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Solvent system selection based on polarity is a common strategy in a countercurrent chromatography (CCC) analysis. However, the solvent selectivity of solvent system is often ignored, despite its significant impact on the separation efficiency of CCC. In this study, the role of solvent in the overall properties of solvent system and the selective classification of solvent system were discussed to improve the solvent system selection based on polarity. Firstly, the mathematical relationship between logarithm of the partition coefficient (log K) of the template molecule and solvent composition of n-hexane/ethyl acetate/alcohol solvents (methanol, ethanol, and isopropanol)/water (HEAwat) system was analyzed and the optimal solvent system (K = 1) of the template molecules was determined. Then, the actual methanol concentration at the column inlet when the analyte peak in a HPLC analysis (B%) and the clustering results of the average polarity (P') of the optimal CCC solvent system were analyzed. Finally, the classification of HEAWat system in terms of its overall solvent properties by deducing equations of selectivity parameters (χ e , χ d , and χ n ) to explain the P' values clustering results. The results showed that HEAWat system was suitable for the separation of analytes with 55 % < B% < 100 %. However, the n-hexane/ethyl acetate/isopropanol/water (HEIWat) system proved more suitable for the separation of large polar compounds to other HEAWat system when the P' value decreased due to the change of alcohol solvents. The selected solvent systems were classified into group III and IV by Snyder's method. The solvent systems in group III were suitable for the separation of analytes with 85 % < B% < 100 %, and the distribution behavior of analytes was mainly influenced by the ratio of each solvent. The solvent systems in group IV were suitable for the separation of analytes with 55 % < B% < 85 %, and the distribution behavior of analytes was mainly influenced by the type of alcohol solvents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study investigated the adsorption mechanisms in a normal-phase system using a cyano-based stationary phase as the sorbent. The minor disturbance method was used to measure the adsorption isotherms of acetone and alcohols with various structures. Excluding data in pure n-hexane revealed that the adsorption behaviors on cyano sites were well described by the Langmuir model. The adsorption equilibrium constants, ranging from 8.86 to 11.15 at 25 °C, showed no significant differences across alcohol structures and decreased with increasing temperature. The saturation adsorption concentration decreased with increasing alcohol molecule size, with branched-chain alcohols showing a lower saturation adsorption amount compared to straight-chain alcohols. The standard state adsorption enthalpies and entropies calculated from the equilibrium constants for various alcohols ranged from -29 to -22 kJ/mol and -78 to -55 J/K·mol, respectively, showing enthalpy-entropy compensation. A discrepancy was observed between these adsorption enthalpies and those obtained from the retention factors of alcohols using pure n-hexane as the mobile phase. This discrepancy may result from the affinity energy distribution of the adsorbent. In pure n-hexane, the adsorption behaviors of adsorbates were considerably affected by high-affinity sites. Moreover, acetone and these alcohol molecules were used as solvent modifiers to investigate the relationship between the retention factor, modifier concentration, and temperature for various solutes with distinct functional groups. The retention curves were converted to enthalpic curves using the van't Hoff equation. A theoretical model was proposed to describe the relationship between the van't Hoff enthalpy change and mobile phase composition. The proposed model effectively described the enthalpic curves, indicating that the enthalpy change follows a saturation curve with increasing modifier concentration. This trend is primarily due to competitive adsorption and complexation behaviors between the solute and modifier molecules., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: The potency of anesthetics with various structures increases exponentially with lipophilicity, which is the Meyer-Overton (MO) correlation discovered over 120 years ago. The MO correlation was also observed with various biological effects and chemicals, including alcohols; thus, the correlation represents a fundamental relationship between chemicals and organisms. The MO correlation was explained by the lipid and protein theories, although the principle remains unknown because these are still debating., Methods: The gentle hydration method was used to form giant unilamellar vesicles (GUVs) consisting of high- and low-melting phospholipids and cholesterol in the presence of n-alcohols (C 2 -C 12 ). Confocal fluorescence microscopy was used to determine the percentage of GUVs with domains in relation to the n-alcohol concentrations., Results: n-Alcohols inhibited the domain formation of GUVs, and the half inhibitory concentration (IC 50 ) in the aqueous phase (C w ) decreased exponentially with increasing chain length (lipophilicity). In contrast, the membrane concentrations (C m ) of alcohols for the inhibition, which is a product of the membrane-water partition coefficient and the IC 50 values, remained constant irrespective of the chain length., Conclusions: The MO correlation is established in GUVs, which supports the lipid theory. When alcohols reach the same critical concentration in the membrane, similar biological effects appear irrespective of the chain length, which is the principle underlying the MO correlation., General Significance: The protein theory states that a highly lipophilic compound targets minor membrane proteins due to the low C w . However, our lipid theory states that the compound targets various membrane proteins due to the high C m ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Redox non-innocent ligands hold the potential to expand the redox chemistry and activity of transition metal catalysts. The impact of the additional redox chemistry of phenol ligands in oxidation catalysis is explored here in the complex μ-oxido-diiron(III) polypyridyl (1) [(L)Fe(III)(μ-O)Fe(III)(L)](ClO 4 ) 2 (where HL is 2-(((di(pyridin-2-yl)methyl) (pyridin-2-ylmethyl) amino)methyl)phenol) and its tert-butyl substituted analog 2, in which each of the Fe(III) centers is coordinated to a phenolato moiety of the ligand. Complex 1 was shown earlier to catalyse the oxidation of benzyl alcohols to aldehydes with H 2 O 2 . In particular acid was found to accelerate the reactions by removal of a lag period before catalysis initiated. Here, we use reaction monitoring with resonance Raman, UV/vis absorption and EPR spectroscopy to show that under catalytic conditions, i.e. with excess H 2 O 2 , rapid (< 5 s) loss of the phenolato moiety occurs, resulting in the formation of an N4 ligated Fe(III) complex. This N4 coordinated complex forms a Fe(III)-OOH species, which is responsible for alcohol oxidation and over time a relatively stable oxido-bridged dinuclear Fe(III) complex forms as a resting state in the catalytic system. The main role of acid in the catalysis is shown to be to facilitate the initial coordination of H 2 O 2 by driving the formation of mononuclear complexes from 1 and 2. The data show that although the phenolato moiety imparts interesting redox properties on complex 1, it does not contribute directly to the oxidation catalysis observed with H 2 O 2 ., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Wesley Browne reports financial support was provided by European Research Council. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

The dynamic combination of aromas and cyclodextrins is an important means to achieve their stability and controllability, and accurately revealing their interaction rules is the key to designing and constructing high-quality aroma nanocarriers. In this study, the inclusion mechanism between alcohol aroma compounds with different structures and β-cyclodextrin (β-CD) was studied by combining molecular dynamics simulation and experimental methods. Results showed that the selected alcohol aroma compounds formed inclusion complexes (ICs) with β-CD in a 1:1 ratio, while alcohol aroma compounds containing cyclic structures were more tightly bound to β-CD. Van der Waals forces were the primary forces driving the formation and stabilization of the ICs. Cinnamyl alcohol/β-CD ICs showed the most significant antimicrobial effect and notably prolonged the shelf life of strawberries. This study aimed to provide theoretical support for precisely designing and preparing highly stable flavours and fragrances, as well as expanding their application range., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this study, a boronic acid incorporated metal organic frameworks (inBA-MIL-100) were prepared via metal-ligand-fragment co-assembly strategy. The prepared frameworks can be served either as enrichment sorbent or SALDI-MS matrix for cis-diol containing molecules. Thus, a dual-modal analysis of cis-diols in traditional Chinese medicine has been established. Several significant advantages of the proposed strategy have been experimentally demonstrated, including high selectivity, high binding capacity (70 mg/g), good generality (5-250 μg/mL for HPLC based sample preparation, 10-500 ng/mL for SALDI-MS), high sensitivity (LOD: 180 ng/mL for HPLC based sample preparation, 5 ng/mL for SALDI-MS) and reliable quantification (RSD<3 % for HPLC based sample preparation, RSD<12 % for SALDI-MS) performance. Finally, the successful analysis of various cis-diols (active component and mycotoxin) in various Chinese traditional medicine was also achieved., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals present in a wide range of commercial and consumer products due to their water-repellency, nonstick, or surfactant properties, resulting from their chemical and thermal stability. This stability, however, often leads to persistence in the environment when they are inevitability released. We utilized microbial microcosms from wastewater treatment plant (WWTP) sludge to determine how employing different functional groups such as heteroatom linkages, varying chain lengths, and hydrofluoroethers (HFEs) will impact the ultimate fate of these novel PFAS structures. A suite of five novel fluorosurfactant building blocks (F 7 C 3 OCHFCF 2 SCH 2 CH 2 OH (FESOH), F 3 COCHFCF 2 SCH 2 CH 2 OH (MeFESOH), F 7 C 3 OCHFCF 2 OCH 2 CH 2 OH (ProFdiEOH), F 7 C 3 OCHFCF 2 CH 2 OH (ProFEOH), and F 3 COCHFCF 2 OCH 2 CH 2 OH (MeFdiEOH)) and their select transformation products, were incubated in WWTP aerobic microcosms to determine structure-activity relationships. The HFE alcohol congeners with a thioether (FESOH and MeFESOH) were observed to transform faster than the ether congeners, while also producing second-generation HFE acid products (F 7 C 3 OCHFC(O)OH (2H-3:2 polyfluoroalkyl ether carboxylic acid [PFECA]) and F 3 COCHFC(O)OH (2H-1:2 PFECA). Subsequent biodegradation experiments with 2H-1:2 PFESA and 2H-1:2 PFECA displayed no further transformation over 74 days. Surface water Photofate experiments compared 2H-1:2 PFECA, and 2H-1:2 polyfluorinated ether sulfonate (PFESA) with their fully fluorinated ether acid counterparts, and demonstrated the potential for both HFE acid species to completely mineralize over extended periods of time, a fate that highlights the value of studying novel PFAS functionalization. Environ Toxicol Chem 2024;43:2297-2305. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

The search for novel synthetic tools to prepare industrial chemicals in a safer and greener manner is a continuing challenge in synthetic chemistry. In this manuscript, we report the discovery, characterization, and synthetic potential of two novel aryl-alcohol oxidases from bacteria which are able to oxidize a variety of aliphatic and aromatic alcohols with efficiencies up to 4970 min -1  mM -1 . Both enzymes have shown a reasonable thermostability (thermal melting temperature values of 50.9 and 48.6 °C for ShAAO and SdAAO, respectively). Crystal structures revealed an unusual wide-open entrance to the active-site pockets compared to that previously described for traditional fungal aryl-alcohol oxidases, which could be associated with differences observed in substrate scope, catalytic efficiency, and other functional properties. Preparative-scale reactions and the ability to operate at high substrate loadings also demonstrate the potential of these enzymes in synthetic chemistry with total turnover numbers > 38000. Moreover, their availability as soluble and active recombinant proteins enabled their use as cell-free extracts which further highlights their potential for the large-scale production of carbonyl compounds. KEY POINTS: • Identification and characterization of two novel bacterial aryl-alcohol oxidases • Crystal structures reveal wide-open active-site pockets, impacting substrate scope • Total turnover numbers and cell-free extracts demonstrate the synthetic potential., (© 2024. The Author(s).)

The reported chemoenzymatic strategy involves the employment of vinyl 3-(dimethylamino)propanoate as an irreversible acyl donor in a chromatography-free lipase-catalyzed kinetic resolution (KR) of racemic sec-alcohols. This biotransformation is achieved in a sequential manner using CAL-B to affect the kinetic resolution, followed by a simple acidic extractive work-up furnishing both KR products with excellent enantioselectivity (E>200; up to 98 % ee). The elaborated method eliminates a single-use silica gel chromatographic separation and significantly reduces organic solvent consumption to foster a more environmentally friendly chemical industry., (© 2024 The Authors. ChemBioChem published by Wiley-VCH GmbH.)

Biocatalysis has emerged as a strong tool for the synthesis of active pharmaceutical ingredients (APIs). In the early twentieth century, whole cell biocatalysis was used to develop the first industrial biocatalytic processes, and the precise work of enzymes was unknown. Biocatalysis has evolved over the years into an essential tool for modern, cost-effective, and sustainable pharmaceutical manufacturing. Meanwhile, advances in directed evolution enable the rapid production of process-stable enzymes with broad substrate scope and high selectivity. Large-scale synthetic pathways incorporating biocatalytic critical steps towards >130 APIs of authorized pharmaceuticals and drug prospects are compared in terms of steps, reaction conditions, and scale with the corresponding chemical procedures. This review is designed on the functional group developed during the reaction forming alcohol functional groups. Some important biocatalyst sources, techniques, and challenges are described. A few APIs and their utilization in pharmaceutical drugs are explained here in this review. Biocatalysis has provided shorter, more efficient, and more sustainable alternative pathways toward existing small molecule APIs. Furthermore, non-pharmaceutical applications of biocatalysts are also mentioned and discussed. Finally, this review includes the future outlook and challenges of biocatalysis. In conclusion, Further research and development of promising enzymes are required before they can be used in industry., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Asymmetric synthesis of chiral chemicals in high enantiomeric excess (ee) is pivotal to the pharmaceutical industry, but classic chemistry usually requires multi-step reactions, harsh conditions, and expensive chiral ligands, and sometimes suffers from unsatisfactory enantioselectivity. Enzymatic catalysis is a much greener and more enantioselective alternative, and cascade biotransformations with multi-step reactions can be performed in one pot to avoid costly intermediate isolation and minimise waste generation. One of the most attractive applications of enzymatic cascade transformations is to convert easily available simple racemic substrates into valuable functionalised chiral chemicals in high yields and ee. Here, we review the three general strategies to build up such cascade biotransformations, including enantioconvergent reaction, dynamic kinetic resolution, and destruction-and-reinstallation of chirality. Examples of cascade transformations using racemic substrates such as racemic epoxides, alcohols, hydroxy acids, etc. to produce the chiral amino alcohols, hydroxy acids, amines, and amino acids are given. The product concentration, ee, and yield, scalability, and substrate scope of these enzymatic cascades are critically reviewed. To further improve the efficiency and practical applicability of the cascades, enzyme engineering to enhance catalytic activities of the key enzymes using the latest microfluidics-based ultrahigh-throughput screening and artificial intelligence-guided directed evolution could be a useful approach., (© 2024 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)

The cuticle is a hydrophobic coating of most aerial plant surfaces crucial for limiting non-stomatal water loss. Plant cuticles consist of the lipid polyester cutin and associated waxes with compositions varying widely between plant species and organs. Here, we aimed to provide a comparative analysis of the dark-glossy adaxial and pale-glaucous abaxial sides of Drimys winteri (Winteraceae) leaves. Scanning electron microscopy showed nanotubular wax crystals lining the entire abaxial side of the leaf (including stomatal pores), while the adaxial side had patches of mixed platelet/tubule crystals and smooth areas between them. Consecutive treatments for wax removal and cutin depolymerization revealed that the waxes were deposited on a cutin network with micron-scale cavities across the entire abaxial surface including the stomata pores, and on a microscopically smooth cutin surface on the adaxial side of the leaf. Gas chromatography coupled to mass spectrometry and flame ionization detection showed that the wax mixtures on both sides of the leaf were complex mixtures of very-long-chain compounds dominated by the secondary alcohol nonacosan-10-ol and alkanediols with one hydroxyl on C-10. It is therefore very likely that the characteristic tubular wax crystals of both leaf sides are formed by these alcohols and diols. Further secondary alcohols and alkanediols, as well as ketols and alkanetriols with one functional group on C-10, were identified based on mass spectral fragmentation patterns. The similarities between all these mid-chain-functionalized compounds suggest that they are derived from nonacosan-10-ol via regio-specific hydroxylation reactions, likely catalyzed by three P450-dependent monooxygenases with different regio-specificities., (© The Author(s) 2024. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists.)

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., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Lignin represents a promising source of renewable energy. The development of CLEO (Cold processed Lignin Ethanol Oil) fuel introduces a novel lignin valorization approach, proposing its potential as maritime biofuel. However, its industrial success depends on enhancing fractionation yields and reducing solvent evaporation, which necessitates a detailed analysis of lignin properties, solvent types, and process parameters. By using novel combinations of biobased solvents, yields improved from 34 wt% to 49-53 wt% by using 30 wt% water or 40 wt% glycerol in ethanol, where Hildebrand Solubility Parameters emerged as indicative tool for increasing yields. Experiments on solid-to-liquid (S:L) ratios revealed a good balance between yield and lignin dispersion concentration at an S:L of 1:2.5. Producing CLEO with an improved solvent composition and S:L ratio resulted in 89 wt% yield while eliminating solvent evaporation requirements. This study highlights the potential for enhancing CLEO production efficiency and advancing it to industrial scale., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Tor Ivan Simonsen reports financial support was provided by The Energy Technology Development and Demonstration Programme. Yohanna Orozco Cabrera has patent #11306264 issued to A.P. MØLLER—MÆRSK A/S, KØBENHAVNS UNIVERSITET., (Copyright © 2024. Published by Elsevier Ltd.)

In this study, based on the self-assembly strategy, we fused CipA with carbonyl reductase LXCAR S154Y derived from Leifsonia xyli by gene coding, and successfully performed the carrier-free immobilization of LXCAR S154Y . The immobilized enzyme was then characterized using scanning electron microscope (SEM), dynamic light scattering (DLS) and fourier transform infrared spectroscopy (FTIR). Compared with the free enzyme, the immobilized LXCAR S154Y exhibited a 2.3-fold improvement in the catalytic efficiency k cat /k m for the synthesis of a chiral pharmaceutical intermediate (R)-3,5-bis(trifluoromethyl)phenyl ethanol ((R)-BTPE) by reducing 3,5-bis(trifluoromethyl)acetophenone (BTAP). Moreover, the immobilized enzyme showed the enhanced stability while maintaining over 61 % relative activity after 18 cycles of batch reaction. Further, when CipA-fused carbonyl reductase was employed for (R)-BTPE production in a continuous flow reaction, almost complete yield (97.0 %) was achieved within 7 h at 2 M (512.3 g/L) of BTAP concentration, with a space-time yield of 1717.1 g·L -1 ·d -1 . Notably, we observed the retention of cofactor NADH by CipA-based enzyme aggregates, resulting in a higher total turnover number (TTN) of 4815 to facilitate this bioreductive process. This research developed a concise strategy for efficient preparation of chiral intermediate with cofactor self-sufficiency via continuous flow biocatalysis, and the relevant mechanism was also explored., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Here, we report a monomer planarity modulation strategy for room-temperature constructing molecularly imprinted-covalent organic frameworks (MI-COFs) for selective extraction of ochratoxin A (OTA). 2,4,6-triformylphloroglucinol (Tp) was used as basic building block, while three amino monomers with different planarity were employed as modulators to explore the effect of planarity on the selectivity of MI-COFs. The MI-TpTapa constructed from Tp and the lowest planarity of monomer Tapa gave the highest selectivity for OTA, and was further used as the adsorbent for dispersed-solid phase extraction (DSPE) of OTA in alcohol samples. Coupling MI-TpTapa based DSPE with high-performance liquid chromatography allowed the matrix-effect free determination of OTA in alcohol samples with the limit of detection of 0.023 μg kg -1 and the recoveries of 91.4-97.6%. The relative standard deviation (RSD, n = 6) of intra and inter day was <3.2%. This work provides a new way to construct MI-COFs for selective extraction of hazardous targets., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

In this study, we utilized 2 H SNIF NMR and chemometric techniques to differentiate the botanical origin of raw materials used in vodka production in Poland, specifically focusing on plants with C 3 metabolism such as grain, potato, and sugar beet. Additionally, for the first time, mixtures of alcohols from different C 3 plants were analysed to detect adulteration. Our goal was to determine if it is possible to detect the addition of a different raw material in vodka made from a mixture of alcohols derived from C 3 plants. Significant isotopic differences were confirmed using analysis of variance and Tukey's tests. Linear relationships in grain-potato, grain-sugar beet, and beet-potato mixtures enabled composition determination. The detectability threshold for adulterants ranged from 10 % to 50 %, depending on the type of raw material. Our findings suggest that 2 H SNIF-NMR is an effective tool for authenticating vodka and detecting adulteration in products marketed as "Polish vodka.", Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The water, alcohols, and their binary mixtures are widely used in molecular simulations. However, the Dreiding force field lacks a generally accepted method for assigning atomic charges to these solvents during simulations. In this study, we propose a universal charge assignment for water and eight water-miscible alcohols in Dreiding. Through extensive molecular simulations, we demonstrate the good accuracy of our charge assignments in displaying characteristic of these solvents and their mixtures, including liquid density and structure. Moreover, we investigate equilibrium snapshot, radial distribution function, coordination number and hydrogen bonding, all of which confirm the miscibility of alcohols with water or ethanol. Notably, we reveal that the structure diversity among different mixtures can be attributed to distinctive characteristic of alcohols, including molecular volume, as well as the number and position of hydroxyls., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

This study reports for the first time the phenomenon of supramolecular solvent formation based on alkyl polyglucoside as an amphiphile and primary alcohol as a coacervation agent. The physical properties (density, kinematic viscosity, phase diagram for ternary system) of the supramolecular solvent were investigated, and a mechanism for its formation was proposed. A green and simple microextraction procedure for preconcentration and determination of phthalates in baby foods packaged in plastic packaging was developed as proof-of-concept example. The microextraction procedure assumed separation of analytes from solid phase sample in micellar solution of decyl glucoside and in situ formation of supramolecular solvent for analytes preconcentration after addition of n-heptanol. The determination of phthalates in obtained extracts was implemented by high-performance liquid chromatography with UV-Vis detection. The limits of detection, calculated from a blank test based on 3σ, were determined to be 10 μg kg -1 for dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, and di-n-octyl phthalate. The developed procedure did not require filtration of sample suspension, and assumed the use of green and biodegradable substances for the supramolecular solvent formation across a wide pH range., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study endeavors to examine the levels of risk factors in alcoholic beverages and propose mitigation strategies. GC-MS analysis was utilized to assess risk factors in various distilled-spirits. The content of such risk factors in spirits ranked as follows: vodka ≈ gin < baijiu < whiskey < brandy, and all were adhering to the Chinese national standard. Additionally, a method was refined to alleviate these risks, employing various reagents for activated carbon modification and evaluating their adsorption efficiency for risk factors reduction. Oxalic acid-modified activated carbon exhibited promising adsorption rates for risk factors with acceptable flavor compounds loss, rendering it a prospective solution for health hazard reduction. Characterization via SEM and nitrogen-adsorption-desorption was conducted on the optimal material, complemented by sensory experiments to optimize its application. This study offers valuable insights into the content of risk factors in alcoholic beverages, aiding in improving quality and safety of alcoholic beverages., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: Most Phalaenopsis cultivars have almost no aroma, with a few exceptions. Phalaenopsis presents significant challenges in fragrance breeding due to its weak aroma and low fertility. It is therefore necessary to identify the aroma components and key regulatory genes in Phalaenopsis cultivars like 'Orange Beauty', 'Brother Sara Gold', 'Purple Martin', 'H026', 'SK16', 'SX098', and 'SH51', to improve the aroma of the common Phalaenopsis., Results: Floral aroma components were tested on nine Phalaenopsis species, using smell identification and headspace gas chromatography-mass spectrometry. The result showed that alcohols, esters, and alkenes were the key specific components in the different species and cultivar aromas and the aroma intensity and component content of cultivars with different colors were different. The main components of the floral aromas in Phalaenopsis were alcohols (including eucalyptol, linalool, citronellol, and 1-hexanol), esters (including hexyl acetate, leaf acetate, and dibutyl phthalate), alkenes (including pinene and sabinene) and arenes (like fluorene). The transcriptome of flowers in the bud stage and bloom stage of P. 'SH51' was sequenced and 5999 differentially expressed genes were obtained. The contributions of the phenylpropionic acid/phenyl ring compound and the terpene compound to the aroma were greater. Sixteen genes related to phalaenopsis aroma were found. TC4M, PAL, CAD6, and HR were related to phenylpropanoid synthesis pathway. SLS, TS10, and P450 were related to the synthesis pathway of terpenes. TS10 and YUCCA 10 were involved in tryptophan metabolism., Conclusion: This is the first report on the floral aroma components and regulatory genes in Phalaenopsis. The proposed method and research data can provide technical support for Phalaenopsis breeding. © 2024 Society of Chemical Industry., (© 2024 Society of Chemical Industry.)

In this work, a microchip gas chromatography (GC) column assembly utilizing a three-dimensional (3D) printed micro oven and a flexible stainless steel capillary column was developed. The assembly's performance and separation capabilities were characterized. The key components include a 3D printed aluminum plate (7.50 × 7.50 × 0.16 cm) with a 3-meter-long circular spiral channel, serving as the oven, and the column coiled on the channel with an inner diameter of 320 μm and a stationary phase of OV-1. A heating ceramic plate was affixed on the opposite side of the plate. The assembly weighed 40.3 g. The design allows for easy disassembly, or stacking of heating devices and columns, enabling flexibility in adjusting column length. When using n-C 13 as the test analyte at 140 °C, a retention factor (k) was 8.5, and 7797 plates (2599 plates/m) were obtained. The assembly, employing resistance heating, demonstrated effective separation performance for samples containing alkanes, aromatics, alcohols and ketones, with good reproducibility. The reduction in theoretical plates compared to oven heating was only 2.95 %. In the boiling point range of C 6 to C 18 , rapid temperature programming (120 °C/min) was achieved with a power consumption of 119.512 W. The assembly was successfully employed to separate benzene series compounds, gasoline and volatile organic compounds (VOCs), demonstrating excellent separation performance. This innovative design addresses the challenges of the complexity and low repeatability of the fabrication process and the high cost associated with microchip columns. Furthermore, its versatility makes it suitable for outdoor analysis applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Alcohols are promising fuels for direct alcohol fuel cells and are common scavengers to identify reactive oxygen species (ROS) in electro-Fenton (EF) systems. However, the side impacts of alcohols on oxygen reduction reactions and ROS generation are controversial due to the complex interactions between electrodes and alcohol-containing electrolytes. Herein, we employed synchrotron-Fourier-transform infrared spectroscopy and electron paramagnetic resonance technologies to directly observe the changes of chemical species and electrochemical properties on the electrode surface. Our studies suggested that alcohols exhibited different limiting degrees on proton (H + ) mass transfer toward the catalytic surface, following an order of methanol < ethanol < isopropanol < tert -butyl alcohol (TBA). In addition, the formation of hydrophobic TBA clusters at high concentrations (>400 mM) resulted in a significant reduction in ionic conductivity and an elevation in charge transfer resistance, which impedes H + mass transfer and raises the energy barrier for 2e - oxygen reduction reaction processes. Moreover, the organic radical • CH 2 (CH 3 ) 2 CH 2 OH produced by the interaction of Fe 3+ and • OH with the alcohol in the EF system serves as a crucial intermediate in facilitating H 2 O 2 regeneration, which complicates the quenching effect of alcohols on • OH identification. Therefore, it is recommended that methanol should be used as the scavenger instead of TBA and the concentration should be less than 400 mM in EF systems.

On-DNA carboxylic acids are important synthetic intermediates in the synthesis of DNA-encoded library (DEL) structures. Herein, we report an oxoammonium salt-mediated, room temperature, solution-phase oxidation of DNA-linked primary alcohols into carboxylic acids. This method exhibits a wide substrate scope, encompassing aliphatic, benzylic, and heterobenzylic alcohols, and is compatible with DEL encoding strategies. This advancement facilitates a DEL strategy to utilize unprotected alcohols as inert, masked carboxylic acids and enables access to noncommercial bifunctional carboxyl intermediates to enhance the accessible chemical diversity within DELs.

Engineering biocatalysts with enhanced stereoselectivity is highly desirable, and active-site loop dynamics play an important role in its regulation. However, knowledge of their precise roles in catalysis and evolution is limited. Here, we used the strategy of Rosetta enzyme design combined molecular dynamic simulations (MDs) to reprogram the landscapes of the key active-site loop dynamics of the carbonyl reductase LfSDR1 to improve stereoselectivity. The key flexible loop in the active site showed the potential to regulate the catalytic properties. A library of virtual variants was produced using the Rosetta design and assessed dynamic effect of the loop with the aid of MDs. A potential candidate was obtained with significant stereoselectivity (ee > 99 %) compared to the wild-type (ee = 42 %) without loss of catalytic activity or thermostability. The molecular basis of the catalytic property enhancement was flanked by MDs, which revealed the role of the G92L mutation in regulating loop dynamics to stabilize the environment of the active site. Finally, a series of the challenge bulky substrate derivatives were assessed using the G92L variant, and all showed improved stereoselectivity ee > 99 %. This study provides novel insights for improving stereoselectivity through rational engineering of the loop dynamics of biocatalysts., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2024. Published by Elsevier B.V.)

In this paper, the experiment of cellulose from corn stalk using 1, 2-propylene glycol (PG) and diethylene glycol (DEG) liquefaction catalyzed by phosphoric acid at atmosphere pressure was carried out. The effect of reaction time on the structural changes of cellulose in the liquefaction process of polyhydric alcohols was investigated, aiming at understanding the mechanism of cellulose liquefaction reaction under the action of acid catalyzed polyhydric alcohols. It was found that the liquefaction yield increased first and then decreased with the extension of reaction time, and reached the highest at 150 min (99.34 %). In the phase of increasing liquefaction yield, cellulose was degraded and translated into glucose, which was then converted into plenty of glycosides with PG/DEG. These glycosides were further converted into low molecular weight (LMW) substances such as hydrocarbons, acids, alcohols, esters, ketones, and ethers. At this time, the biofuel contained 70 %-85 % compounds with carbon number less than 25 and 5 %-10 % compounds with carbon number more than 25. As the prolongation of reaction time (after 150 min), quantities of unstable free radicals formed by cellulose degradation could combine with each other or with hydrogen atoms provided by PG/DEG to produce relatively stable macromolecular substances. That is, the polydispersity (M w /M n , abbreviated Р= 1.28) of the generated biofuel at this stage no longer decreased. However, liquefaction residue produced at 240 min had changed essentially, which was completely different from the liquefaction residue produced in the early stage of liquefaction. In conclusion, this paper revealed the partial reaction process of cellulose by studying the structural changes in the liquefaction process of polyhydric alcohols, which laid a theoretical foundation for exploring the liquefaction mechanism of cellulose., Competing Interests: Declaration of competing interest Authors don't have any conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Polyene cyclizations are among the most complex and challenging transformations in biology. In a single reaction step, multiple carbon-carbon bonds, ring systems and stereogenic centres are constituted from simple, acyclic precursors 1-3 . Simultaneously achieving this kind of precise control over product distribution and stereochemistry poses a formidable task for chemists. In particular, the polyene cyclization of (3E,7E)-homofarnesol to the valuable naturally occurring ambergris odorant (-)-ambrox is recognized as a longstanding challenge in chemical synthesis 1,4-7 . Here we report a diastereoselective and enantioselective synthesis of (-)-ambrox and the sesquiterpene lactone natural product (+)-sclareolide by a catalytic asymmetric polyene cyclization by using a highly Brønsted-acidic and confined imidodiphosphorimidate catalyst in the presence of fluorinated alcohols. Several experiments, including deuterium-labelling studies, suggest that the reaction predominantly proceeds through a concerted pathway in line with the Stork-Eschenmoser hypothesis 8-10 . Mechanistic studies show the importance of the enzyme-like microenvironment of the imidodiphosphorimidate catalyst for attaining exceptionally high selectivities, previously thought to be achievable only in enzyme-catalysed polyene cyclizations., (© 2024. The Author(s).)

Chiral alcohols are essential building blocks of numerous pharmaceuticals and fine chemicals. Aldo-keto reductases (AKRs) constitute a superfamily of oxidoreductases that catalyze the reduction of aldehydes and ketones to their corresponding alcohols using NAD(P)H as a coenzyme. Knowledge about the crucial roles of AKRs immobilization in the biocatalytic synthesis of chiral alcohols is expanding. Herein, we reviewed the characteristics of various AKRs immobilization approaches, the applications of different immobilization materials, and the prospects of continuous flow bioreactor construction by employing these immobilized biocatalysts for synthesizing chiral alcohols. Finally, the opportunities and ongoing challenges for AKR immobilization are discussed and the outlook for this emerging area is analyzed., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Yajun Wang reports financial support was provided by National Key Research and Development Program of China. Yajun Wang reports financial support was provided by Zhejiang Provincial Department of Science and Technology. none. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A method for the reduction of aldehydes with pinacolborane catalyzed by pincer cobalt complexes based on a triazine backbone is developed in this paper. The presented methodology allows for the transformation of several aldehydes bearing a wide range of electron-withdrawing and electron-donating groups under mild conditions. The presented procedure allows for the direct one-step hydrolysis of the obtained intermediates to the corresponding primary alcohols. A plausible reaction mechanism is proposed.

In spite of the widespread use of alkanols as penetration enhancers, their effect on vesicular formulations remains largely unexplored. These can affect the stability and integrity of the phospholipid bilayers. In this study, we have investigated the interaction of linear (ethanol, butanol, hexanol, octanol) and branched alkanols (t-amylol and t-butanol) with three phospholipids (soya lecithin, SL; soy L-α-phosphatidylcholine, SPC; and 1,2-dipalmitoyl- sn -glycero-3-phosphocholine, DPPC). Thermodynamic and structural aspects of these interactions were studied as a function of the alkanol concentration and chain length. Our interpretations are based on isothermal titration calorimetry (ITC) and dynamic light scattering (DLS) experiments. We observed one-site interactions wherein hydroxyl and acyl groups interacted with the polar and nonpolar regions of the phospholipid, respectively. The stability and structural integrity of bilayers appeared to be dependent upon (a) the hydrocarbon chain length and concentration of alcohols, and (b) the degree of unsaturation in the phospholipid molecule. We found that these interactions triggered a reduction in the enthalpy which was compensated by increased entropy, keeping free energy negative. Drop in enthalpy indicates reversible disordering of the bilayer which enables the diffusion of alcohol without triggering destabilization. Ethanol engaged predominantly with the interface, and it resulted in higher enthalpic changes. Interactions became increasingly unfavorable with longer alcohols - a cutoff point was recorded with hexanol. The overall sequence of membrane disordering capability was recorded as follows: ethanol < butanol < octanol < hexanol. Octanol's larger size restricted its penetration in the bilayer, and hence it caused less enthalpic changes relative to hexanol. This could also be verified from the trends in the area ratio of these vesicles obtained from the DLS data. Branched alkanols displayed a lower binding affinity with the phospholipids relative to their linear counterparts. These data are useful while contemplating the inclusion of short-chain alcohols as penetration enhancers in phospholipid vesicles.

Recently, alcohol-based draw solute (DS), i.e., alcohol with water, is one of the trending research topics in forward osmosis (FO) because of its performance and ease of regeneration. Nevertheless, the higher reverse solute flux (RSF) of the alcohol-based DS hinders its commercialization in water and wastewater treatment applications. This research aims to minimize the RSF of the alcohol-based DS in FO by investigating the possibility of using alcohol-alcohol-based draw solutes for the first time. Three alcohol-alcohol-based draw solutions, namely, (1) E70 + IPA30 (ethanol: 70% + isopropanol: 30%), (2) E40 + IPA60 (ethanol: 40% + isopropanol: 60%), and (3) E10 + IPA90 (ethanol: 10% + isopropanol: 90%), were prepared and the properties (including osmolality, shear stress, and viscosity) of the DS were first investigated followed by the parametric investigation (concerning temperature and concentration). The results were further analyzed with the fixed-point iterative method in MATLAB to obtain the performance parameters. Results reveal that the E10 + IPA90 mixture yields a lower RSF of 40.62 g/m 2 /h and specific reverse solute flux of 3.78 g/L with a considerably good water flux and recovery percentage of 11.47 LMH and 26.29%, respectively, as compared to other DS E70 + IPA30 and E40 + IPA60 at 25 °C. Thus, E10 + IPA90 is recommended as a potential candidate to be used as a DS in FO., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Heteroatom-doped porous carbon-based materials with high surface area compared to their metal-based homologs are considered environmentally friendly and ideal catalysts for organic reactions. In this paper, a new method for the convenient fabrication, cost-effective, and high efficiency of nitrogen/selenium co-doped porous carbon-based catalysis (marked as N/SePC-T) was designed. The N/SePC-T catalysts were created from the direct pyrolysis of a eutectic solvent containing choline chloride/urea as the nitrogen-rich carbon source, selenium dioxide as a source of heteroatom and chitosan as a secondary carbon source in different temperatures (T). The efficacy of the carbonization temperature on the pore structure, morphology, and catalytic activity of the N/SePC-T materials was investigated and displayed, the N/SePC-900 (having a surface area of 562.01 m 2 /g and total pore volume of 0.2351 cm 3  g -1 ) has the best performance. The morphology, structure, and physicochemical properties of N/SePC-900 were characterized using various analyses including XRD, TEM, TGA, FE-SEM, EDX, FT-IR, XPS, and Raman. The optimized N/SePC-900 catalyst indicated excellent catalytic performance in the oxidation of benzylalcohols to corresponding aldehydes in very mild conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The ability to tame high-energy intermediates is important for synthetic chemistry, enabling the construction of complex molecules and propelling advances in the field of synthesis. Along these lines, carbenes and carbenoid intermediates are particularly attractive, but often unknown, high-energy intermediates 1,2 . Classical methods to access metal carbene intermediates exploit two-electron chemistry to form the carbon-metal bond. However, these methods are usually prohibitive because of reagent safety concerns, limiting their broad implementation in synthesis 3-6 . Mechanistically, an alternative approach to carbene intermediates that could circumvent these pitfalls would involve two single-electron steps: radical addition to metal to forge the initial carbon-metal bond followed by redox-promoted α-elimination to yield the desired metal carbene intermediate. Here we realize this strategy through a metallaphotoredox platform that exploits iron carbene reactivity using readily available chemical feedstocks as radical sources and α-elimination from six classes of previously underexploited leaving groups. These discoveries permit cyclopropanation and σ-bond insertion into N-H, S-H and P-H bonds from abundant and bench-stable carboxylic acids, amino acids and alcohols, thereby providing a general solution to the challenge of carbene-mediated chemical diversification., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

Alkoxyalkylation and hydroxyalkylation methods utilizing oxo-compound derivatives such as aldehydes, acetals or acetylenes and various alcohols or water are widely used tools in preparative organic chemistry to synthesize bioactive compounds, biosensors, supramolecular compounds and petrochemicals. The syntheses of such molecules of broad relevance are facilitated by acid, base or heterogenous catalysis. However, degradation of the N -analogous Mannich bases are reported to yield alkoxyalkyl derivatives via the retro -Mannich reaction. The mutual derivative of all mentioned species are quinone methides, which are reported to form under both alkoxy- and aminoalkylative conditions and via the degradation of the Mannich-products. The aim of this review is to summarize the alkoxyalkylation (most commonly alkoxymethylation) of electron-rich arenes sorted by the methods of alkoxyalkylation (direct or via retro -Mannich reaction) and the substrate arenes, such as phenolic and derived carbocycles, heterocycles and the widely examined indole derivatives.

A homologous series of 20 substituted alcohol-imidazole-acetate model complexes imitating the charge relay system in Ser-His-Asp catalytic triad of serine proteases is considered quantum-chemically. We show qualitatively that the geometries of alcohol-imidazole and imidazole-acetate short hydrogen bonds are strongly coupled via the central imidazole and such complexes are capable of effectively relaying the charge from acetate to alcohol moiety upon relatively small concerted proton displacements. We hypothesize an alternative catalytic mechanism of serine proteases that does not require two complete proton transfers or hydrogen bond breakage between Ser and His residues., (© 2024 Wiley-VCH GmbH.)

In this study, Fe 3 O 4 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.

The modulation of whole-cell activity presents a considerable challenge in biocatalysis. Conventional approaches to whole-cell catalysis, while having their strengths, often rely on complex and deliberate enzyme designs, which could result in difficulties in activity modulation and prolonged response times. Additionally, the activity of intracellular enzymes in whole-cell catalysis is influenced by temperature. To address these limitations, we introduced a relationally designed nanobiohybrid system that utilized light to modulate whole-cell catalysis for chiral alcohol production. By incorporating platinum nanoparticles onto Rhodotorula sp. cell surfaces, the nanobiohybrid capitalized on the photothermal properties of the nanoparticles to regulate the overall cell activity. When exposed to light, the Pt nanoparticles generate heat through the photothermal effect, consequently leading to an increase in the catalytic activity of the whole cells. This innovative approach facilitates control over whole-cell production and provides an efficient method for regulating biocatalytic processes. The findings of this study demonstrate the significant potential of switchable control strategies in biomanufacturing across a wide range of industries., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Alcohol dehydrogenases (ADHs) mediated biocatalytic asymmetric reduction of ketones have been widely applied in the synthesis of optically active secondary alcohols with highly reactive hydroxyl groups ligated to the stereogenic carbon and divided into (R)- and (S)-configurations. Stereocomplementary ADHs could be applied in the synthesis of both enantiomers and are increasingly accepted as the "first of choice" in green chemistry due to the high atomic economy, low environmental factor, 100 % theoretical yield, and high environmentally friendliness. Due to the equal importance of complementary alcohols, development of stereocomplementary ADHs draws increasing attention. This review is committed to summarize recent advance in discovery of naturally evolved and tailor-made stereocomplementary ADHs, unveil the molecular mechanism of stereoselective catalysis in views of classification and functional basis, and provide guidance for further engineering the stereoselectivity of ADHs for the industrial biosynthesis of chiral secondary alcohol of industrial relevance., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Alcohol is ubiquitous with unparalleled structural diversity and thus has wide applications as a native functional group in organic synthesis. It is highly prevalent among biomolecules and offers promising opportunities for the development of chemical libraries. Over the last decade, alcohol has been extensively used as an environmentally friendly chemical for numerous organic transformations. In this review, we collectively discuss the utilisation of alcohol from 2015 to 2023 in various organic transformations and their application toward intermediates of drugs, drug derivatives and natural product-like molecules. Notable features discussed are as follows: (i) sustainable approaches for C-X alkylation (X = C, N, or O) including O -phosphorylation of alcohols, (ii) newer strategies using methanol as a methylating reagent, (iii) allylation of alkenes and alkynes including allylic trifluoromethylations, (iv) alkenylation of N-heterocycles, ketones, sulfones, and ylides towards the synthesis of drug-like molecules, (v) cyclisation and annulation to pharmaceutically active molecules, and (vi) coupling of alcohols with aryl halides or triflates, aryl cyanide and olefins to access drug-like molecules. We summarise the synthesis of over 100 drugs via several approaches, where alcohol was used as one of the potential coupling partners. Additionally, a library of molecules consisting over 60 fatty acids or steroid motifs is documented for late-stage functionalisation including the challenges and opportunities for harnessing alcohols as renewable resources.

In aqueous binary solvents with fluorinated alcohols, 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), and aliphatic alcohols, ethanol (EtOH) and 2-propanol (2-PrOH), the denaturation of hen egg white lysozyme (HEWL) with increasing alcohol mole fraction x A has been investigated in a wide view from the molecular vibration to the secondary and ternary structures. Circular dichroism (CD) measurement showed that the secondary structure of α-helix content of HEWL increases on adding a small amount of the fluorinated alcohol to the aqueous solution, while the β-sheet content decreases. On the contrary, the secondary structure does not significantly change by the addition of the aliphatic alcohols. Correspondingly, the infrared (IR) spectroscopic measurements revealed that the amide I band red-shifts on the addition of the fluorinated alcohol. However, the band remains unchanged in the aliphatic alcohol systems with increasing alcohol content. To observe the ternary structure of HEWL, small-angle neutron scattering (SANS) experiments with H/D substitution technique have been applied to the HEWL solutions. The SANS experiments were successful in revealing the details of how the geometry of the HEWL changes as a function of x A . The SANS profiles indicated the spherical structure of HEWL in all of the alcohol systems in the x A range examined. The mean radius of HEWL in the two fluorinated alcohol systems increases from ∼16 to ∼18 Å during the change in the secondary structure against the increase in the fluorinated alcohol content. On contrast, the radius does not significantly change in both aliphatic alcohol systems below x A = 0.3 but expands to ∼19 Å as the alcohol content is close to the limitation of the HEWL solubility. According to the present results, together with our knowledge of the alcohol cluster formation and the interaction of the trifluoromethyl (CF 3 ) groups with the hydrophobic moieties of biomolecules, the effects of alcohols on the denaturation of the protein have been discussed on a molecular scale.

Objective: This research aims to elucidate critical impurities in process validation batches of tacrolimus injection formulations, focusing on identification and characterization of previously unreported impurity at RRT 0.42, identified as the tacrolimus alcohol adduct. The potential root causes for the formation of new impurity was determined using structured risk assessment by cause and effect fishbone diagram. The primary objective was to propose mitigation plan and demonstrate the control of impurities with 6 month accelerated stability results in development batches., Methods: The investigation utilizes method validation and characterization studies to affirm the accuracy of quantifying the tacrolimus alcohol adduct. The research methodology employed different characterization techniques like rotational rheometer, ICP‒MS, MALDI-MS, 1 H NMR, 13 C NMR, and DEPT-135 NMR for structural elucidation. Additionally, the exact mass of the impurity is validated using electrospray ionization mass spectra., Results: Results indicate successful identification and characterization of the tacrolimus alcohol adduct. The study further explores the transformation of Tacrolimus monohydrate under various conditions, unveiling the formation of Tacrolimus hydroxy acid and proposing the existence of a novel degradation product, the Tacrolimus alcohol adduct. Six-month data from development lots utilizing Manufacturing Process II demonstrate significantly lower levels of alcohol adducts., Conclusions: Manufacturing Process II, selectively locates Tacrolimus within the micellar core of HCO-60, this prevent direct contact of ethanol with Tacrolimus which minimizes impurity alcohol adduct formation. This research contributes to the understanding of tacrolimus formulations, offering ways to safeguard product integrity and stability during manufacturing and storage., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

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.

In most species of moths, the female produces and releases a volatile sex pheromone from a specific gland to attract a mate. Biosynthesis of the most common type of moth sex pheromone component (Type 1) involves de novo synthesis of hexadecanoate (16:Acyl), followed by modification to various fatty acyl intermediates, then reduction to a primary alcohol, which may be acetylated or oxidized to produce an acetate ester or aldehyde, respectively. Our previous work on the moth Chloridea virescens (Noctuidae) showed that females produce 90% of the major pheromone component, (Z)-11-hexadecenal (Z11-16:Ald), via a direct and rapid route of de novo biosynthesis with highly labile intermediates, and ca. 10% from an indirect route that likely mobilizes a pre-synthesized 16-carbon skeleton, possibly, (Z)-11-hexadecenoate (Z11-16:Acyl) or hexadecanoate (16:Acyl). In this paper, we use stable isotope tracer/tracee techniques to study the dynamics of the precursor alcohol (Z)-11-hexadecenol (Z11-16:OH) and stores of Z11-16:Acyl and 16:Acyl to determine their roles in biosynthesis of Z11-16:Ald. We found: (i) that intracellular Z11-16:OH is synthesized at roughly the same rate as Z11-16:Ald, indicating that translocation and oxidation of this moiety does not rate limit biosynthesis of Z11-16:Ald, (ii) intracellular Z11-16:OH consists of two pools, a highly labile one rapidly translocated out of the cell and converted to Z11-16:Ald, and a less labile one that mostly remains in gland cells, (iii) during pheromone biosynthesis, net stores of Z11-16:Acyl increase, suggesting it is not the source of Z11-16:Ald produced by the indirect route, and (iv) no evidence for the gland synthesizing stored 16:Acyl prior to (up to 2 days before eclosion), or after, synthesis of pheromone commenced, suggesting the bulk of this stored moiety is synthesized elsewhere and transported to the gland prior to gland maturation. Thus, the pheromone gland of C. virescens produces very little stored fat over its functional lifetime, being optimized to produce sex pheromone., (© 2024. The Author(s).)

The development of bimolecular homolytic substitution (S H 2) catalysis has expanded cross-coupling chemistries by enabling the selective combination of any primary radical with any secondary or tertiary radical through a radical sorting mechanism 1-8 . Biomimetic 9,10 S H 2 catalysis can be used to merge common feedstock chemicals-such as alcohols, acids and halides-in various permutations for the construction of a single C(sp 3 )-C(sp 3 ) bond. The ability to sort these two distinct radicals across commercially available alkenes in a three-component manner would enable the simultaneous construction of two C(sp 3 )-C(sp 3 ) bonds, greatly accelerating access to complex molecules and drug-like chemical space 11 . However, the simultaneous in situ formation of electrophilic and primary nucleophilic radicals in the presence of unactivated alkenes is problematic, typically leading to statistical radical recombination, hydrogen atom transfer, disproportionation and other deleterious pathways 12,13 . Here we report the use of bimolecular homolytic substitution catalysis to sort an electrophilic radical and a nucleophilic radical across an unactivated alkene. This reaction involves the in situ formation of three distinct radical species, which are then differentiated by size and electronics, allowing for regioselective formation of the desired dialkylated products. This work accelerates access to pharmaceutically relevant C(sp 3 )-rich molecules and defines a distinct mechanistic approach for alkene dialkylation., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

This study addresses the pressing issues of energy production and consumption, in line with global sustainable development goals. Focusing on the potential of alcohols as "green" alternatives to traditional fossil fuels, especially in biofuel applications, we investigate the thermochemical properties of three alcohols (n-propanol, n-butanol, n-pentanol) blended with sunflower oil. The calorimetric analysis allows for the experimental determination of excess enthalpies in pseudo-binary mixtures at 303.15 K, revealing similarities in the trends of the curves (dependence on concentrations) but with different values for the excess enthalpies for each mixture. Despite the structural differences of the alcohols studied, the molar excess enthalpy values exhibit uniformity, suggesting consistent mixing behavior. The peak values of excess enthalpies for systems with sunflower oil and n-propanol, n-butanol and n-pentanol are, respectively, 3255.2 J/mole, 3297.4 J/mole and 3150.1 J/mole. Both the NRTL and Redlich-Kister equations show satisfactory agreement with the obtained values.

Polysaccharide nanoporous structures are suitable for various applications, ranging from biomedical scaffolds to adsorption materials, owing to their biocompatibility and large surface areas. Pectin, in particular, can create 3D nanoporous structures in aqueous solutions by binding with calcium cations and creating nanopores by phase separation; this process involves forming hydrogen bonds between alcohols and pectin chains in water and alcohol mixtures and the resulting penetration of alcohols into calcium-bound pectin gels. However, owing to the dehydration and condensation of polysaccharide chains during drying, it has proven to be challenging to maintain the 3D nanoporous structure without using a freeze-drying process or supercritical fluid. Herein, we report a facile method for creating polysaccharide-based xerogels, involving the co-evaporation of water with a nonsolvent (e.g., a low-molecular-weight hydrophobic alcohol such as isopropyl or n -propyl alcohol) at ambient conditions. Experiments and coarse-grained molecular dynamics simulations confirmed that salt-induced phase separation and hydrogen bonding between hydrophobic alcohols and pectin chains were the dominant processes in mixtures of pectin, water, and hydrophobic alcohols. Furthermore, the azeotropic evaporation of water and alcohol mixed in approximately 1:1 molar ratios was maintained during the natural drying process under ambient conditions, preventing the hydration and aggregation of the hydrophilic pectin chains. These results introduce a simple and convenient process to produce 3D polysaccharide xerogels under ambient conditions.

The replacement of a functional group with its corresponding bioisostere is a widely employed tactic during drug discovery campaigns that allows medicinal chemists to improve the ADME properties of candidates while maintaining potency. However, the incorporation of bioisosteres typically requires lengthy de novo resynthesis of potential candidates, which represents a bottleneck in their broader evaluation. An alternative would be to directly convert a functional group into its corresponding bioisostere at a late stage. Herein, we report the realization of this approach through the conversion of aliphatic alcohols into the corresponding difluoromethylated analogues via the merger of benzoxazolium-mediated deoxygenation and copper-mediated C(sp 3 )-CF 2 H bond formation. The utility of this method is showcased in a variety of complex alcohols and drug compounds.

The standard GAFF2 force field parameterization has been refined for the fluorinated alcohols 2,2,2-trifluoroethanol (TFE), 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and 1,1,1,3,3,3-hexafluoropropan-2-one (HFA), which are commonly used to study proteins and peptides in biomimetic media. The structural and dynamic properties of both proteins and peptides are significantly influenced by the biomimetic environment created by the presence of these cosolvents in aqueous solutions. Quantum mechanical calculations on stable conformers were used to parameterize the atomic charges. Different systems, such as pure liquids, aqueous solutions, and systems formed by melittin protein and cosolvent/water solutions, have been used to validate the new models. The calculated macroscopic and structural properties are in agreement with experimental findings, supporting the validity of the newly proposed models., (© 2023 The Authors. Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd.)

The success of colloidal semiconductor nanocrystals (NCs) in science and optoelectronics is inextricable from their surfaces. The functionalization of lead halide perovskite NCs 1-5 poses a formidable challenge because of their structural lability, unlike the well-established covalent ligand capping of conventional semiconductor NCs 6,7 . We posited that the vast and facile molecular engineering of phospholipids as zwitterionic surfactants can deliver highly customized surface chemistries for metal halide NCs. Molecular dynamics simulations implied that ligand-NC surface affinity is primarily governed by the structure of the zwitterionic head group, particularly by the geometric fitness of the anionic and cationic moieties into the surface lattice sites, as corroborated by the nuclear magnetic resonance and Fourier-transform infrared spectroscopy data. Lattice-matched primary-ammonium phospholipids enhance the structural and colloidal integrity of hybrid organic-inorganic lead halide perovskites (FAPbBr 3 and MAPbBr 3 (FA, formamidinium; MA, methylammonium)) and lead-free metal halide NCs. The molecular structure of the organic ligand tail governs the long-term colloidal stability and compatibility with solvents of diverse polarity, from hydrocarbons to acetone and alcohols. These NCs exhibit photoluminescence quantum yield of more than 96% in solution and solids and minimal photoluminescence intermittency at the single particle level with an average ON fraction as high as 94%, as well as bright and high-purity (about 95%) single-photon emission., (© 2023. The Author(s).)

Alcohol dehydrogenases are a well-known group of enzymes in the class of oxidoreductases that use electron transfer cofactors such as NAD(P) + /NAD(P)H for oxidation or reduction reactions of alcohols or carbonyl compounds respectively. These enzymes are utilized mainly as purified enzymes and offer some advantages in terms of green chemistry. They are environmentally friendly and a sustainable alternative to traditional chemical synthesis of bulk and fine chemicals. Industry has implemented several whole-cell biocatalytic processes to synthesize pharmaceutically active ingredients by exploring the high selectivity of enzymes. Unlike the whole cell system where cofactor regeneration is well conserved within the cellular environment, purified enzymes require additional cofactors or a cofactor recycling system in the reaction, even though cleaner reactions can be carried out with fewer downstream work-up problems. The challenge of producing purified enzymes in large quantities has been solved in large part by the use of recombinant enzymes. Most importantly, recombinant enzymes find applications in many cascade biotransformations to produce several important chiral precursors. Inevitably, several dehydrogenases were engineered as mere recombinant enzymes could not meet the industrial requirements for substrate and stereoselectivity. In recent years, a significant number of engineered alcohol dehydrogenases have been employed in asymmetric synthesis in industry. In a parallel development, several enzymatic and non-enzymatic methods have been established for regenerating expensive cofactors (NAD + /NADP + ) to make the overall enzymatic process more efficient and economically viable. In this review article, recent developments and applications of microbial alcohol dehydrogenases are summarized by emphasizing notable examples.