Organic Cosolvents Research Articles

A Green Asymmetric Bicyclic Co-Solvent Molecule for High-Voltage Aqueous Lithium-Ion Batteries.

Hybridizing aqueous electrolytes with organic co-solvents can effectively expand the voltage window of aqueous electrolytes while reducing salt usage, but most reported co-solvents are usually flammable and toxic, hardly achieving compatibility between safety and electrochemical performance. Here, a new non-flammable and non-toxic low-salt-concentration (1.85 m) aqueous electrolyte is reported using the green co-solvent isosorbide dimethyl ether (IDE). Owing to its unique 3D molecular structure, IDE can form a five-membered ring structure by binding the Li ion. The steric hindrance effect from IDE weakens its solvation ability, generating anion-participated solvation structures that produce a robust and uniform LiF-rich solid electrolyte interphase layer while containing elastic IDE-derived organics. Moreover, the multiple O atoms in IDE can effectively regulate the intermolecular hydrogen bonding networks, reducing H2O molecule activity and expanding the electrochemical window. Such unique solvation structures and optimized hydrogen bonding networks enabled by IDE effectively suppress electrode/electrolyte interfacial side reactions, achieving a 4.3 V voltage window. The as-developed Li4Ti5O12(LTO)||LiMn2O4(LMO) full cell delivers outstanding cycling performance over 450 cycles at 2 C. The proposed green hybrid aqueous electrolyte provides a new pathway for developing high-voltage aqueous lithium batteries.

A critical factor in reactive oxygen species (ROS) studies: the need to understand the chemistry of the solvent used: the case of DMSO.

Reactive oxygen species (ROS) play critical roles in normal physiological processes including cellular signaling and immune responses. Various pathological conditions including infections of various types, inflammation, cancer, and respiratory conditions are associated with elevated levels of ROS. Therefore, there is widespread interest in understanding ROS concentrations under various pathophysiological conditions for diagnostic and therapeutic applications including ROS-triggered drug delivery. However, in determining ROS concentration, there are major concerns of inappropriate use of various methods that lead to erroneous results; this has prompted the publication of a consensus paper in Nature Metabolism by a group of ROS experts stating "Unfortunately, the application and interpretation of these measurements are fraught with challenges and limitations. This can lead to misleading claims." Along this line, we have identified an overlooked factor, which can significantly skew the results and results interpretation: the organic co-solvent. DMSO is one of the most widely used organic co-solvents to dissolve a reagent for bioassays. Herein, we describe the rapid oxidation of DMSO by hypochlorite and how this oxidation impacts results of ROS determination in buffer, cell culture media, cell culture, and cell lysates. We hope to use this one example to draw attention to the convoluted roles that DMSO and possibly other organic co-solvents can play and skew experimental results. We also hope to stimulate additional studies to bring more rigor to studying ROS concentration and biology.

Block copolymer synthesis in ionic liquid via polymerisation-induced self-assembly: a convenient route to gel electrolytes.

We report for the first time a reversible addition-fragmentation chain transfer polymerisation-induced self-assembly (RAFT-PISA) formulation in ionic liquid (IL) that yields worm gels. A series of poly(2-hydroxyethyl methacrylate)-b-poly(benzyl methacrylate) (PHEMA-b-PBzMA) block copolymer nanoparticles were synthesised via RAFT dispersion polymerisation of benzyl methacrylate in the hydrophilic IL 1-ethyl-3-methyl imidazolium dicyanamide, [EMIM][DCA]. This RAFT-PISA formulation can be controlled to afford spherical, worm-like and vesicular nano-objects, with free-standing gels being obtained over a broad range of PBzMA core-forming degrees of polymerisation (DPs). High monomer conversions (≥96%) were obtained within 2 hours for all PISA syntheses as determined by 1H NMR spectroscopy, and good control over molar mass was confirmed by gel permeation chromatography (GPC). Nanoparticle morphologies were identified using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and further detailed characterisation was conducted to monitor rheological, electrochemical and thermal characteristics of the nanoparticle dispersions to assess their potential in future electronic applications. Most importantly, this new PISA formulation in IL facilitates the in situ formation of worm ionogel electrolyte materials at copolymer concentrations >4% w/w via efficient and convenient synthesis routes without the need for organic co-solvents or post-polymerisation processing/purification. Moreover, we demonstrate that the worm ionogels developed in this work exhibit comparable electrochemical properties and thermal stability to that of the IL alone, showcasing their potential as gel electrolytes.

In Vitro Studies on the Effects of Water Miscible Organic Co-Solvents on Select Drug Metabolizing Enzyme Activities

In Vitro Studies on the Effects of Water Miscible Organic Co-Solvents on Select Drug Metabolizing Enzyme Activities

Ether-type co-solvents of excellence for aqueous base-free Pt-catalyzed oxidation of concentrated 5-(hydroxymethyl)furfural to 2,5-furandicarboxylic acid

The biomass-derived 5-(hydroxymethyl)furfural (5-HMF) is readily converted in water to 2,5-furandicarboxyl acid (FDCA) that is well known as a renewable diacid monomer. However, the limited solubility of FDCA in water posed serious challenges to process development. Herein, the base-free Pt-catalyzed oxidation of 5-HMF was explored in aqueous binary solvent systems containing organic co-solvents such as dimethyl sulfoxide, N,N-dimethylformamide, gamma-valerolactone, dioxane, diethylene glycol dimethyl ether, and 1,2-dimethoxyethane (DME). The FDCA solubility and 5-HMF oxidation performance were investigated in co-solvent/H2O systems with different co-solvent fractions. When correlated with the solvatochromic parameters of co-solvents, the FDCA yield appeared to be in harmony with their polarizability and hydrogen bonding acceptance ability. Thus, infrared spectra were collected with three systems such as co-solvent/H2O, 5-HMF in co-solvent, and 5-HMF in co-solvent/H2O. The employed co-solvent was found to have different abilities to interact with the O–H and C=O moieties of 5-HMF via H-bonding and dipole-induced dipole attraction (related with the polarizability), respectively. Consequently, a high FDCA yield was achieved using three ether-type co-solvents in which these interactions are relatively weak. In a continuous-flow pattern for the base-free oxidation of 3 wt% 5-HMF solution, a FDCA yield of >98 % was achieved with 60 wt% DME/H2O under the optimized conditions.

A Novel Lipase from Streptomyces exfoliatus DSMZ 41693 for Biotechnological Applications

Genome mining of Streptomyces exfoliatus DSMZ 41693 has allowed us to identify four different lipase-encoding sequences, and one of them (SeLipC) has been successfully cloned and extracellularly expressed using Rhodococcus sp. T104 as a host. SeLipC was purified by one-step hydrophobic interaction chromatography. The enzyme is a monomeric protein of 27.6 kDa, which belongs to subfamily I.7 of lipolytic enzymes according to its phylogenetic analysis and biochemical characterization. The purified enzyme shows the highest activity at 60 °C and an optimum pH of 8.5, whereas thermal stability is significantly improved when protein concentration is increased, as confirmed by thermal deactivation kinetics, circular dichroism, and differential scanning calorimetry. Enzyme hydrolytic activity using p-nitrophenyl palmitate (pNPP) as substrate can be modulated by different water-miscible organic cosolvents, detergents, and metal ions. Likewise, kinetic parameters for pNPP are: KM = 49.6 µM, kcat = 57 s−1, and kcat/KM = 1.15 × 106 s−1·M−1. SeLipC is also able to hydrolyze olive oil and degrade several polyester-type polymers such as poly(butylene succinate) (PBS), poly(butylene succinate)-co-(butylene adipate) (PBSA), and poly(ε-caprolactone) (PCL). Moreover, SeLipC can catalyze the synthesis of different sugar fatty acid esters by transesterification using vinyl laurate as an acyl donor, demonstrating its interest in different biotechnological applications.

Fractionation of lignin using eco-friendly organic cosolvent and preparation of light-colored lignin micro-nanoparticles for sustainable natural sunscreens

The inherent challenges posed by lignin, such as its high heterogeneity, complex structure and dark color, have impeded its widespread high-value utilization. In the present study, a green cosolvent system comprising ethanol (EtOH) and dimethyl carbonate (DMC) was employed for the fractional separation of alkali lignin. Through careful manipulation of the solvent ratio, interactions between the solvents and lignin were effectively regulated, leading to the reduction of lignin heterogeneity and the isolation of lignin fractions with distinct properties. Notably, a high yield of up to 35.65% of lignin with desirable characteristics, including a light color, low molecular weight, and high hydroxyl groups content, was achieved. Furthermore, this specific lignin fraction exhibited enhanced UV absorption and antioxidative properties, rendering it highly suitable for potential applications in sun protection products. When incorporated as micro-nano particles, it exhibited great compatibility with hand creams and elevated their sun protection factor (SPF). This innovative approach not only presents a green and straightforward lignin fractionation process but also highlights the untapped potential of lignin in the realm of sun protection applications.

ZIF-8 with exceptional thermal stability: Role of organic cosolvents in phase control and structure stabilization

Thermal stability is one of the key factors in catalysis and high-temperature industrial applications. The thermal degradation of ZIF-8, particularly its nanocrystals, could result in a significant loss of surface area and crystallinity, limiting its large-scale applicability. In this study, ZIF-8 nanocrystals with improved thermal stability were synthesized at room temperature (RT) through a facile, one-pot method – an ultrasound-assisted, solvent-guided ZIF-8 growth. The effect of synthesis variables, including the type and concentration of solvent, ultrasonication, and synthesis time, in improving the material’s thermal stability was studied systematically. The as-prepared samples were analyzed by TGA/DSC, XRD, SEM/TEM, FTIR, and BET to monitor the weight loss with temperature, sample crystallinity, crystal morphology, chemical structure, and surface area. Notably, synthesis with 5 v/v% of n-hexane (ZIF-8new-ref) demonstrated the formation of highly-crystalline ZIF-8 nanocrystals with extraordinary thermal stability (with only ∼2.0–3.0 % weight loss up to 600 °C), large surface area (i.e., 975 m2 g−1), and an excellent particle size distribution in the range of 0.2–0.4 μm. More importantly, the short synthesis time (2 h) and sonication-assisted pretreatment of the precursor (for promoting solvent-ligand interaction) proved effective and played a crucial role in controlling ZIF-8’s thermal stability. The mechanism for the thermal stability enhancement was thus proposed. The highly thermally stable ZIF-8 nanocrystals were also synthesized with significantly reduced chemical usage, e.g., 1/11 of the normal ligand-to-metal ratio (70), achieving cost-effective and environmentally friendly synthesis.

Biocatalytic characterization of an alcohol dehydrogenase variant deduced from Lactobacillus kefir in asymmetric hydrogen transfer

Hydrogen transfer biocatalysts to prepare optically pure alcohols are in need, especially when it comes to sterically demanding ketones, whereof the bioreduced products are either essential precursors of pharmaceutically relevant compounds or constitute APIs themselves. In this study, we report on the biocatalytic potential of an anti-Prelog (R)-specific Lactobacillus kefir ADH variant (Lk-ADH-E145F-F147L-Y190C, named Lk-ADH Prince) employed as E. coli/ADH whole-cell biocatalyst and its characterization for stereoselective reduction of prochiral carbonyl substrates. Key enzymatic reaction parameters, including the reaction medium, evaluation of cofactor-dependency, organic co-solvent tolerance, and substrate loading, were determined employing the drug pentoxifylline as a model prochiral ketone. Furthermore, to tap the substrate scope of Lk-ADH Prince in hydrogen transfer reactions, a broad range of 34 carbonylic derivatives was screened. Our data demonstrate that E. coli/Lk-ADH Prince exhibits activity toward a variety of structurally different ketones, furnishing optically active alcohol products at the high conversion of 65–99.9% and in moderate-to-high isolated yields (38–91%) with excellent anti-Prelog (R)-stereoselectivity (up to >99% ee) at substrate concentrations up to 100 mM.

Isomerization of Hemicellulose Aldoses to Ketoses Catalyzed by Basic Anion Resins: Catalyst Screening and Stability Studies

Isomerization of aldoses to ketoses is an essential step in carbohydrate valorization routes in biorefineries to produce a wide variety of bioproducts. In this work, selective isomerization of aldoses into ketoses was investigated using different commercial Brønsted basic anion resins at low temperature conditions. Weak and strong basic resins were tested under different reaction conditions. Amberlite IRA-900 and Amberlyst A-26 (strong resins) and Amberlite IRA-67 and Amberlyst A-21 (weak resins) were tested to assess their catalytic properties. Strong basic resins provided high yields of fructose. IRA-900 was also tested in the isomerization of different sugar monosaccharides conventionally present in lignocellulosic biomass (xylose, arabinose, galactose, glucose and mannose) aiming to explore the performance of this material in hemicellulose-derived sugar mixtures. Very promising performance was observed for IRA-900, yielding fructose selectivity higher than 75% and fructose yield of 27% in the isomerization reaction. Notably, basic anionic resins were not suitable for reuse in different reaction cycles, although the use of organic cosolvents, specifically ethanol, improved the reusability of the tested resins.

EFFECT OF SKIN FAT ON CAPSAICIN TRANSFERSOME GEL: IN VITRO PENETRATION STUDIES USING FRANZ DIFFUSION CELLS

Objective: Capsaicin is a highly lipophilic substance that generally uses an organic cosolvent added to diffusion medium in penetration tests to increase penetration by fluidizing fat. This study aims to determine the effect of subcutaneous fat on the penetration of capsaicin as lipophilic substances formulated into transfersome and compare it to hydrophilic substances, namely vitamin C. Methods: The thin layer method was used to develop the transfersome formulation using Phospholipon 90G and Tween 80. Vesicle size, zeta potential, deformability index, morphology, and entrapment efficiency were all characterized. The transfersome suspension was then developed into a gel formulation using 1% carbomer. The in vitro penetration test was performed using a Franz diffusion cell of rat skin with and without subcutaneous fat. Results: The cumulative amount of penetration on fat-free membranes compared to membranes with fat for capsaicin transfersome gel 920.28±3.42 μg/cm2 and 762.22±1.73 μg/cm2, respectively, then for non-transfersome capsaicin gel was 833.33±0.84 μg/cm2 and 595.80±0.32 μg/cm2 respectively, and for vitamin C non-transfer some gel 776.45±1.19 μg/cm2 and 654.69±3.36 μg/cm2 respectively. Conclusion: According to these results, it can be concluded that the presence of subcutaneous fat affects inhibiting the penetration of lipophilic substances.

Encapsulation of recombinant Escherichia coli cells harboring nitrilase in surface-crosslinked hydrogel particles: A robust and durable biocatalyst for the hydrolysis of nitrile

Surface-crosslinked hydrogel particles encapsulating E. coli cells harboring nitrilase were constructed and used as a durable biocatalyst in the synthesis of gabapentin intermediate. E. coli cells (50 g/L) expressing nitrilase were encapsulated in 2% (w/v) alginate hydrogel, 0.5%(w/v) glutaraldehyde and 1%(w/v) polyethyleneimine were sequentially used as crosslinker. The constructed alginate particles with GA&PEI composite crosslinking had a similar catalytic capacity compared to equivalent free cells, which could completely hydrolyze 1.0 M substrate 1-cyanocyclohexaneacetonitrile within 4 h at pH 7.5 and 35 °C, and have a specific activity of 134.6 U/g, an optimum temperature at 55 °C and a corresponding half-life up to 19.1 ± 1.9 h. The particles showed excellent storage stability, reusability and mechanical strength, which retained 90.3% activity after 2-month storage at 4 °C, and 83.2% activity after 14-day storage at 35 °C. In batch reactions, 50 g/L particles could be reused for maximum 32 cycles, maintained 63.5% residual activity and 50.7% particle integrity, providing an average product yield of 94.6% in the first 30 batches and a productivity of 1467.03 g/L/day. Besides, the stability and catalytic activity of the particles were almost unaffected in several organic co-solvents and in purified water, showing their good industrial potential.

Evolution of Organic Solvent-Resistant DNA Polymerases.

The introduction of thermostable polymerases revolutionized the polymerase chain reaction (PCR) and biotechnology. However, many GC-rich genes cannot be PCR-amplified with high efficiency in water, irrespective of temperature. Although polar organic cosolvents can enhance nucleic acid polymerization and amplification by destabilizing duplex DNA and secondary structures, nature has not selected for the evolution of solvent-tolerant polymerase enzymes. Here, we used ultrahigh-throughput droplet-based selection and deep sequencing along with computational free-energy and binding affinity calculations to evolve Taq polymerase to generate enzymes that are both stable and highly active in the presence of organic cosolvents, resulting in up to 10% solvent resistance and over 100-fold increase in stability at 97.5 °C in the presence of 1,4-butanediol, as well as tolerance to up to 10 times higher concentrations of the potent cosolvents sulfolane and 2-pyrrolidone. Using these polymerases, we successfully amplified a broad spectrum of GC-rich templates containing regions with over 90% GC content, including templates recalcitrant to amplification with existing polymerases, even in the presence of cosolvents. We also demonstrated dramatically reduced GC bias in the amplification of genes with widely varying GC content in quantitative polymerase chain reaction (qPCR). By expanding the scope of solvent systems compatible with nucleic acid polymerization, these organic solvent-resistant polymerases enable a dramatic reduction of sequence bias not achievable through thermal resistance alone, with significant implications for a wide range of applications including sequencing and synthetic biology in mixed aqueous-organic media.

HERBAL INFUSIONS AS INHIBITORS OF TRYPSIN ACTIVITY IN WATER AND POLAR ORGANIC SOLVENT–WATER SYSTEMS

The inhibition of digestive enzyme trypsin by polyphenolic compounds derived from mountainous herbal infusions, as well as the effect of polarity and acidity of the media on this process were studied by virtue of UV-Vis absorption spectroscopy at 293.15 K. Mountainous herbal infusions (thyme, peppermint) are well known due to their biomedical significance and wide use as a beverage. The binding constant (Kb) and standard Gibbs energy change (ΔG0) were calculated. The obtained results show that polyphenols extracted from herbal infusions significantly inhibit trypsin. Moreover, the effect of thyme infusion is stronger compared with that of peppermint. The results show that the change of both polarity and H-bonding ability of polar organic cosolvent significantly alters the value of Kb, indicating that H-bonds and electrostatic interactions are the main driving forces in these interactions.

WATER PHASE CONCENTRATE SOLUBILITY TEST SNAKEHEAD FISH EXTRACT (Channa Striata) IN ORGANIC COSOLVENT

Snakehead fish extract has been recognized for its potential in healing postoperative wounds and burns. The extract contains albumin, which aids in tissue formation and healing processes. To create a high-quality wound healing drug, the extract needs to be formulated into a concentrated form and combined with a solvent that can effectively dissolve its active substances. Understanding the solubility profile of the extract and the composition of the solvent is crucial for this purpose. This study aims to determine the solubility profile of the aqueous phase concentrate of snakehead fish extract in an organic co-solvent. Solubility is an important parameter as it can impact the release rate and therapeutic effectiveness of the drug. A solubility test was conducted to assess the solubility of the aqueous phase concentrate in various solvents. The results of the solubility test indicated that the aqueous phase concentrate of snakehead fish extract exhibited good solubility in aquadest (20%), slight solubility in propylene glycol (8.5%) and honey (2%), and was insoluble in ethanol, glycerin, mannitol, and sorbitol (0%). These findings provide valuable information for formulating the extract into a wound healing drug with an appropriate solvent composition, ensuring optimal solubility and therapeutic efficacy according to pharmacopeial standards. Keywords: Concentrate; Aqueous phase of snakehead fish extract; Solubility; Solvent; Polarity Properties

FhuA: From Iron-Transporting Transmembrane Protein to Versatile Scaffolds through Protein Engineering.

ConspectusProtein engineering has emerged as a powerful methodology to tailor the properties of proteins. It empowers the design of biohybrid catalysts and materials, thereby enabling the convergence of materials science, chemistry, and medicine. The choice of a protein scaffold is an important factor for performance and potential applications. In the past two decades, we utilized the ferric hydroxamate uptake protein FhuA. FhuA is, from our point of view, a versatile scaffold due to its comparably large cavity and robustness toward temperature as well as organic cosolvents. FhuA is a natural iron transporter located in the outer membrane of Escherichia coli (E. coli). Wild-type FhuA consists of 714 amino acids and has a β-barrel structure composed of 22 antiparallel β-sheets, closed by an internal globular "cork" domain (amino acids 1-160). FhuA is robust in a broad pH range and toward organic cosolvents; therefore, we envisioned FhuA to be a suitable platform for various applications in (i) biocatalysis, (ii) materials science, and (iii) the construction of artificial metalloenzymes.(i) Applications in biocatalysis were achieved by removing the globular cork domain (FhuA_Δ1-160), thereby creating a large pore for the passive transport of otherwise difficult-to-import molecules through diffusion. Introducing this FhuA variant into the outer membrane of E. coli facilitates the uptake of substrates for downstream biocatalytic conversion. Furthermore, removing the globular "cork" domain without structural collapse of the ß-barrel protein allowed the use of FhuA as a membrane filter, exhibiting a preference for d-arginine over l-arginine.(ii) FhuA is a transmembrane protein, which makes it attractive to be used for applications in non-natural polymeric membranes. Inserting FhuA into polymer vesicles yielded so-called synthosomes (i.e., catalytic synthetic vesicles in which the transmembrane protein acted as a switchable gate or filter). Our work in this direction enables polymersomes to be used in biocatalysis, DNA recovery, and the controlled (triggered) release of molecules. Furthermore, FhuA can be used as a building block to create protein-polymer conjugates to generate membranes.(iii) Artificial metalloenzymes (ArMs) are formed by incorporating a non-native metal ion or metal complex into a protein. This combines the best of two worlds: the vast reaction and substrate scope of chemocatalysis and the selectivity and evolvability of enzymes. With its large inner diameter, FhuA can harbor (bulky) metal catalysts. Among others, we covalently attached a Grubbs-Hoveyda-type catalyst for olefin metathesis to FhuA. This artificial metathease was then used in various chemical transformations, ranging from polymerizations (ring-opening metathesis polymerization) to enzymatic cascades involving cross-metathesis. Ultimately, we generated a catalytically active membrane by copolymerizing FhuA and pyrrole. The resulting biohybrid material was then equipped with the Grubbs-Hoveyda-type catalyst and used in ring-closing metathesis.The number of reports on FhuA and its various applications indicates that it is a versatile building block to generate hybrid catalysts and materials. We hope that our research will inspire future research efforts at the interface of biotechnology, catalysis, and material science in order to create biohybrid systems that offer smart solutions for current challenges in catalysis, material science, and medicine.

Hydrophilic interaction liquid chromatography with methanol-water eluent on a zeolite

BackgroundHydrophilic interaction chromatography (HILIC) works with organic solvent-water mixtures as eluent and is based on the formation of a water enriched liquid phase on the surface of a hydrophilic stationary phase. Hydrophilic solutes are retained on that stagnant water-rich film depending on the difference of solvation compared to the mobile phase composition. However, the enhancement of selectivity by increasing the fraction of organic cosolvent is coupled with a limitation the analyte solubility, and the improvement of the HILIC principle by new hydrophilic stationary phases is the remaining option. ResultsY-zeolite (faujasite, FAU type) in the Na+-form with an average particle diameter of 5 μm was used as packing material in a 125 mm long HPLC column. The chromatographic response of the column was tested in methanol-water mixtures as eluent after injection of several aliphatic alcohols, polyols and monosaccharides with eluent conditions where no separation occurs on diol functionalized silica. On the zeolite the retention time increases according to ethylene glycol < glycerol < erythritol < sorbitol < inositol. The separation principle is explained to be superposed by two effects: firstly, a partition equilibrium between the water-rich phase in the zeolite micropores exists, and secondly, selective interactions with the inner crystalline pore surface and fixed-position Na+ ions, both serving to enhance the selectivity. Furthermore, arabinose and fructose monosaccharides could be separated into their tautomeric forms. Only upon increasing the temperature from 20 to 60 °C the tautomeric pattern merges into a single peak. Significance and noveltyInstead of the stagnant water rich surface layer, zeolite micropores now take over that function. As a result, the selectivity among polyols and between α/β-arabinopyranose and β-fructopyranose/β-fructofuranose tautomers is extraordinary superior towards conventional hydrophilic interaction liquid chromatography (HILIC).

Polyamide composite membrane with 3D honeycomb-like structure via acetone-regulated interfacial polymerization for high-efficiency organic solvent nanofiltration

High-performance organic solvent nanofiltration (OSN) membranes play an indispensable role in chemical separation processes. However, conventional OSN membranes such as thin-film composite polyamide (TFC-PA) membranes exhibit insufficient perm-selectivity. In this study, we developed a high-performance TFC-PAOSN membrane on a porous polyketone (PK) support by regulating interfacial polymerization (IP) with acetone as an organic co-solvent. The effect of the acetone co-solvent on the IP reaction and PA nanofilm morphology was investigated. Acetone serves as a regulator to mediate the IP reaction by facilitating the convective diffusion of monomers at the aqueous/organic interface. Furthermore, experimental results and molecular dynamics (MD) simulation analysis confirmed that the addition of acetone increases the width of the IP reaction zone, facilitates more violent exothermic reactions, and induces aggravated vaporization of acetone, resulting in the formation of a 3D honeycomb-like structure with an ultrahigh specific surface area. Compared with the TFC-PA membrane prepared by the conventional IP method, the TFC-PA-acetone membrane prepared by acetone-regulated IP (ARIP) exhibited 2.6 times higher methanol solvent permeance (7.0 LMH/bar) and comparable methyl orange rejection (94.6%). This work explores the underlying mechanism of acetone-regulated IP, providing a facile strategy for tailoring the membrane morphology with high-efficiency organic solvent nanofiltration.

How Medium Affects the Activity and Stereopreference of Thermoanaerobacter ethanolicus Secondary Alcohol Dehydrogenase Catalyzed Reduction of Ketones

Abstract: The activity and selectivity of W110G Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase were altered by cosubstrate and cosolvent at varying temperatures. A sharp drop in the enantiomeric excess (ee) was observed at 60 oC in the first 3 h, suggesting increased selectivity mistakes in the reduction of 4-phenyl-2-butanone to the expected (S)-4-phenyl-2-butanol using 5% v/v of 2-propanol as a cosubstrate. The ee increased exponentially with cosubstrate concentration, reaching ≥94% with 30-70% v/v 2-propanol. However, a decrease in enzyme activity was noticed at ≥30% v/v 2-propanol by a sharp drop in conversion. The lowest ee (&lt;3%) was registered using 5% v/v 2- propanol at 30-40 oC, which prolonged enzyme life that allowed reversible redox reaction with selectivity mistakes to give the R-alcohol compared to ≥18% ee at 50-60 oC, where faster reaction rates promoted selectivity mistake, but enzyme life was shortened by protein denaturation at the elevated temperatures. Water-miscible and immiscible organic cosolvents (25% v/v) increased enzyme selectivity. For methanol, ethanol, ethylene glycol and tert-butanol, the activity/conversion decreased with an increase in pKa and log P while the stereoselectivity/ee increased.

Effect of trifluoroethanol on antibodies binding properties

The studies on the influence of organic co-solvents on the structure and function of antibodies are of key interest, especially in view of antibodies broad use as recognizing elements in different analytical systems. Here we studied the effect of co-solvent 2,2,2-trifluoroethanol (TFE) on the ability of anti-ovalbumin monoclonal antibodies to interact with its specific antigen. Antibody affinity to antigen and the rate constants of antibody binding to immobilized antigen were analyzed. Changes in antibody reactivity with incubation time which depended on TFE concentration and temperature were revealed. When treatment of antibodies with TFE was carried out at 0°C, we observed nonlinear, non-monotonous changes of antibody reactivity with initial fast decrease and substantial increase that may be related to the loss of antigen binding reactivity by some part of antibodies at the start but its restoration when the incubation proceeds. Keywords: 2;2;2-trifluoroethanol, antibody affinity, antigen-antibody interaction, monoclonal antibodies, ovalbumin