oxide to form cyclic carbonates. Although employing TBAI (tetra‐n‐butylammonium iodide), TBAC, tetrabutylammonium chloride, and TBAB (tetra butyl ammonium bromide) as cocatalyst, the optimized catalytic system exhibits the best conversion of epoxide in presence of TBAI under the reaction temperature and time, respectively, 90°C and 6 hr, respectively. The ring opening polymerization of ε‐caprolactone is also appraised subjecting the Al derivatives, 1–3, as catalysts in presence of benzyl alcohol and all the conversions of ε‐caprolactone reach over 95% at the reaction condition of 100°C and 1 hr. [ABSTRACT FROM AUTHOR]

Photothermal catalysis has attracted great attention owing to high solar energy utilization efficiency, and great progress has been achieved in gas‐phase catalysis. However, photothermal catalysis in liquid‐phase shows a limited performance, due to high specific heat capacity of liquid. Herein, an interfacial photothermal catalytic (IPC) strategy applying an IPC leaf was designed for liquid‐phase catalysis using benzyl alcohol oxidation as the model reaction. On even ground, the benzaldehyde generation rate (8.7 mmol gcat−1 h−1) of the IPC system with Ce‐doped MnO2 as photothermal catalyst was almost 4.8 times and 3 times of bulk photothermal catalysis and the relative bulk thermal catalysis. Experimental results proved that this excellent catalytic performance could be attributed to both the high temperature achieved and the enhanced lattice oxygen activity by solar irradiation. This IPC system also exhibited good universality and long‐term durability. Our work innovatively created a green strategy to obtain fine chemicals with only solar irradiation. [ABSTRACT FROM AUTHOR]

Benzyl alcohol (BnOH) is a widely‐used preservative in a variety of cosmetics, but the excess addition (≥1.0 %) may cause strong symptoms such as nausea, gastrointestinal irritation, convulsion, even death, making it crucial to monitor and control the addition quantity. Herein, we have developed a test‐strip‐like BnOH detection method via tailoring a galactose oxidase (GOase) towards BnOH oxidation and preparing a self‐powered electrochromic strip for BnOH concentration visualization. A double‐substituted GOase variant (Y329S/R330F), on the basis of the reported GOase M1, has been obtained by semi‐rational design with a 24.6‐fold improved activity towards BnOH compared to GOase M1. The GOase Y329S/R330F electrode has a response to BnOH with a linear range of 0.04 to 3.25 mM (R2=0.9985), a sensitivity of 122.78 μA mM−1 cm−2, and a detection limit of 0.03 mM (S/N=3). Coupling an electrochromic Prussian blue (PB) cathode helps the successful sensing visualization without any further power supply. The present sensing is more convenient and user‐friendly than the generally used gas chromatography (GC) and high performance liquid chromatography (HPLC), and brings a more accessible solution to the field of quality controlling. [ABSTRACT FROM AUTHOR]

The palladium‐catalyzed direct oxidative coupling reaction between 2‐aroylimidazoles with aromatic aldehydes or benzyl alcohols under oxidation conditions has been achieved to furnish a variety of carbonyl functionalized 2‐aroylimidazoles in moderate to good yields. The obtained products could be selectively transformed to the corresponding phthalazines and phthalazin‐1(2H)‐ones with hydrazine hydrate as the cyclization partner under different reaction temperature and construct an array of structurally diverse nitrogen‐containing heterocycles. [ABSTRACT FROM AUTHOR]

A metal and light‐free Minisci‐type acylation approach of 8‐aminoquinoline amides with general primary alcohols was demonstrated under tBu4NCl/K2S2O8 system. Simultaneously, the C2−H alkylation can be realized by accident for special benzyl alcohols bearing strong electron‐donating groups. Most N‐heterocycles were also compatible to afford corresponding acylated products. Furthermore, the mechanism investigation reveals that chlorine radical induced the original ketyl radical generation through abstracting the α‐C−H from the alcohols, then underwent nucleophilic carbon‐centered radicals addition, deprotonation, and oxidation to provide the target acylation products. [ABSTRACT FROM AUTHOR]

Selective photooxidation of aromatic alcohols to corresponding aldehydes is a widely used model reaction for evaluation of performance of heterogeneous photocatalysts. A top example is the photocatalytic production of hydrogen peroxide via reduction of dioxygen with concomitant photooxidation of benzyl alcohol to benzaldehyde. Herein we demonstrate the ability of benzaldehyde to promote the auto‐photocatalytic oxidation of benzyl alcohol and produce large quantities of H2O2 in solvent‐free (no water) or biphasic (with water) systems even under nominally visible (>420 nm cut‐off filter) light irradiation. These results shed critical light on the plethora of research reports on photocatalytic H2O2 production in which benzyl alcohol was employed as electron donor. Since the autocatalytic pathway based on the photocatalytic activity of benzaldehyde formed during photocatalysis under such conditions cannot be neglected, the interpretations of photocatalytic performance are likely contentious and distorted in such reports. The use of benzyl alcohol as a model electron donor in photocatalytic studies should be therefore definitely discouraged. On the other hand, as we found that benzaldehyde‐mediated photocatalysis of H2O2 production proceeds also using alternative electron donors (e. g. ethanol), our results highlight the possible prospects for a more general use of benzaldehyde and other aromatic aldehydes in visible light‐driven photocatalysis. [ABSTRACT FROM AUTHOR]

This work presents two mixed‐valent μ3‐oxo‐bridged trinuclear [(Co2+)2Co3+] complexes 1 and 2 and a μ4‐oxo‐bridged tetranuclear [Co2+4] complex 3. Crystal structures of 1 and 2 showed the presence of triangular complexes having two Co2+ and one Co3+ centers bridged by a μ3‐oxo group. In contrast, complex 3 exhibited a tetrahedrally arranged μ4‐oxo‐bridged [Co2+4] core. A significant feature is the stabilization of unusual μ‐oxo‐bridged complexes exclusively supported with all nitrogen donor ligands. The X‐ray photoelectron spectroscopy confirmed the multiple oxidation states of cobalt ions in these complexes. Such oxo‐bridged cobalt complexes were investigated for their catalytic activity towards H2O2‐mediated oxidation of assorted benzyl alcohols. [ABSTRACT FROM AUTHOR]

A dioxidotungsten(VI) complex, [WO2L(CH3OH)]·0.5(CH3OH) (1), was prepared by the reaction of WCl6 and tridentate ONO‐donor Schiff base ligand (H2L) that was obtained from the reaction of 2‐hydroxy‐1‐naphthaldehyde with 4‐aminobenzoic hydrazide. Both H2L and 1 were characterized by various analyses including nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT‐IR) and UV–Vis spectroscopy, and elemental analysis. Single crystal X‐ray analysis was used to determine the crystal structure of the complex, which revealed that there is a free ‐NH2 group in its structure. Therefore, the heterogeneous catalyst was obtained by supporting of 1 on propionyl chloride‐functionalized silica gel. The synthesized supported catalyst (Si‐W) was characterized by diffuse reflectance spectroscopy (DRS), thermogravimetric analysis (TGA), FT‐IR, scanning electron microscope (SEM), X‐ray photoelectron spectroscopy (XPS), energy‐dispersive spectroscopy (EDS), and X‐ray powder diffraction (XRD) analyses. The heterogeneous catalyst (Si‐W) was utilized in the oxidation of benzyl alcohol derivatives with H2O2 under reflux condition at air atmosphere. The effects of the concentration of oxidant, temperature, and the nature of solvent on catalytic performance of the resulting compound were investigated and the results indicated that they have considerable effect on the activity and selectivity of Si‐W. The heterogeneous catalyst was recovered several times and reused for oxidation reaction. The results of various analyses including FT‐IR spectroscopy, SEM, TGA, EDS, and XRD indicated that there are no considerable differences between recovered catalyst and the fresh one. The results show that the synthesized silica supported dioxidotungsten(VI) complex is active and stable catalyst for oxidation of benzylic alcohols and its selectivity depends on the reaction condition. [ABSTRACT FROM AUTHOR]

New water soluble neutral and cationic palladium complexes were synthesized using 8‐aminoquinoline (8‐AQ) and 2‐methyl 8‐aminoquinoline (2‐Me 8‐AQ) ligands and their catalytic properties were evaluated. The neutral trimeric complexes having a Pd3N3 core were found to form when Pd(OAc)2 was reacted with 8‐AQ or 2‐Me 8‐AQ irrespective of the stoichiometry between the 2 reagents. Controlled addition of triflic acid to the neutral trimeric complex resulted in the formation of a trimeric cationic palladium complex as well as a monomeric cationic complex. A cationic palladium complex having two units of 2‐Me‐8AQ ligand was also synthesized from the cationic monomeric complex. Crystal structures of the new palladium complexes are reported in this study. The water‐soluble neutral palladium complex showed catalytic activity for the oxidation of benzyl alcohols to benzaldehydes, while the cationic palladium complexes were found to be efficient catalysts for the oxidation of styrenes to methyl ketones. [ABSTRACT FROM AUTHOR]

Front Cover: A Borrowing Hydrogen Strategy for Dehydrative Coupling of Aminoisoquinolines with Benzyl Alcohols in Water (Eur. J. Org. B The Front Cover b shows a borrowing hydrogen strategy for a palladium-catalyzed dehydrative coupling of 2-aminoisoquinoline with benzyl alcohol in water. B The Front Cover b shows a borrowing hydrogen strategy for a palladium-catalyzed dehydrative coupling of 2-aminoisoquinoline with benzyl alcohol in water. [Extracted from the article]

A convenient and effective method for the construction of C−S bond under transition‐metal free conditions was reported. Thus, diverse thiocarbamide esters could be smoothly obtained in moderate to good yields from inexpensive and readily available starting materials, such as phenyl isothiocyanate, alcohols and benzyl halides. This method features mild conditions, easy operation, short reaction time and broad substrate scopes, providing a facile and convenient strategy for the preparation of some compounds with potential biological activities. [ABSTRACT FROM AUTHOR]

The standard heparin lock for dialysis catheters in US dialysis units is 1000 units/ml, though its use has significant limitations and problems. The alternative catheter lock of 4% sodium citrate is used in some patients, but a 7% solution would maintain catheter patency better than the 4% concentration. In spite of the failure of two prior catheter locks to become widely used in the US (highly concentrated citrate and Zuragen™), Ash Access worked with a compounding pharmacy to produce 7% sodium citrate with preservative in single‐patient use frangible vials, at a reasonable cost to users. The product had early acceptance by a number of dialysis units and hospitals, but then follow‐up orders were few. Where the project goes from here is unclear. [ABSTRACT FROM AUTHOR]

Family VIII esterases present similarities to class C β‐lactamases, which show nucleophilic serines located at the S‐X‐X‐K motif instead of the G‐X‐S‐X‐G or G‐D‐S‐(L) motif shown by other carboxylesterase families. Here, we report the crystal structure of a novel family VIII (subfamily VIII. I) esterase (EH7; denaturing temperature, 52.6 ± 0.3 °C; pH optimum 7.0–9.0) to deepen its broad substrate range. Indeed, the analysis of the substrate specificity revealed its capacity to hydrolyse nitrocefin as a model chromogenic cephalosporin substrate (40.4 ± 11.4 units·g−1), and a large battery of 66 structurally different esters (up to 1730 min−1), including bis(2‐hydroxyethyl)‐terephthalate (241.7 ± 8.5 units·g−1) and the mycotoxin T‐2 (1220 ± 52 units·g−1). It also showed acyltransferase activity through the synthesis of benzyl 3‐oxobutanoate (40.4 ± 11.4 units·g−1) from benzyl alcohol and vinyl acetoacetate. Such a broad substrate scope is rare among family VIII esterases and lipolytic enzymes. Structural analyses of free and substrate‐bound forms of this homooctamer esterase suggest that EH7 presents a more opened and exposed S1 site having no steric hindrance for the entrance of substrates to the active site, more flexible R1, R2 and R3 regions allowing for the binding of a wide spectrum of substrates into the active site, and small residues in the conserved motif Y‐X‐X containing the catalytic Tyr enabling the entrance of large substrates. These unique structural elements in combination with docking experiments allowed us to gain valuable insights into the substrate specificity of this esterase and possible others belonging to family VIII. [ABSTRACT FROM AUTHOR]

Cover Feature: Au-Pd Selectivity-switchable Alcohol-oxidation Catalyst: Controlling the Duality of the Mechanism using a Multivariate Approach (ChemCatChem 13/2019) Keywords: SrCO3; Au-Pd nanoparticles; alcohol oxidation; factorial design SrCO3, Au-Pd nanoparticles, alcohol oxidation, factorial design. [Extracted from the article]

A novel and effective dual catalysis system, copper combined with pyridoxal phosphate, which is anchored in maghemite nanoparticles were designed and applied to synthesize α‐aminonitriles from benzyl alcohols. This catalytic system has the potential ability to perform oxidation reactions and subsequently synthesize alpha‐amino nitrile in a reaction environment. Thus, the purpose of this paper is introducing a heterogeneous, sustainable and recyclable catalytic system to perform reactions that require a transition metal catalyst and organocatalyst continuously to achieve a target molecule. The catalysis system is examined and investigated with seven useful analyses such as FT‐IR, TGA, VSM, SEM, TEM, XRD, and ICP. Here, we have demonstrated A new expedient dual catalysis system with high efficiency to synthesize α‐aminonitriles from benzyl alcohol. [ABSTRACT FROM AUTHOR]

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal‐organic frameworks (MOFs, NH2−MIL‐125 and MIL‐125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon‐excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti8O8(OH)4 cluster) of the MOF structure, and the plasmon‐excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4‐benzenedicarboxylate−NH2). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular‐level manipulation of interface charge transfer on plasmonic photocatalysts. [ABSTRACT FROM AUTHOR]

Fifteen aroma compounds have been determined in their free and glycosylated forms in grapes using dispersive liquid‐liquid microextraction with gas chromatography‐mass spectrometry. The sample treatment includes a previous solid‐liquid extraction stage and subsequent parallel microextraction approaches to preconcentrate total aroma content and the free fraction. Thus, the extraction of the total content of analytes requires previous enzymatic hydrolysis of the bound forms. For preconcentration, chloroform (250 μl) and acetonitrile (1.5 ml) were added to 10 ml of the sample extract in the presence of 0.5 g sodium chloride. The absence of matrix effect in the samples allowed quantification against aqueous external standards. Limits of detection ranged between 5 and 30 ng/g, depending on the compound. Method accuracy was studied through recovery assays, with recoveries in the 82–115% range being obtained. Relative standard deviations for repeatability studies were lower than 12%. Four different samples of grapes were analyzed, being quantified linalool in its free form at concentrations in the 359–470 ng/g range, and benzyl alcohol, 2‐phenylethanol, and linalool oxide I and II in their bound forms between 52 and 464 ng/g. [ABSTRACT FROM AUTHOR]

For the (aut)oxidation of toluene to benzyl hydroperoxide, benzyl alcohol, benzaldehyde, and benzoic acid, the thermochemical profiles for various radical-generating reactions have been compared. A key intermediate in all of these reactions is benzyl hydroperoxide, the heat of formation of which has been estimated by using results from CBS-QB3, G4, and G3B3 calculations. Homolytic OO bond cleavage in this hydroperoxide is strongly endothermic and thus unlikely to contribute significantly to initiation processes. In terms of reaction enthalpies the most favorable initiation process involves bimolecular reaction of benzyl hydroperoxide to yield hydroxy and benzyloxy radicals along with water and benzaldehyde. The reaction enthalpy and free energy of this process is significantly more favorable than those for the unimolecular dissociation of known radical initiators, such as dibenzoylperoxide or dibenzylhyponitrite. [ABSTRACT FROM AUTHOR]