Search

BACKGROUND: 'Xynisteri' is considered as the reference white grape cultivar in Cyprus with remarkable adaptation to adverse edaphoclimatic conditions and appreciable oenological properties that renders it as an appropriate cultivar for studies within a global context due to climate change. To this aim, two distinct non‐irrigated plots with different climatic conditions, soil properties and levels of rainfall were selected; Koilani [KO, altitude 800 m, 76% calcium carbonate (CaCO3) content, pH 7.97, average temperature: 16.5 °C, rainfall: 229 mm] and Kyperounda (KY, altitude 1200 m, CaCO3‐free soil, pH 6.47, average temperature: 14.9 °C, rainfall: 658 mm). An array of physiological, biochemical and qualitative indices during successive developmental stages (BBCH 75–89) were determined. During the advanced on‐vine developmental stages (BBCH 85–89), the aromatic profile of grapes was assessed with the employment of gas chromatography–mass spectrometry (GC–MS). Such analysis was complemented with non‐destructive chemometric analyses. RESULTS: Berry ripening process substantially differed on the examined plots; BBCH 89 stage reached at 267 and 303 Julian days for KO and KY, respectively. Results indicated that berry weight, soluble solids content (SSC) and α‐amino nitrogen were higher in KO than in KY, with exception made for ammonium nitrogen content. A total of 75 compounds, including aliphatic alcohols, benzenic compounds, phenols, vanillins, monoterpenes and C13‐norisoprenoids were identified and quantified. The variations of mesoclimatic conditions affected the volatile organic compound (VOC) profiles at the fully‐ripe stage, showing a considerable rise in glycosylated aroma compounds, especially monoterpenes and benzenic compounds. In particular, the higher amount of glycosylated aroma compounds were obtained in KY berries up to mid‐ripe, whereas KO showed higher glycosylated aroma compounds at fully‐ripe stage. Results reported herein indicate that aroma profile of 'Xynisteri' grapes varied substantially in the examined terroirs. Interestingly, the limited rainfall in KΟ non‐irrigated vine did not compromise qualitative and aromatic properties of berries. CONCLUSIONS: The present study aimed at dissecting the impact of terroir on bush‐trained, non‐irrigated grapevines of a cultivar appropriate for extreme climate change scenarios. The volatilome fingerprint was highly variable among the examined plots; such results can be further exploited at vinification level towards production of single vineyard premium end products. © 2024 The Author(s). Journal of the Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Ethers are high value organic compounds widely applied in chemical industry, natural products, material, pharmaceuticals, argochemicals, as well as modern organic synthesis. Herein, we report an adaptive TFA-catalyzed cross-coupling of alcohols with various oxygen nucleophiles (nitro-, halogen-, sulfur-, nitrogen-, aryl-, and alkynyl-substituted aliphatic alcohols), delivering diverse unsymmetrical ethers under mild conditions and simple operation. This protocol features a broad range of substrate scope and high catalytic efficiency (54 examples, up to 99% yield). The decagram scale performance and one-step synthesis of drug molecules evidenced the potential industrial production and practicability of this protocol. [ABSTRACT FROM AUTHOR]

Micelles, a unique structural arrangement, function as nano-dimensional vessels in organic reactions, facilitating numerous catalytic transformations in water. This comprehensive study aims to explore the potential impact of two anionic surfactants (sodium dodecylsulphate or SDS or SC12S and sodium tetradecylsulphate or STS or SC14S) having dissimilar alkyl chain lengths and the hydrophobicity of the aliphatic alcohols (propanol and pentanol) as well on the overall kinetic profile of the oxidation study. The SDS micellar medium significantly encourages the reaction rate compared to STS micellar media. In the case of aliphatic alcohols with varying hydrophobicity, the same kind of rate is observed as with surfactants: (kobs)SDS-Propanol ~ 13-folds > (kobs)SDS-Pentanol ~ 11-folds > (kobs)STS-Propanol ~ 2.4-folds > (kobs)STS-Pentanol ~ 2-folds. The rate of the reaction improves as the aliphatic alcohol and surfactant hydrophobicity reduces. Herein, the effectiveness of micellar catalysis is greatly influenced by the surface charge of the micelle and surfactant-alcohol hydrophobic interaction. The kinetic observations are elucidated with conductometry, fluorometry, UV–Vis spectroscopy, FT-IR, 1H-NMR, DLS, FESEM, TEM, and Zeta potential analysis. The Piszkiewicz's kinetic model has also been applied to enlighten the linear rate acceleration in both micellar media. [ABSTRACT FROM AUTHOR]

Herein, we report the use of an air‐stable iridium pyrazolato complex as an effective catalyst for the α‐alkylation of ketones and arylacetonitriles with primary alcohols, employing borrowing hydrogen strategy. The alkylation reactions were efficiently conducted at 120 °C in toluene utilizing a very low catalyst loading (0.1 mol %). A broad range of ketones and arylacetonitriles, in combination with various aromatic and aliphatic primary alcohols, were successfully transformed into the corresponding α‐alkylated products. Additionally, quinoline derivatives were synthesized from 2‐aminobenzylalcohol and ketones using dehydrogenative coupling strategy. A mechanistic investigation unveiled that the key step involved alcohol activation via metal‐ligand cooperation. [ABSTRACT FROM AUTHOR]

The synthesis of indole phytoalexin-like analogs related to alkyl (((1-(4-substitutedphenyl)-3-oxo-3-phenylpropyl)thio)carbonothioyl)-ʟ-tryptophanate 1a–d and the evaluation of their antifungal activity against the phytopathogen Fusarium oxysporum is reported. The target compounds were synthesized in the following two stages: (1) the initial esterification of ʟ-tryptophan, which reacted with trimethyl silane chloride and simple aliphatic alcohols (R = Me, Et) under microwave irradiation (MWI) at 100 °C to obtain the respective alkyl ester 2a–b; (2) the resulting mixture of ʟ-tryptophanates 2a–b with carbon disulfide and (E)-chalcone 3a–b under MWI at 50 °C during 60 min, followed by purification through classical column chromatography (55–76% yields). The products were obtained as mixtures of (S,R) and (S,S) diastereoisomers. An LC-DAD-MS analysis allowed us to establish the ratio of these diastereoisomers, and subsequent DFT/B3LYP-based computational calculations of the NMR 1H chemical shifts suggested that the major diastereoisomer involved an (S,R) absolute configuration, comprising more than 60% of the mixture. The compounds 1a–d were subjected to an antifungal activity test against the phytopathogen F. oxysporum using an amended medium-based assay. Compound series 1 showed inhibition percentages of 80% at the first concentration and IC50 values between 0.33 and 5.71 mM, demonstrating greater potential as antifungal agents compared to other ʟ-tryptophan derivatives like alkyl (2S)-3-(1H-indol-3-yl)-2-{[(1Z)-3-oxobut-1-en-1-yl]amino}propanoate, which presented lower inhibition percentages. In summary, phytoalexin analogs derived from ʟ-tryptophan and (E)-chalcones significantly inhibited the mycelial growth of Fusarium oxysporum, indicating their potential as effective antifungal agents. [ABSTRACT FROM AUTHOR]

Many people convicted for drunken driving suffer from an alcohol use disorder and some traffic offenders consume denatured alcohol for intoxication purposes. Venous blood samples from people arrested for driving under the influence of alcohol were analyzed in triplicate by headspace gas chromatography (HS-GC) using three different stationary phases. The gas chromatograms from this analysis sometimes showed peaks with retention times corresponding to acetone, ethyl methyl ketone (2-butanone), 2-propanol, and 2-butanol in addition to ethanol and the internal standard (1-propanol). Further investigations showed that these drink-driving suspects had consumed an industrial alcohol (T-Red) for intoxication purposes, which contained > 90% w/v ethanol, acetone (~ 2% w/v), 2-butanone (~ 5% w/v) as well as Bitrex to impart a bitter taste. In n = 75 blood samples from drinkers of T-Red, median concentrations of ethanol, acetone, 2-butanone, 2-propanol and 2-butanol were 2050 mg/L (2.05 g/L), 97 mg/L, 48 mg/L, 26 mg/L and 20 mg/L, respectively. In a separate GC analysis, 2,3-butanediol (median concentration 87 mg/L) was identified in blood samples containing 2-butanone. When the redox state of the liver is shifted to a more reduced potential (excess NADH), which occurs during metabolism of ethanol, this favors the reduction of low molecular ketones into secondary alcohols via the alcohol dehydrogenase (ADH) pathway. Routine toxicological analysis of blood samples from apprehended drivers gave the opportunity to study metabolism of acetone and 2-butanone without having to administer these substances to human volunteers. [ABSTRACT FROM AUTHOR]

Ethanol production by fermentation results in obtaining, in addition to the main product, ethyl alcohol, by-products and secondary products, which include carbon dioxide, fusel oil, and ester–aldehyde cut. Fusel oil, despite its low yield and the large volume of ethanol production, accumulates at distilleries, which ultimately raises the question of its disposal or the rational use of this by-product. Fusel oil, being a complex mixture, can serve as a source of technical alcohols used in various sectors of the economy, including the food industry, pharmaceuticals, organic synthesis, perfume, and cosmetics industries, as well as the production of paints and varnishes. However, the complexity of using fusel oil lies in its difficult separation. The reason for this is the presence of water, which forms low-boiling azeotropes with aliphatic alcohols. Our study aimed to develop a process flow diagram (PFD) that allows individual components from fusel oil to be obtained without extraneous separating agents (not inherent in fusel oil). This condition is necessary to obtain products labeled as natural for further use in the food, perfume, cosmetic, and pharmaceutical industries. The distinctive feature of this work is that the target product is not only isoamyl alcohol but also all other alcohols present in the composition of fusel oil. To achieve this goal and create a mathematical model, the Aspen Plus V14 application, the Non-Random Two Liquid (NRTL) thermodynamic model, and the Vap-Liq/Liq-Liq phase equilibrium were used. Fusel oil separation was modeled using a continuous separation PFD to obtain ethanol, water, isoamyl alcohol, and raw propanol and butanol cuts. The Sorel and Barbet distillation technique was used to isolate ethanol. The isolation of isopropanol and 1-propanol, as well as isobutanol and 1-butanol, was modeled using the batch distillation method. The isolation of fusel oil components was based on their thermodynamic properties and the selection of appropriate techniques for their separation, such as extraction, distillation, pressure swing distillation, and decantation. The simulation of fusel oil separation PFD showed the possibility of obtaining the components of a complex mixture without separating agents, as discussed earlier. Ethanol corresponds to the quality of rectified ethyl alcohol, and 1-butanol and isoamyl alcohols to anhydrous alcohols, whereas isopropanol (which contains an admixture of ethanol), 1-propanol, and isobutanol are obtained as aqueous solutions of different concentrations of alcohols. However, due to a distillation boundary in the raw propanol and butanol cuts, these mixtures cannot be separated completely, which leads to the production of intermediate fractions. To eliminate intermediate fractions and obtain anhydrous isopropanol, 1-propanol, and isobutanol in the future, it is necessary to solve the dehydration problem of either fusel oil or the propanol–butanol mixture. [ABSTRACT FROM AUTHOR]

A general cobalt-catalyzed α-alkylation of nitriles with alcohols is reported. Utilizing this straightforward borrowing hydrogen methodology, a series of substituted and functionalized nitriles can be easily coupled with benzylic, heterocyclic, and aliphatic alcohols to prepare diverse functionalized nitriles in good to excellent yields (>70 examples). Key for this synthesis is the use of specific cobalt-nanoparticles supported on N-doped carbon, which were conveniently prepared by pyrolysis of a templated material generated in situ by mixing cobalt chloride, zinc chloride, D -glucosamine hydrochloride, and colloidal silica, and subsequent removal of the silica. [ABSTRACT FROM AUTHOR]

Tandem reactions via electrocatalytic annulations have emerged as a strategy for the construction of heterocycles. Herein, a two‐component electrochemical annulation via sequential reduction, oxidation, and condensation steps to synthesize valuable benzimidazoles motifs is reported. This reaction, which utilizes electricity as both the oxidants and reductants, tolerates a broad range of functional groups. Detailed mechanistic studies including control experiments, cyclic voltammetry (CV) analysis, and key reaction intermediate characterization, reveals an intermolecular electrochemical redox/cyclization pathway. [ABSTRACT FROM AUTHOR]

The daunting challenges in converting alcoholic O−H bonds with high bond‐dissociation energy (BDE) to alkoxy radicals and harnessing those unruly reaction species largely limit exploiting free alcohols in C(sp3)−H functionalization. Herein we describe a novel radical alkynylation and allylation of unactivated C(sp3)−H bonds with unmodified aliphatic alcohols. The use of phenyliodine bis(trifluoroacetate) (PIFA) enables the formation of alkoxy radicals under mild photochemical conditions. α‐Methyl styrene serves as a sacrificial‐reagent that significantly improves the reaction outcomes. This transition‐metal free protocol further features broad substrate scope, exclusive site‐selectivity, high product diversity, and simple operation, supplying a robust manifold for C(sp3)−H functionalization using easily available aliphatic alcohols as feedstock. [ABSTRACT FROM AUTHOR]

A process combining aldol condensation and hydrogenation of bio‐based cyclopentanone (CPO) in a one‐pot reaction is proposed. Cu‐based bifunctional catalysts obtained from hydrotalcite‐type precursors were found highly active in mild reaction conditions (i.e., 130–170 °C), producing valuable bicyclic (C10) and tricyclic (C15) aliphatic alcohols/ketones with interesting application as sustainable aviation fuel (SAF) precursors with enhanced properties. The presence of surficial strong basic sites active in aldol condensation, together with the formation of highly dispersed copper nanoparticles able to catalyze C═C and C═O hydrogenation (TOF of 0.06–0.16 s−1), assured high catalytic efficiency and fine control of the products nature and distribution. From the optimization of both catalysts formulation and reaction conditions it was found that, properly tuning the Cu content, it is possible to drive products distribution towards the production of bicyclic (C10) aliphatic alcohol with high selectivity (75% at total CPO conversion, when Cu = 10 wt %, at 170 °C, 1.0 MPa of H2) and short reaction time (4 h). The optimized catalyst formulation showed impressive stability over multiple reaction/regeneration cycles, demonstrating the high potential of the proposed catalytic process for future applications in sustainable biofuels production. [ABSTRACT FROM AUTHOR]

A series of N,N‐chelate half‐sandwich iridium complexes were synthesized by a simple method with good yields. The dehydrogenation of a series of aromatic and aliphatic primary alcohols to corresponding carboxylic acids has been successfully achieved by the prepared air stable iridium complexes under mild reaction conditions. Carboxylic acids were obtained in high yields under open flask condition with broad substrates and good tolerance to sensitive functional groups. Such a half‐sandwich iridium catalyst system showed desirable stability and catalytic activity, and the achievement of a high TOF of 372.0 h−1 could be observed with an extremely low catalyst loading of only 0.05 mol%. Furthermore, the sustainable catalyst could be reused for a minimum of five cycles without obviously losing its activity, highlighting its potential application in industry. Structure of N,N‐chelate iridium complexes 1 and 3 were determined by single‐crystal X‐ray analysis. [ABSTRACT FROM AUTHOR]

A simple, economical, and safe method for the synthesis of mesoionic 1,3-diaryltetrazolium derivatives bearing a para -substituted phenyl group at the 1- or 3-position via thiosemicarbazides was established. Such compounds were directly obtained from the corresponding para -substituted anilines instead of aryl isothiocyanates and arylhydrazines. The newly synthesized mesoionic compounds were successfully converted into the corresponding nitrosotetrazolium salts, which were utilized as catalysts for oxidation of an aliphatic alcohol and analyzed by cyclic voltammetry to determine the correlation between the catalytic efficiencies and redox potentials. The proposed method can be widely applied and is valuable for investigating the substituent effects in mesoionic and related compounds. [ABSTRACT FROM AUTHOR]

A new approach to managing the extraction properties of eutectic solvents based on aliphatic alcohols is proposed. Aliphatic alcohols, when functioning as hydrogen bond donors within a eutectic solvent, significantly enhance the solvent's efficiency in extracting metal ions. Conversely, when the alcohol acts as a hydrogen bond acceptor, its extraction properties diminish. Molecular modelling reveals that the extraction efficiency of these alcohols is directly proportional to the intermolecular interaction energy between the components of the eutectic solvent. [ABSTRACT FROM AUTHOR]

In the prodrug-based self-assembled nanoassemblies, prodrugs usually consist of drug modules, response modules, and modification modules. Modification modules play a critical role in regulating the nano-assembly ability of the prodrugs. Herein, we carried out a "fatty alcoholization" strategy and chose various lengths of aliphatic alcohol chains (AC) as modification modules to construct disulfide bond bridged paclitaxel (PTX) prodrug nanoassemblies. The PTX-AC prodrugs would self-assemble into nanoassemblies (PTX-AC PNs) with higher drug loading, stability, and tumor selectivity than commercial preparations. After comprehensive exploration, we found the chain length (AC 12 , AC 16 , AC 20 , AC 24) of modification modules affected the assembly of PTX-AC PNs, further leading to disparate in vivo fate and antitumor efficacy. With the increase of the chain length of the modification modules (from AC 12 to AC 20), the assembly ability of the nanoassemblies was improved, attributed to the appropriate enhancement of hydrophobic force. When the chain length was further increased to AC 24 , the excessive hydrophobic force will lead to the aggregation of prodrugs and weaken the assembly ability. Therefore, PTX-AC 20 PNs with proper chain length may solve the paradox of efficacy and tolerance in 4 T1 breast tumor owing to their optimal nano-assembly stability and modest redox-sensitivity. In short, this work highlighted the importance of screening optimal modification modules in developing prodrug nanoassemblies. PTX-AC 20 with modest chain length of modification modules stood out for the superior self-assemble ability, modest redox-sensitivity, and favorable tolerance. [Display omitted] • The "fatty alcoholization" strategy was endowed PTX with self-assembly ability. • The role of modification modules in PTX prodrug nanoassemblies was clarified. • The optimal chain length was modest in constructing PTX prodrug nanoassemblies. • PTX-AC 20 PNs with proper chain length outperformed in efficacy and tolerance. [ABSTRACT FROM AUTHOR]

Two oxidovanadium(IV) complexes [VO(xbp‐sc)] (1) and [VO(xbp‐tc)] (2) were prepared using hydrazine‐ether mixed functionality ligands Hxbp‐sc (I) and Hxbp‐tc (II), respectively. Complexes 1 and 2 were carefully grafted separately into imidazole‐modified chloromethylated polystyrene (Ps−Im) and unmodified chloromethylated polystyrene (PS−Cl) beads. Successfully anchored vanadium complexes Ps−Im‐[VO(xbp‐sc)] (3), Ps−Im‐[VO(xbp‐tc)] (4), Ps‐[VO(xbp‐sc)] (5), and Ps‐[VO(xbp‐tc)] (6) were tested for their catalytic potential towards the oxidation of aliphatic alcohols in the presence of hydrogen peroxide. Polymer‐grafted catalysts display excellent substrate conversion compared to most recent reports and good recyclability up to three cycles without losing much reactivity. High TOF values in the range of 183–591 h−1 are observed for the supported catalysts 3–6. The highest substrate conversion is observed for ethanol (63–97 %) under the optimized reaction conditions. Mainly, better substrate conversion is obtained with imidazole‐modified polymer beads grafted catalysts 3 and 4 than those grafted on unmodified polymer beads (5 and 6). Moreover, catalysts with the semicarbazide group in their ligand framework (3 and 5) show better reactivity towards alcohol with fewer carbon atoms. On the contrary, alcohols with longer carbon chains oxidize more easily in the presence of the catalyst with thiosemicarbazide frameworks (4 and 6). [ABSTRACT FROM AUTHOR]

α,ω-Dicarboxylic acids, ω-aminoalkanoic acids, and α,ω-diaminoalkanes are valuable building blocks for the production of biopolyesters and biopolyamides. One of the key steps in producing these chemicals is the oxidation of ω-hydroxycarboxylic acids using alcohol dehydrogenases (e.g., ChnD of Acinetobacter sp. NCIMB 9871). However, the reaction and structural features of these enzymes remain mostly undiscovered. Thereby, we have investigated characteristics of ChnD based on enzyme kinetics, substrate-docking simulations, and mutation studies. Kinetic analysis revealed a distinct preference of ChnD for medium chain ω-hydroxycarboxylic acids, with the highest catalytic efficiency of 18.0 mM−1s−1 for 12-hydroxydodecanoic acid among C6 to C12 ω-hydroxycarboxylic acids. The high catalytic efficiency was attributed to the positive interactions between the carboxyl group of the substrates and the guanidino group of two arginine residues (i.e., Arg62 and Arg266) in the substrate binding site. The ChnD_R62L variant showed the increased efficiency and affinity, particularly for fatty alcohols (i.e., C6–C10) and branched-chain fatty alcohols, such as 3-methyl-2-buten-1-ol. Overall, this study contributes to the deeper understanding of medium-chain primary aliphatic alcohol dehydrogenases and their applications for the production of industrially relevant chemicals such as α,ω-dicarboxylic acids, ω-aminoalkanoic acids, and α,ω-diaminoalkanes from renewable biomass. • ChnD prefers oxidizing longer ω-hydroxycarboxylic acids, particularly 12-hydroxydodecanoic acid. • Carboxyl groups in ω-hydroxycarboxylic acids significantly enhance efficiency by interacting with arginine residue. • The ChnD_R62L variant shows improved efficiency and affinity for fatty and branched-chain alcohols. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides (OPPs) are a group of pesticides that are most widely used in the agricultural sector, and farmers are exposed to these chemicals more than other members of society. In this work, an environmentally friendly, simple, and safe ultrasound-assisted dispersive liquid-liquid microextraction (USA–DLLME) method using alcohol-based hydrophobic deep eutectic solvents (HDESs) followed by gas chromatography-mass spectroscopy (GC–MS) was developed for the extraction and determination of OPPs in the blood of farmers studied in Ravansar cohort. DESs synthesized from thymol as hydrogen bond donor (HBD) and aliphatic alcohols as hydrogen bond acceptor (HBA) have been used as extractants. Under optimal experimental conditions, the reproducibility of the method based on 7 replicate measurements of 10 µg L−1 of OPPs in blood samples was in the range of 1.4–3.8%. The method showed a linearity in the range of 0.01–150 µg L−1. The limits of detection and limits of quantification were between 0.003 and 0.02 µg L−1 and 0.01–0.05 µg L−1, respectively. The matrix effect and accuracy of the method were confirmed by spiking different amounts of OPPs in real blood samples and obtaining relative recoveries in the range of 91–112%. The results showed that the concentration of OPPs in the case group was significantly higher than in the control group, which is because the case group was exposed to OPPs during the spraying of agricultural products. [ABSTRACT FROM AUTHOR]

Transition metal–catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp3)–O functionalization step have precluded general methods. Here, we describe computationally guided transition metal–ligand design that positions a hydrogen-bond acceptor anion at the reactive site to promote functionalization. A general cross-coupling of primary, secondary, and tertiary aliphatic alcohols with terminal olefins to furnish >130 ethers is achieved. The mild conditions tolerate functionality that is prone to substitution, elimination, and epimerization and achieve site selectivity in polyol settings. Mechanistic studies support the hypothesis that the ligand’s geometry and electronics direct positioning of the phosphate anion at the π-allyl-palladium terminus, facilitating the phosphate’s hydrogen-bond acceptor role toward the alcohol. Ligand-directed counteranion positioning in cationic transition metal catalysis has the potential to be a general strategy for promoting challenging bimolecular reactivity. [ABSTRACT FROM AUTHOR]

Hierarchical Co3O4/triple-shelled carbon nitride (Co3O4/TSCN) composite nanocapsules were designed via a multi-step procedure in a controlled manner as a solar-light-driven photocatalyst based Z-scheme system for selective aerobic photooxidation of alcohols (primary and secondary aliphatic and benzylic) to corresponding aldehydes/ or ketones in green media. The structure of the as-prepared photocatalyst was characterized by a series of measurement techniques including FT-IR, XRD, BET, TEM, FE-SEM, EDX, EDX-mapping, TGA, UV–vis DRS, and ICP-OES. The hierarchical Co3O4/TSCN composite nanocapsules demonstrated superior photocatalytic activity in selective aerobic oxidation of alcohols under solar light irradiation in comparison to pure TSCN and Co3O4 NPs. The shell number of the composite nanocapsules and the formation of the hierarchical Co3O4/TSCN Z-scheme photocatalyst can significantly affect the photocatalytic activity. The results indicate the efficient electron transfer, relatively high specific surface area, high donor density, and low band gap as well as the coexistence of micro-, meso- and macropores and also nano-sized crystalline structure (from 1.2 to 95 nm) in heterojunction composite. This novel photocatalytic system kept relatively high catalytic activity after five recycle runs under the same reaction conditions. [ABSTRACT FROM AUTHOR]

Even though industrial biotechnology is successfully used for the production of some chemicals, for many other chemicals it is not yet competitive with conventional petrochemical production. Usually, fermentation as well as downstream processing requires improvement. Downstream processing has to deal with low product concentrations, microorganisms, impurities and thermodynamic constraints (e.g., azeotropes), which often makes it very challenging and expensive, especially on a large scale. However, downstream processing of biochemicals has not attracted as much attention as upstream fermentation processes. In that context, this perspective paper offers a lightly referenced scholarly opinion about the downstream processing performance of different bioalcohols after fermentation. Due to the stronger toxicity effects on microbes, the achievable concentrations of monohydric aliphatic alcohols in the fermentation broth decrease with the increasing chain length. Specifically, the concentrations used here are 6.14, 5.00, 1.61 and 0.24 wt% of ethanol, isopropanol, isobutanol and hexanol, respectively. More dilute fermentation broths lead to more complex recovery processes. According to our previous work, the total purification costs increase from 0.080 USD kg−1 for ethanol, 0.109 USD kg−1 for isopropanol and 0.161 USD kg−1 for isobutanol to 0.529 USD kg−1 for hexanol. A similar trend is noticeable for the energy usage (0.960, 1.348, 2.018 and 3.069 kWthh kg−1, respectively) and the related CO2 emissions (0.164, 0.221, 0.449 and 0.555 kgCO2 kg−1, respectively). This work shows that advanced separation and purification based on process intensification principles are crucial for overall efficient production processes. The achievable product concentration in the fermentation broth – and not so much the alcohol chain length – has the biggest influence on the performance of downstream processing. Therefore, simultaneous development of both upstream and downstream processing is necessary to ensure the competitiveness and viability of industrial fermentation processes. © 2024 The Author(s). Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

The conceptual merger of relay catalysis with dynamic kinetic resolution strategy is reported to enable regio‐ and enantioselective C(sp3)‐H bond arylation of aliphatic alcohols, forming enantioenriched β‐aryl alcohols typically with >90 : 10 enantiomeric ratios (up to 98 : 2 er) and 36–74 % yields. The starting materials bearing neighbouring stereogenic centres can be converted to either diastereomer of the β‐aryl alcohol products, with >85 : 15 diastereomeric ratios determined by the catalysts. The reactions occur under mild conditions, ensuring broad compatibility, and involve readily available aryl bromides, an inorganic base, and commercial Ru‐ and Pd‐complexes. Mechanistic experiments support the envisioned mechanism of the transformation occurring through a network of regio‐ and stereoselective processes operated by a coherent Ru/Pd‐dual catalytic system. [ABSTRACT FROM AUTHOR]

Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities. [ABSTRACT FROM AUTHOR]

Chiral secondary alcohols, serving as essential structural motifs, hold significant potential for diverse applications. The exploration of effective synthetic strategies toward these compounds is both attractive and challenging. Herein, we present an asymmetric oxa‐Michael reaction involving aliphatic alcohols as nucleophiles and β‐fluoroalkyl vinylsulfones catalyzed by bifunctional phosphonium salt (BPS), achieving high yields and excellent enantioselectivities (up to 98 % yield and 98 % ee). Additionally, a sequential process including asymmetric oxa‐Michael and debenzylation, facilitated by BPS/Lewis acid cooperation, was revealed for synthesizing diverse chiral secondary alcohol compounds in high yields (81–88 %) with consistent stereoselectivities. Furthermore, mechanistic explorations and subsequent results unveiled that the enantioselectivity originates from hydrogen‐bonding and ion‐pair interactions between the BPS catalyst and the substrates. [ABSTRACT FROM AUTHOR]

Silyl ethers fulfil a fundamental role in synthetic organic chemistry as protecting groups and their selective cleavage is an important factor in their application. We present here for the first time two enzymes, SilE−R and SilE−S, which are able to hydrolyse silyl ethers. They belong to the stress‐response dimeric A/B barrel domain (DABB) family and are able to cleave the Si−O bond with opposite enantiopreference. Silyl ethers containing aromatic, cyclic or aliphatic alcohols and, depending on the alcohol moiety, silyl functions as large as TBDMS are accepted. The X‐ray crystal structure of SilE−R, determined to a resolution of 1.98 Å, in combination with mutational studies, revealed an active site featuring two histidine residues, H8 and H79, which likely act synergistically as nucleophile and Brønsted base in the hydrolytic mechanism, which has not previously been described for enzymes. Although the natural function of SilE−R and SilE−S is unknown, we propose that these 'silyl etherases' may have significant potential for synthetic applications. [ABSTRACT FROM AUTHOR]

In this study, Fe3O4 nanoparticles (FeNPs) decorated with halogenated perylene diimides (PDIs) have been used for capturing VOCs (volatile organic compounds) through noncovalent binding. Concretely, we have used tetrachlorinated/brominated PDIs as well as a nonhalogenated PDI as a reference system. On the other hand, methanol, ethanol, propanol, and butanol were used as VOCs. Experimental studies along with theoretical calculations (the BP86-D3/def2-TZVPP level of theory) pointed to two possible and likely competitive binding modes (lone pair–π through the π-acidic surface of the PDI and a halogen bond via the σ-holes at the Cl/Br atoms). More in detail, thermal desorption (TD) experiments showed an increase in the VOC retention capacity upon increasing the length of the alkyl chain, suggesting a preference for the interaction with the PDI aromatic surface. In addition, the tetrachlorinated derivative showed larger VOC retention times compared to the tetrabrominated analog. These results were complemented by several state-of-the-art computational tools, such as the electrostatic surface potential analysis, the Quantum Theory of Atoms in Molecules (QTAIM), as well as the noncovalent interaction plot (NCIplot) visual index, which were helpful to rationalize the role of each interaction in the VOC···PDI recognition phenomena. [ABSTRACT FROM AUTHOR]

Nickel‐catalyzed cross‐electrophile coupling reactions of two aliphatic alcohol derivatives remain a challenge. Herein, we report a nickel‐catalyzed reductive methylation reaction of aliphatic mesylates with methyl tosylate. This reaction provides straightforward access to compounds bearing aliphatic methyl groups from alkyl alcohol derivatives. Isotopically labelled substrates and reagents can be employed in the reaction to provide perdeuterated and 13C‐labelled products. This transformation can be achieved by employing stoichiometric Mn reductant or electrochemically. Additionally, mechanistic experiments show that alkyl iodides are key intermediates in the transformation which undergo a stereoablative reaction via radical intermediates. [ABSTRACT FROM AUTHOR]

Policosanol is a mixture of long-chain aliphatic alcohols (LCAAs) derived from various plant and insect origins that are marketed by various companies with distinct formulations and brand names. Policosanols offer several beneficial effects to treat dyslipidemia and hypertension; however, a comprehensive functionality comparison of various policosanol brands has yet to be thoroughly explored. In the present study five distinct policosanol brands from different origins and countries, Raydel-policosanol, Australia (PCO1), Solgar-policosanol, USA (PCO2), NutrioneLife-monacosanol, South Korea (PCO3), Mothernest-policosanol, Australia (PCO4), and Peter & John-policosanol, New Zealand (PCO5) were compared via dietary supplementation (1% in diet, final wt/wt) to zebrafish for six weeks to investigate their impact on survivability, blood lipid profile, and functionality of vital organs under the influence of a high-cholesterol diet (HCD, final 4%, wt/wt). The results revealed that policosanol brands (PCO1–PCO5) had a substantial preventive effect against HCD-induced zebrafish body weight elevation and hyperlipidemia by alleviating total cholesterol (TC) and triglycerides (TG) in blood. Other than PCO3, all the brands significantly reduced the HCD's elevated low-density lipoprotein cholesterol (LDL-C). On the contrary, only PCO1 displayed a significant elevation in high-density lipoprotein cholesterol (HDL-C) level against the consumption of HCD. The divergent effect of PCO1–PCO5 against HCD-induced hepatic damage biomarkers, aspartate aminotransferase (AST) and alanine aminotransferase (ALT), was observed. PCO1, PCO2, and PCO4 efficiently curtailed the AST and ALT levels; however, PCO3 and PCO5 potentially aggravated the HCD's elevated plasma AST and ALT levels. Consistently, the hepatic histology outcome revealed the least effectiveness of PCO3 and PCO5 against HCD-induced liver damage. On the contrary, PCO1 exhibited a substantial hepatoprotective role by curtailing HCD-induced fatty liver changes, cellular senescent, reactive oxygen species (ROS), and interleukin-6 (IL-6) production. Likewise, the histological outcome from the kidney, testis, and ovary revealed the significant curative effect of PCO1 against the HCD-induced adverse effects. PCO2–PCO5 showed diverse and unequal results, with the least effective being PCO3, followed by PCO5 towards HCD-induced kidney, testis, and ovary damage. The multivariate interpretation based on principal component analysis (PCA) and hierarchical cluster analysis (HCA) validated the superiority of PCO1 over other policosanol brands against the clinical manifestation associated with HCD. Conclusively, different brands displayed distinct impacts against HCD-induced adverse effects, signifying the importance of policosanol formulation and the presence of aliphatic alcohols on the functionality of policosanol products. [ABSTRACT FROM AUTHOR]

The traditional methacrylic esterification process, which couples reaction–distillation/rectification, suffers from issues such as prolonged reaction time, high risk of self-polymerization, and low utilization rate of methacrylic acid. By optimizing the esterification reaction of methacrylic acid through reaction–thin film evaporation coupling, compared to the reaction–distillation coupling process, the reaction time could be reduced by 37.50%, the reaction temperature could be lowered by over 15 °C, and the yield of etherification of dodecanol could be decreased by 81.25%, which significantly mitigates the risk of self-aggregation and reduces energy consumption. Furthermore, the feasibility of recovery of methacrylic acid from aqueous phase through extraction with higher aliphatic alcohol was verified, the recovery rate of methacrylic acid could reach above 96.95%, and the extracted phase could be directly utilized for preparing raw material for esterification reaction without requiring further separation steps, which effectively enhances the process economy and atomic utilization. [ABSTRACT FROM AUTHOR]

This work describes a new well-defined, air-stable, phosphine free palladium(II) [Pd(L)Cl] (1) catalyst. This catalyst was utilized for N-alkylation of amines and indole synthesis where H2O was found to be the by-product. A broad range of aromatic amines were alkylated using this homogeneous catalyst with a catalyst loading of 0.1 mol%. Greener aromatic and aliphatic primary alcohols were utilized and a hydrogen auto-transfer strategy via a metal–ligand cooperative approach was investigated. The precursor of the antihistamine-containing drug molecule tripelennamine was synthesized on a gram scale for large-scale applicability of the current synthetic methodology. A number of control experiments were performed to investigate the possible reaction pathway and the outcomes of these experiments indicated the azo-chromophore as a hydrogen reservoir during the catalytic cycle. [ABSTRACT FROM AUTHOR]

This article explores the nickel-catalyzed transesterification of methyl esters, which is an important process in synthetic chemistry. The authors discuss the challenges of activating esters for cross-coupling reactions and the development of a reversible transformation using a nickel catalyst and SIPr. They also investigate the optimization of the reaction and the identification of effective ligands for different types of esters. The goal is to develop a transesterification method that is different from traditional acid- and base-mediated pathways. The article presents the development of a catalytic transesterification reaction using methyl esters and aliphatic alcohols, with optimized conditions and successful formation of diverse esters. The reaction is advantageous because it only produces methanol as waste and does not require the use of acids or bases. Mechanistic studies suggest that the cleavage of the C(acyl)-O bond is reversible, and ongoing research is being conducted on the use of methyl esters as cross-coupling electrophiles. [Extracted from the article]

Direct catalytic methanol fuel cells (DCMFCs) have been studied for several years for energy conversion. Less extensive is the investigation of their analytical properties. In this paper, we demonstrate that the behavior of both the discharge and charger curves of DCMFCs depends on the chemical composition of the solution injected in the fuel cell. Their discharge and charge curves, analyzed using a chemometric data fusion method named ComDim, enable the identification of various types of aliphatic alcohols diluted in water. The results also show that the identification of alcohols can be obtained from the first portion of the discharge and charge curves. To this end, the curves have been described by a set of features related to the slope and intercept of the initial portion of the curves. The ComDim analysis of this set of features shows that the identification of alcohols can be obtained in a time that is about thirty times shorter than the time taken to achieve steady-state voltage. [ABSTRACT FROM AUTHOR]

In the research presented herein, low-valent-tungsten-catalyzed hydroboration of esters and nitriles was investigated. Aromatic and aliphatic substrates were smoothly reduced to corresponding alcohol derivatives and N,N-diborylamines in the presence of W(CO)4(NCMe)2. Valuable derivatives were conveniently accessed by introducing a further functionalization process to crude hydroboration mixtures in one pot. [ABSTRACT FROM AUTHOR]

In this study, we have investigated the potential use of post-consumer primary lithium metal batteries (LMBs) commonly used in portable electronic devices to recover lithium and manganese in the form of industrially important materials. A direct reaction of lithium-containing electronic waste with a naturally sourced ester, methyl salicylate, combined with a wide range of aliphatic alcohols has been used as a general method for recovering lithium in the form of lithium aryloxides of different nuclearities [Li(OAr)(HOMe)2] (1), [Li(OAr)(HOAr)] (2), [Li(OAr)(HOEt)]2 (3), [Li(OAr)(H2O)]2 (4), [Li4(OAr)4(EGME)2] (5), [Li6(OAr)6] (6-8) for ArOH = methyl salicylate (1, 2, 4, 6), ethyl salicylate (3, 7), 2-methoxyethyl salicylate (5, 8), and EGME = 2-methoxyethanol. The hydrolysis of 7was then used to synthesize lithiumsalicylate [Li(Sal)(H2O)]n (10), which is an important antioxidant in the production of oils and grease. The discharged cathode material of Li-MnO2 batteries was investigated as a source from which LiClO4, Li2 CO3, LiMn2O4, and Mn2O3 can be recovered by means of water-alcohol extraction or calcination. Particular emphasis was placed on the detailed characterization of all battery components and their decomposition products. LMBs were completely recycled for the first time, and materials were recovered from the cathode and the anode. [ABSTRACT FROM AUTHOR]

One new aliphatic alcohol glycoside (1), together with eight known compounds (2-9) were isolated from the whole plant of Lomatogonium rotatum (L.) Fr. Their structures were established from spectroscopic data (1D, 2D NMR, and HR-ESI-MS) and comparison with the literature. Among them, compounds 2, 3 and 8, 9 were reported from the Gentianaceae family for the first time, compounds 4–7 had not been reported previously from the genus Lomatogonium. [ABSTRACT FROM AUTHOR]

Bactrocera tryoni (Froggatt) and Bactrocera neohumeralis (Hardy) are sibling fruit fly species that are sympatric over much of their ranges. Premating isolation of these close relatives is thought to be maintained in part by allochrony—mating activity in B. tryoni peaks at dusk, whereas in B. neohumeralis , it peaks earlier in the day. To ascertain whether differences in pheromone composition may also contribute to premating isolation between them, this study used solid-phase microextraction and gas chromatography-mass spectrometry to characterize the rectal gland volatiles of a recently collected and a more domesticated strain of each species. These glands are typical production sites and reservoirs of pheromones in bactrocerans. A total of 120 peaks were detected and 50 were identified. Differences were found in the composition of the rectal gland emissions between the sexes, species, and recently collected versus domesticated strains of each species. The compositional variation included several presence/absence and many quantitative differences. Species and strain differences in males included several relatively small alcohols, esters, and aliphatic amides. Species and strain differences in females also included some of the amides but additionally involved many fatty acid esters and 3 spiroacetals. While the strain differences indicate there is also heritable variation in rectal gland emissions within each species, the species differences imply that compositional differences in pheromones emitted from rectal glands could contribute to the premating isolation between B. tryoni and B. neohumeralis. The changes during domestication could also have significant implications for the efficacy of Sterile Insect Technique control programs. [ABSTRACT FROM AUTHOR]

Despite the importance of heteroatom‐substituted cyclopropane derivatives in drug design and organic synthesis, cyclopropanethiols remain critically underexplored. Inspired by the wide use of the Newman‐Kwart rearrangement to access valuable thiophenols from phenol feedstocks, we report the development of a photocatalytic approach for efficient ambient temperature aliphatic O‐ to S‐rearrangement on tertiary cyclopropanol derivatives. After demonstrating that a range of cyclopropanethiols—that are difficult to access by other methods—can be obtained with this strategy, we show that these rearranged products can be easily hydrolyzed and further derivatized. We conclude this study with mechanistic findings that enabled an initial extension of this approach toward other classes of aliphatic alcohols. [ABSTRACT FROM AUTHOR]

Radical difunctionalization of aliphatic alkynes provides direct access to valuable multi‐substituted alkenes, but achieving a high level of chemo‐ and stereo‐control remains a formidable challenge. Herein a novel photoredox neutral alkyne di‐functionalization is reported through functional group migration followed by a radical‐polar crossover and energy transfer‐enabled stereoconvergent isomerization of alkenes. In this sequence, a hydroxyalkyl and an aryl group are incorporated concomitantly into an alkyne, leading to diversely functionalized E‐allyl alcohols. The scope of alkynes is noteworthy, and the reaction tolerates aliphatic alkynes containing hydrogen donating C─H bonds that are prone to intramolecular hydrogen atom transfer. The protocol features broad functional group compatibility, high product diversity, and exclusive chemo‐ and stereoselectivity, thus providing a practical strategy for the elusive radical di‐functionalization of unactivated alkynes. [ABSTRACT FROM AUTHOR]

The construction of C(sp3)–heteroatom bonds represents a fundamental research field in synthetic chemistry. We report herein an electrochemical dehydroxymethylative functionalization reaction of aliphatic alcohols under mild and catalyst-free conditions, representing a new paradigm for forging various C(sp3)–heteroatom bonds between diverse alkanols and N- or O-centered nucleophiles. In addition, detailed mechanistic investigations have been carried out, revealing that these reactions proceed through a β-scission/anodic oxidation/nucleophilic addition sequence. [ABSTRACT FROM AUTHOR]

The vegetation of the Canary Islands is characterized by a large number of endemic species confined to different altitudinal levels. It can be assumed that these circumstances determine the characteristic features of the chemical composition of local beekeeping products, including propolis. We report, for the first time, the chemical composition of propolis from Tenerife (Canary Islands). The volatile emissions of three propolis samples collected from different apiaries are represented by 162 C1–C20 compounds, of which 144 were identified using the HS-SPME/GC-MS technique. The main group of volatiles, consisting of 72 compounds, is formed by terpenoids, which account for 42–68% of the total ion current (TIC) of the chromatograms. The next most numerous groups are formed by C6–C17 alkanes and alkenes (6–32% TIC) and aliphatic C3–C11 carbonyl compounds (7–20% TIC). The volatile emissions also contain C1–C6 aliphatic acids and C2–C8 alcohols, as well as their esters. Peaks of 138 organic C3–C34 compounds were recorded in the chromatograms of the ether extracts of the studied propolis. Terpene compounds form the most numerous group, but their number and content in different samples is within very wide limits (9–63% TIC), which is probably due to the origin of the samples from apiaries located at different altitudes. A peculiarity of the chemical composition of the extractive substances is the almost complete absence of phenylcarboxylic acids and flavonoids, characteristic of Apis mellifera propolis from different regions of Eurasia and North America. Aromatic compounds of propolis from Tenerife are represented by a group of nine isomeric furofuranoid lignans, as well as alkyl- and alkenyl-substituted derivatives of salicylic acid and resorcinol. [ABSTRACT FROM AUTHOR]

We report a study on the hydrogen bonding mechanisms of three aliphatic alcohols (2-propanol, methanol, and ethanol) and one diol (ethylene glycol) in water solution using a time-domain ellipsometer in the THz region. The dielectric response of the pure liquids is nicely modeled by the generalized Debye–Lorentz equation. For binary mixtures, we analyze the data using a modified effective Debye model, which considers H-bond rupture and reformation dynamics and the motion of the alkyl chains and of the OH groups. We focus on the properties of the water-rich region, finding anomalous behavior in the absorption properties at very low solute molar concentrations. These results, first observed in the THz region, are in line with previous findings from different experiments and can be explained by taking into account the amphiphilic nature of the alcohol molecules. [ABSTRACT FROM AUTHOR]

Homogeneous and heterogeneous reactions wherein the resulting products remain dissolved in solvents generally require complicated separation and purification process, despite the advantage of heterogeneous systems allowing retrieval of catalysts. Herein, we have developed an efficient approach for the one‐pot tandem synthesis of quinazolines, quinazolinones and benzothiadiazine 1,1‐dioxides from alcohols and amines utilizing a bifunctional bipyridinium photocatalyst with redox and Lewis acid sites using air as an oxidant. Through solvent‐modulation strategy, the photocatalytic system exhibits high performance and enables most products to separate spontaneously. Consequently, the homogeneous catalyst can be reused by direct centrifugation isolation of the products. Notably, the method is also applicable to the less active substrates, such as heterocyclic alcohols and aliphatic alcohols, and thus provides an efficient and environmentally friendly photocatalytic route with spontaneous separation of N‐heterocycles to reduce production costs and meet the needs of atomic economy and green chemistry. [ABSTRACT FROM AUTHOR]

A highly efficient, heterogeneous copper(I)-catalyzed aerobic oxidation of primary aliphatic, allylic, propargylic and benzylic alcohols to aldehydes has been achieved under open-air and base-free conditions in MeCN at room temperature in the presence of 3 mol% of 1,1-di(pyridin-2-yl)urea-functionalized SBA-15-anchored copper iodide complex [Dpu-SBA-15-CuI] and 4 mol% of TEMPO, delivering a wide range of the corresponding aliphatic, α,β-unsaturated and aromatic aldehydes in good to excellent yields. This new heterogeneous copper(I) complex can be easily prepared via a simple procedure from readily available and inexpensive reagents and recycled at least ten times without any remarkable loss of activity. The use of reusable copper catalyst and air as the oxidant, as well as mild and base-free conditions make this protocol attractive for environmentally sustainable processes. A highly efficient, heterogeneous copper(I)-catalyzed aerobic oxidation of primary aliphatic, allylic, propargylic and benzylic alcohols to aldehydes under open-air and base-free conditions is described. [ABSTRACT FROM AUTHOR]

Large natural magnesium resources, consisting primarily of magnesium chloride hexahydrate, are being wasted and not used efficiently in certain areas of the world. With the shortage of aluminum and iron resources, the transformation of natural magnesium resources into products has become a challenging task. Ethanol, a lower, saturated monohydric aliphatic alcohol known for being green, non-toxicity, and capable of dissolving magnesium chloride hexahydrate, offers a potential solution. This paper focuses on introducing magnesium chloride hexahydrate into ethanol and investigating the recovered samples from the magnesium chloride-ethanol solution by isothermal evaporation at different temperatures, to explore the possibility of extracting magnesium chloride hexahydrate from magnesium salt minerals using ethanol. Results showed that magnesium chloride hexahydrate can be completely recovered at 130 °C. The composition of the recovered sample is mainly magnesium chloride hexahydrate. The good thermal stability is due to high crystallinity and the existence of a strong coordination bond of ethanol in the magnesium chloride crystal structure. All recovered samples have a high current density in ethanol. This research shows that introducing magnesium salt minerals into ethanol to extract magnesium chloride hexahydrate can be a viable option for recycling natural magnesium resources. [ABSTRACT FROM AUTHOR]

The present study elucidates the oxidation of alcohols to terpene ketones using dichloro(p-cymene) ruthenium (II) dimer catalyst by continuous flow process using a metal plate reactor. The synthesized products were separated and validated using GC, GCMS, 1H-NMR, and 13C-NMR techniques. The reaction process exhibited product yield in the range of 80-95% on a scale of 1-80 grams. Optimization studies were conducted to calibrate the reaction conditions to improve the product yield. The scope of the reaction was explored using aromatic, cyclic, and aliphatic alcohols under optimized conditions, which resulted in high yields of terpene ketones. A reaction mechanism is proposed for the oxidation of alcohols by a continuous flow process. The significant advantages of the current protocol include synthesis at mild conditions, safer handling of reagents, flexibility to tune reaction conditions, and straightforward scale-up in the range of 1-80 grams with high efficiency and reproducibility. [ABSTRACT FROM AUTHOR]

Small-molecule prodrug nanoassemblies have emerged as efficient antitumor drug delivery systems. However, in the case of camptothecins-based prodrug nanoassemblies, linear aliphatic side chain modification often results in rod-shaped or irregularly shaped nanoassemblies, which are highly unfavorable for sterilization through filtration, and may cause capillary blockage upon intravenous injection. The rational design of camptothecins-based prodrug nanoassemblies remains a challenge. Herein, we propose that branched aliphatic alcohol (BAA) functionalization could fine-tune the structure-tolerance-antitumor efficacy axis of prodrug nanoassemblies. Correspondingly, four SN38-BAA prodrugs were synthesized by conjugating 7-ethyl-10-hydroxycamptothecin (SN38) with BAAs of varying lengths via a tumor redox-responsive disulfide bond, which self-assemble into uniform spherical nanoparticles. The length of BAA was found to significant impact the multiple drug delivery process, including colloidal stability, drug release profiles and pharmacokinetics. Overall, SN38-C21 NPs (SN38-11-heneicosanol nanoparticles), featuring the longest BAA, showcased multiple therapeutic advantages, ultimately culminating the optimal antitumor efficacy and tolerance. The findings underscore the potential of BAA functionalization in strengthening the therapeutic outcomes of prodrug nanoassemblies, and provide valuable insights for developing translational camptothecins-based nanomedicines. [ABSTRACT FROM AUTHOR]

Two new oxidovanadium(IV) complexes [CH2{VIVO(sal-sc)}2]·SO4 (1) and [CH2{VIVO(sal-tc)}2]·SO4 (2) and dioxidovanadium(V) complexes K2[CH2{VVO2(sal-sc)}2] (3) and K2[CH2{VVO2(sal-tc)}2] (4) were synthesised. Thoroughly characterized dioxidovanadium(V) complexes 3 and 4 were covalently grafted on the nano-surface of graphene oxide and heterogeneous catalysts GO-[CH2{VVO2(sal-sc)}2] (5) and GO-[CH2{VVO2(sal-tc)}2] (6) were isolated. Both the supported catalysts 5–6 efficiently catalyzed a series of straight-chain primary aliphatic alcohols and cyclic secondary aliphatic alcohols in the presence of H2O2 without any additional solvent. Straight-chain primary alcohols show better reactivity than cyclic secondary alcohols. Moreover, the alcohols with fewer carbon atoms are more reactive, and reactivity decreases with increasing carbon chain length of the alcohols. With 96% and 92% substrate conversion in the presence of 5 and 6, respectively, ethanol showing the highest reactivity among the examined alcohols. All the listed primary aliphatic alcohols exhibit more than 65% substrate conversion. Irrespective of the substrate 5 shows better performance than 6. The catalytic reaction proceeds through a radical mechanism wherein the in situ generated reactive species CH2{VVO(O)2(sal-sc)}2].MeOH detected through HR-MS analysis is believed to be the active component responsible for the oxidation of the alcohols. [ABSTRACT FROM AUTHOR]

A protocol for efficient N-alkylation of benzamides with alcohols in the presence of cobalt-nanocatalysts is described. Key to the success of this general methodology is the use of highly dispersed cobalt nanoparticles supported on carbon, which are obtained from the pyrolysis of cobalt(II) acetate and o-phenylenediamine as a ligand at suitable temperatures. The catalytic material shows a broad substrate scope and good tolerance to functional groups. Apart from the synthesis of a variety of secondary amides (>45 products), the catalyst allows for the conversion of more challenging aliphatic alcohols and amides, including biobased and macromolecular amides. The practical applicability of the catalyst is underlined by the successful recycling and reusability. [ABSTRACT FROM AUTHOR]

Supercritical carbon dioxide (SC-CO2) extraction of policosanol (PC) from grape marc was investigated for the first time. Employing the broken plus intact cells (BIC) model (Sovová's model) the investigation focused on analyzing the SC-CO2 process to extract the nonpolar fraction from grape marc efficiently. Operating conditions for SC-CO2 extraction—280 bar pressure, 70 °C temperature, and a flow rate of 10 kgCO2/h—yielded the highest policosanol content. The extracted policosanol ranged between 3922 and 4083 mg/kgDM, constituting approximately 8 % of the total extraction yield. Surprisingly, this amount of PC was of the same order of magnitude found in beeswax yellow, a well-known rich natural source of PC. The primary aliphatic alcohols found in the PC from grape marc were hexacosanol, octacosanol, and triacontanol. These findings were consistent with grape marc samples from other Italian regions. Furthermore, a comparative analysis between SC-CO2 and Soxhlet extraction methods for PC was carried out.