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This study investigates the interface between ice and organic solvents using atomic force microscopy (AFM). Atomically flat ice surfaces were prepared and observed by AFM in 1-octanol, 1-hexanol, and 1-butanol. The results show differences in surface roughness influenced by the interaction of ice and alcohols. Young's modulus of ice was analyzed by force curve measurements, providing valuable insights into the properties of ice in liquid environments. The results showed the characteristics of the ice surface in different solvents, suggesting potential applications in understanding surface and interface phenomena associated with ice under realistic conditions. [ABSTRACT FROM AUTHOR]

In this novel attempt to enhance the removal of oils and organic solvents from wastewater, making water safer and cleaner for use, poly(ethylene-co-vinyl acetate was blended with organically modified montmorillonite (OMMT) nanoclay following a green pathway by melt blending in a Brabender plasticoder. The prepared nanocomposites exhibited excellent adsorption capacity for various oils and organic solvents. To further increase the adsorption capacity of the nanocomposites, NaCl was added as a porogen in the melt mixing process, followed by the leaching of NaCl in water to generate a highly porous nanocomposite material. The adsorption tests revealed excellent efficiency, with an adsorption capacity of 40 g g−1 in dichloromethane (DCM), 11 g g−1 in gasoline, and 5 g g−1 in crude oil. The nanocomposites demonstrated excellent recycling capability and could be reused for more than 30 adsorption–desorption cycles. FTIR, XRD, SEM, and TEM analyses were conducted to delineate the structure and morphology of the nanocomposite. [ABSTRACT FROM AUTHOR]

Existing adsorption materials with drawbacks in the weak organic solvents/oil retention ability, slow adsorption speed and low adsorption capacity for alkanes still hardly meet demands of the application field, especially in emergencies. The copolymerization of the long‐chain alkenes, 1‐octene, with isoprene was designed in this paper to synthesize an adsorption resin (PIOT), instead of acrylate monomers reported in the literature. And trimethylolpropane triacrylate was designed as a crosslinking agent. Results show that the PIOT grows in the form of powders, which are the loose accumulation of nanoflakes with a diameter of about 47.89 ± 11.06 nm. In view of the chain structure and morphology of the PIOT, it can quickly reach the maximum adsorption within 10 s along with a high adsorption capacity for various solvents and kerosene. Even for hexane, the adsorption capacity of the PIOT increases by 345.2% compared with the reported adsorption resin. The oil retention rate of PIOT can be maintained at 86 ± 6% after centrifugation at 1000–3000 rpm for 5–25 min. Compared with commercial activated carbon, the PIOT has outstanding advantages in recycling property and oil retention rate and compared with the reported acrylate adsorption resin, the PIOT has made a great breakthrough in adsorption capacity for alkanes. [ABSTRACT FROM AUTHOR]

Laccases act as green catalysts for oxidative cross-coupling of phenolic antioxidnt compounds, but low stability and non-recyclability limit its application. To address that, metal–organic frameworks Cu-BTC and Cr-MOF were synthesized as supports to immobilize the efficient laccase from Cerrena sp. HYB07. The Brunauer–Emmett–Teller surface area of Cu-BTC and Cr-MOF were 1213.2 and 907.1 m2/g, respectively. The two carriers respectively presented pore diameters of 1.2–10 nm and 1.4–12 nm as octahedron, indicating nano-scale mesoporosity. These Cu-BTC and Cr-MOF carriers could adsorb laccase with enzyme loading of 1933.2 and 1564.4 U/g carrier, respectively. The stability and organic solvent tolerance of Cu-BTC-laccase and Cr-MOF-laccase were both obviously improved compared to free laccase. Thermal inactivation kinetics showed that both the two immobilized laccases displayed lower thermal inactivation rate constants. Importantly, the Cu-BTC-laccase and Cr-MOF-laccase both showed much higher activity for cross-coupling of ethyl ferulate than free laccase, which had 2.5-fold higher cross-coupling efficiency than that by free laccase. The ethyl ferulate coupling product was also analyzed by mass spectroscopy and the synthesis pathway of ethyl ferulate dimer was proposed. The cross coupling of ethyl ferulate required the formation of radical intermediates of ethyl ferulate generated by laccase mediated oxidation. This work paved the way for MOFs immobilized laccase for cross coupling of antioxidant phenols. [ABSTRACT FROM AUTHOR]

Tomato peel by-products contain high levels of lycopene, which has traditionally been extracted using organic solvents. This research focuses on the optimisation of a sustainable method to obtain a lycopene-rich extract using the biodegradable anionic surfactant sodium dodecyl sulphate (SDS). A Plackett–Burman experimental design was used to investigate the effect of seven factors on the extraction of carotenoids from tomato peels using sodium dodecyl sulphate (SDS volume and concentration, homogenisation intensity and time, sonication phase, extraction time and ultracentrifugation intensity). Based on the responses of total carotenoid extraction, the SDS volume, the use of ultrasound and the extraction time significantly influenced the extraction yield and were selected for optimisation using a Box–Wilson experimental design. The final green extraction protocol (1 g sample + 11.9 ml SDS 0.3%, homogenisation at 13,500 rpm for 2 min, ultrasound phase, agitation for 8.2 h and ultracentrifugation) was selected after quantification of total carotenoids by UV–VIS and HPLC-DAD. Finally, we used nuclear magnetic resonance to demonstrate a high lycopene purity in the carotenoid extract obtained. Furthermore, using transmission electron microscopy, we observed the presence of intact chromoplasts in the extract, protecting the carotenoids from the exposure to external agents. Thus, this work reports an optimised method for the sustainable extraction of carotenoids and demonstrates the viability of the degradable solvent SDS for the extraction of liposoluble bioactive compounds, like carotenoids and mainly lycopene. The lycopene extract could be used for the technological and nutritional enrichment of new foods and/or the design of nutraceuticals. [ABSTRACT FROM AUTHOR]

A novel and efficient method has been developed for synthesizing benzothioamide from benzonitrile in supercritical CO2, which could be used to synthesize various benzothioamide derivatives efficiently with yields of up to 98% without the need for organic solvent. Notably, some H2S-based salts were designed and prepared, and they were found to be effective catalysts in promoting the thiolysis of benzonitrile to produce benzothioamide in an excellent yield. Furthermore, the utilization of supercritical CO2 as a solvent has demonstrated a remarkable increase in the yield of the desired product compared to conventional solvents for promoting benzonitrile thiolysis. Additionally, the investigation of the reaction mechanism has revealed that the acid–base properties of the reaction solution played a crucial role in the thiolysis of benzonitrile mediated by the H2S-based salts. [ABSTRACT FROM AUTHOR]

Cross-linkable hole-transporting materials with a new cross-linking group, benzocyclobutene, are designed and synthesized. These materials dissolve well in common organic solvents and exhibit excellent solvent resistance after thermal cross-linking. Electroluminescent (EL) devices were fabricated using these two hole-transporting materials. [ABSTRACT FROM AUTHOR]

A novel and efficient method has been developed for synthesizing benzothioamide from benzonitrile in supercritical CO2, which could be used to synthesize various benzothioamide derivatives efficiently with yields of up to 98% without the need for organic solvent. Notably, some H2S-based salts were designed and prepared, and they were found to be effective catalysts in promoting the thiolysis of benzonitrile to produce benzothioamide in an excellent yield. Furthermore, the utilization of supercritical CO2 as a solvent has demonstrated a remarkable increase in the yield of the desired product compared to conventional solvents for promoting benzonitrile thiolysis. Additionally, the investigation of the reaction mechanism has revealed that the acid–base properties of the reaction solution played a crucial role in the thiolysis of benzonitrile mediated by the H2S-based salts. [ABSTRACT FROM AUTHOR]

This study focuses on the development a green synthesis of epoxy fatty acids (EFAs) which are commonly used as the plasticizer in polymer industries. The intracellular lipases of Candida catenulata cells as a whole-cell biocatalyst (WCB) were examined in the bio-epoxidation of free fatty acids (FFAs) with hydrogen peroxide. The FFAs in soybean soap stock, an industrial by-product of vegetable oil factories, was used as the feedstock of the process. To remove phosphates from soap stock a degumming process was tested before the bio-epoxidation reaction and results revealed that the EFAs yield was improved using the degummed fatty acids (DFAs). The attachments of magnetic Fe 3 O 4 nanoparticles to the surface of WCBs facilitated the recovery of the biocatalyst, and were improved stabilities. The activation energy for the magnetic whole-cell biocatalysts (MWCB) was 48.54 kJ mol−1, which was lower than the WCB system (51.28 kJ mol−1). The EFA yield was about 47.1 % and 33.8 % after 3 h for the MWCBs and 2 h for the WCBs, respectively. The MWCBs displayed acceptable reusability in the repetitious bio-epoxidation reaction with maintaining 59 % of the original activity after 5 cycles whereas the performance of the WCBs was 5.9 % at the same conditions. The effects of influential factors such as reaction time, molar ratio of H 2 O 2 to C C, and batch and semi-batch operations were investigated for both biocatalyst systems. The quality of EFAs was characterized by FTIR and GC-MS analyses. • A novel intracellular lipase of C. catenulata were introduced for epoxidation of free fatty acids. • A oil refinery waste after pretreatment was used as the feedstock of epoxy fatty acid production. • Magnetic whole-cell biocatalyst was developed by loading of Fe 3 O 4 nanoparticles on cell-surface. • The presence of water, organic solvent, and different molar ratios of H 2 O 2 /C C were examined. • The bare whole cells and magnetic whole cells were examined in batch and semi-batch experiments. [ABSTRACT FROM AUTHOR]

Seaweed is an increasingly recognized source of secondary metabolites with a significant role as a plant biostimulant. With the rising popularity of organic farming, there is a pressing need to investigate the utilization of organic solvents derived from natural sources for seaweed extraction. Understanding the composition of these extracts is crucial for elucidating their role as biostimulants in plant growth. Hence, the present study aimed to explore the phytochemical composition and untargeted metabolomics of four extracts of Caulerpa racemosa (SW), prepared organically using vinegar, fermented buttermilk, and cow urine, in comparison with the conventionally used solvent, water. Approximately 95 volatile metabolites that belong to 22 chemical classes were identified through GC--MS analysis. The major classes detected include benzene and its substituted derivatives (24%), fatty acyls (17%), phenols (12%), benzofurans (8%), organo-oxygen compounds (6%), steroids and steroid derivatives (5%), and indole and its derivatives (4%). A significant shift in the composition of volatile metabolites was observed among the organic extracts as determined through a combination of various statistical analyses. A principal component analysis (PCA) highlighted seven principal components (PCs), which accounted for 99.9% of the total variance. Hierarchical cluster analysis delineated two distinct clusters, which signify a clear differentiation among the organic extracts. Furthermore, partial least squares discriminant analysis (PLS-DA) highlighted 49 volatile metabolites of significant importance, evident from variable importance in projection (VIP) scores of more than 1. These results underscore the intricate and distinct metabolomes inherent in Caulerpa racemosa organic extracts, hinting at their potential as biostimulants for plant growth. This study establishes a foundation for deeper investigations into seaweed extraction utilizing easily accessible organic solvents, presenting potential benefits for farmers. [ABSTRACT FROM AUTHOR]

Simultaneously achieving high-efficiency, deep-red emission, and solution-processed organic light-emitting diodes (OLEDs) remains a huge challenge. In this work, a thermally activated delayed fluorescent (TADF) material of CzPXZ that exhibits aggregation-induced emission property and a deep-red phosphorescent emitter of Ir(dmppy)(piq)2(od) are developed to build effective energy transfer pathways by dissolving them in a non-polar organic solvent. The electroluminescent emission peaks of CzPXZ:Ir(III)-based OLEDs are located at deep-red 626 nm, demonstrating efficient energy transfer from CzPXZ to the Ir(III) complex. Furthermore, an optimized DPEPO hole-blocking layer is utilized in such Ir(III)-doped OLEDs to enhance the radiative recombination. Therefore, a high external quantum efficiency of 43.76% is achieved for CzPXZ:Ir(III)-based OLEDs. This work sheds light on the great potential of energy transfer from AIE-TADF to red phosphorescent emitters for high-efficiency, solution-processed, deep-red OLEDs. [ABSTRACT FROM AUTHOR]

Objective: The goal of the research presented here is to determine if methods previously developed for the aqueous extraction of PrPSc from formalin-fixed paraffin-embedded tissue (FFPET) are applicable to the detection PrPSc by real-time quaking induced conversion (RT-QuIC). Previous work has utilized aqueous extraction of FFPET for detection of transmissible spongiform encephalopathies (TSEs) utilizing western blot and ELISA. This research extends the range of suitable methods for detection of TSEs in FFPET to RT-QuIC, which is arguably the most sensitive method to detect TSEs. Results: We found complete agreement between the TSE status and the results from RT-QuIC seeded with the aqueous extract of FFPET samples. The method affords the diagnostic assessment TSE status by RT-QuIC of FFPET without the use of organic solvents that would otherwise create a mixed chemical-biological waste for disposal. [ABSTRACT FROM AUTHOR]

Laccase is a multicopper enzyme that plays a unique role in bioremediation of environmental pollutants. Bacteria were isolated from hospital wastewater and screened for laccase production. The laccase production process condition was optimised, and the laccase obtained was characterised. The 16S rRNA molecular analysis conducted on the best laccase producer revealed a Bacillus sp. NU2 identified. The process conditions: pH5, 45°C, 100 rpm, 5% inoculum, and growth constituents viz: tangerine peel and wheat bran agro-wastes, beef extract, ammonium persulfate, glucose, galactose, xylose, sorbitol, fructose carbon sources; and 4-aminophenol inducer optimally stimulated laccase production. The Bacillus sp. NU2 laccase was optimal at pH and temperature conditions of 8.0°C and 60°C, with a noteworthy pH and thermal stability observed. Furthermore, NU2 laccase showed a moderate/high tolerance and relative activity effect on various chemical inhibitors, halides and surfactant of triton x-100 (105 ± 0.92%), PMSF (107 ± 0.81%), and NaCl (94 ± 0.81%) at 1, 3, and 6 (mM) concentration. Additionally, NU2 laccase maintained a relative activity of 101%, 104%, and 102% for Mg2+, Zn2+, and Fe3+ at 1, 3, and 6 mM respectively. Acetone and propanol significantly upregulated laccase activity at 114 ± 0.0008% and 118.24 ± 0.35 and also at 30 and 20 (%) concentrations. Conclusively, the tolerant effect of Bacillus sp. NU2 laccase in pH, temperature, inhibitors and organic solvents suggests its potential for biotechnological application and promotion of a greener environment. [ABSTRACT FROM AUTHOR]

AbstractBiodegradation of plastic is the most eco-friendly degradation process conferred by various microbial enzymes, especially the lipase enzymes. The lipase enzymes depict a broad substrate range, high regio/stereoselectivity, and stability in organic solvents. However, enhancing the catalytic activity of lipases for industrial production remains a challenge, predominantly due to the need for their extensive mechanistic characterization. Here, we employed a multidisciplinary approach to illustrate the comprehensive physiochemical and mechanical properties of 102 lipase sequences from six different groups of plastic-degrading microorganisms. Molecular docking-based evaluation of the binding efficiencies of selected lipases with the most common plastic polymers- polyurethane (PUR) and polyethylene terephthalate (PET), revealed that the archaeal lipase had the lowest binding energy of −7.1 kcal/mol with PET. Remarkably, the molecular dynamic simulation studies (up to 100 ns) and very low RMSD (0.3 nm) and RMSF (0.25 nm) values further ascertained the stability of archaeal lipase after binding with PET polymer. Further, a 2.19 nm radius of gyration (Rg) within 100 ns simulation time, binding free energy ΔGTOTAL with −24.36 kcal/mol and entropy factor -TΔS 7.65 kcal/mol also indicated strong binding of archaeal lipase with PET polymer. The mechanistic exploration of archaeal lipase yielded valuable insights into its effective binding with PET polymer, paving the way for future lipase enzyme engineering and harnessing its industrial potential for plastic biodegradation. [ABSTRACT FROM AUTHOR]

The development of cleaner, more environmentally friendly processes in polymerization technology is crucial due to the prevalent use of volatile organic solvents (VOCs), which are harmful and toxic. Future regulations are likely to limit or ban VOCs. This review explores the use of supercritical solvents, specifically supercritical CO2 (scCO2), in polymerization processes. The study focuses on reversible addition‐fragmentation chain‐transfer (RAFT) induced homo‐polymerization of various monomers using specific chain transfer agents (CTAs) in scCO2. RAFT polymerization, a reversible deactivation radical polymerization (RDRP) polymerization, relies heavily on the choice of CTA, which significantly influences the dispersity and molar mass of the resulting polymers. Stabilizers are also crucial in controlling product specifications for polymerizations in supercritical CO2, except for fluor‐based polymers, although they must be removed and preferably recycled to ensure product purity and sustainability. The review notes that achieving high molar mass through RAFT polymerization in scCO2 is challenging due to solubility limits, which lead to polymer precipitation. Despite this, RAFT polymerization in scCO2 shows promise for sustainable, circular production of low molar mass polymers, although these cannot yet be fully considered green products. [ABSTRACT FROM AUTHOR]

Amino acids have a crucial role in the field of asymmetric organocatalysis for the production of chiral compounds with high added value and specific biological activity. In particular, proline offers high activity and stereoselectivity for catalyzing aldol reactions in organic solvents. However, proline‐based catalysts often lack water‐solubility, accessibility, catalytic performance, or recovery in aqueous media. This work reports the design of proline‐functionalized poly(methyl methacrylate) (PMMA) nanoparticles with a magnetic core that offer high availability of chiral units in water and high recyclability. A proline‐based copolymerizable surfactant is designed and integrated onto the surface of PMMA nanoparticles through a miniemulsion polymerization process without using additional surfactants. The miniemulsion technique allows the incorporation of magnetite to the system to create a magnetically separable catalyst. The chiral nanocatalyst presents a high diastereoselective catalytic activity for the intermolecular aldol reaction between p‐nitrobenzaldehyde and cyclohexanone in water. [ABSTRACT FROM AUTHOR]

Picric acid is known as one of the most dangerous explosive materials and it has become one of the main pollutants in soil and, inter alia, groundwater. To date, many organic or inorganic probes have been reported to detect picric acid, especially in organic solvent systems. Nonetheless, the detection and adsorption of trace (sub-ppm or ppb level) picric acid in aqueous media remain challenging. Herein, we describe the facile synthesis of a tetraphenylethylene-based superphane cage via [6 + 2] condensation of dialdehyde and hexakis-amine, followed by a NaBH4–mediated reduction. This purely covalent organic cage was found able to show aggregation enhanced emission in a mixture of tetrahydrofuran and water (1:9, v/v), which can be utilised as a probe for detection of picric acid with ultrahigh sensitivity (as low as 0.9 ppb) and selectivity (against other tested nitroaromatic compounds). More importantly, this new superphane cage can serve as a new nonporous amorphous superadsorbent (NAS) material for adsorption of picric acid with an exceptional maximum uptake capability of 454 mg g−1. It also proved able to eliminate trace picric acid from aqueous media with up to 99% removal efficiency, meeting the discharge standard (<1.0 ppb). As such, we believe that this study offers new insight into the design and synthesis of NAS-based advanced materials for sensitive and selective detection and adsorption of trace pollutants from complex aqueous wastes. [ABSTRACT FROM AUTHOR]

Converting lignin into aromatic chemicals is a promising strategy for the high‐value utilization of lignocellulosic feedstock. However, the inherent heterogeneity of lignin poses a significant obstacle to achieving efficient conversion and optimal product yields within bio‐refinery systems. Herein, we employed a one‐step fractionation method to enhance lignin homogeneity and utilized the THF/DMSO‐EtONa (tetrahydrofuran/dimethyl sulfoxide‐sodium ethoxide) system to depolymerize the fractionated lignin. Three protic and three aprotic solvents were used for fractionation. The impact of the solvent properties on the structure and the depolymerization efficiency of the fractionated lignin was investigated. Methanol‐fractionated lignin generated the benzoic acid compounds with a yield of 30 wt%, 50 % higher than that of the unfractionated lignin. The polarities (δP), hydrogen bonding abilities (δH), and viscosities (η) of selected protic solvents showed strong linear correlation with molecular weight (Mw), polymer dispersity index (PDI), and syringyl/guaiacyl ratio (S/G ratio) of the fractionated lignin, as well as the total yield of benzoic acid compounds derived from the β‐O‐4 bond cleavage. This study elucidates the relationship between solvent properties and lignin structure and proposes a promising approach for refining lignin to enhance utilization efficiency, thereby presenting a potential strategy for value‐added application of complex lignin polymers. [ABSTRACT FROM AUTHOR]

Pyrylium salts based on a cationic oxygen heterocycle are a key class of chromophores. However, synthesis of these salts generally requires use of harsh acids, copious organic solvents, and in many cases, hazardous conditions. This work provides a two-pot synthesis for substituted triphenyl pyrylium salts wherein chalcone intermediates are first prepared and then mild methanesulfonic acid is used in combination with a dehydrating agent to drive pyrylium cyclization. Purification is achieved through a simple, aqueous workup involving counterion metathesis which avoids the need for environmentally unfriendly organic solvents. This mild, green approach has been applied to synthesize a collection of known pyryliums as well as a new family of red-shifted pyrylium chromophores bearing p -pyrrolidinylphenyl substituents. The synthesis of the latter group demonstrates that unlike other current methods, our approach offers enhanced functional group tolerance as well as finer control over substituent placement. [ABSTRACT FROM AUTHOR]

Carotenoids are high added-value products primarily known for their intense coloration and high antioxidant activity. They can be extracted from a variety of natural sources, such as plants, animals, microalgae, yeasts, and bacteria. Gordonia alkanivorans strain 1B is a bacterium recognized as a hyper-pigment producer. However, due to its adaptations to its natural habitat, hydrocarbon-contaminated soils, strain 1B is resistant to different organic solvents, making carotenoid extraction through conventional methods more laborious and inefficient. Ionic liquids (ILs) have been abundantly shown to increase carotenoid extraction in plants, microalgae, and yeast; however, there is limited information regarding bacterial carotenoid extraction, especially for the Gordonia genus. Therefore, the main goal of this study was to evaluate the potential of ILs to mediate bacterial carotenoid extraction and develop a method to achieve higher yields with fewer pre-processing steps. In this context, an initial screening was performed with biomass of strain 1B and nineteen different ILs in various conditions, revealing that tributyl(ethyl)phosphonium diethyl phosphate (IL#18), combined with ethyl acetate (EAc) as a co-solvent, presented the highest level of carotenoid extraction. Afterward, to better understand the process and optimize the extraction results, two experimental designs were performed, varying the amounts of IL#18 and EAc used. These allowed the establishment of 50 µL of IL#18 with 1125 µL of EAc, for 400 µL of biomass (cell suspension with about 36 g/L), as the ideal conditions to achieve maximal carotenoid extraction. Compared to the conventional extraction method using DMSO, this novel procedure eliminates the need for biomass drying, reduces extraction temperatures from 50 °C to 22 ± 2 °C, and increases carotenoid extraction by 264%, allowing a near-complete recovery of carotenoids contained in the biomass. These results highlight the great potential of ILs for bacterial carotenoid extraction, increasing the process efficiency, while potentially reducing energy consumption, related costs, and emissions. [ABSTRACT FROM AUTHOR]

The recovery of scandium (Sc) from highly acidic industrial effluents is currently hindered by the use of large quantities of flammable and toxic organic solvents. This study developed an extraction system using ionic liquids (ILs) and phenylphosphinic acid (PPAH) as diluents and an extractant, respectively, to selectively recover Sc from the aqueous phase. The effect of IL chemical structure, aqueous pH and temperature on the extraction of Sc was systematically investigated and the findings revealed that ILs with longer alkyl side chains had reduced Sc extraction ability due to the presence of continuous nonpolar domains formed by the self-aggregation of the IL alkyl side chain. The IL/PPAH system maintained high extraction ability toward Sc across a wide temperature range (288 K to 318 K) and the extraction efficiency of Sc could be improved significantly by increasing the aqueous pH. The extraction process involved proton exchange, resulting in the formation of a metal−ligand complex (Sc(PPA)3). [ABSTRACT FROM AUTHOR]

Levulinic acid (LA) is one of the top bio‐based platform molecules that can be converted into many valuable chemicals. Herein, we report the sustainable synthesis of LA acid from various sugars using heteropolyacid catalysts. By using a Box–Behnken design of experiment, both LA yield (up to 69 mol%) and complete suppression of parasitic humin formation could be achieved within a 5 h reaction time at 140°C using fructose as a substrate. The effects of various reaction parameters like temperature, sugar concentration, addition of organic co‐solvent and reaction time on LA yield and humin formation were examined in a three‐dimensional space. Moreover, the results could be successfully transferred to other sugars like glucose or cellobiose, paving the way for an atom‐efficient and sustainable LA synthesis process. [ABSTRACT FROM AUTHOR]

With the industrialization and development of modern science, the application of enzymes as green and environmentally friendly biocatalysts in industry has been increased widely. Among them, lipase (EC. 3.1.1.3) is a very prominent biocatalyst, which has the ability to catalyze the hydrolysis and synthesis of ester compounds. Many lipases have been isolated from various sources, such as animals, plants and microorganisms, among which microbial lipase is the enzyme with the most diverse enzymatic properties and great industrial application potential. It therefore has promising applications in many industries, such as food and beverages, waste treatment, biofuels, leather, textiles, detergent formulations, ester synthesis, pharmaceuticals and medicine. Although many microbial lipases have been isolated and characterized, only some of them have been commercially exploited. In order to cope with the growing industrial demands and overcome these shortcomings to replace traditional chemical catalysts, the preparation of new lipases with thermal/acid-base stability, regioselectivity, organic solvent tolerance, high activity and yield, and reusability through excavation and modification has become a hot research topic. [ABSTRACT FROM AUTHOR]

Protists, including ciliates retain crystals in their cytoplasm. However, their functions and properties remain unclear. To comparatively analyze the crystals of Paramecium bursaria, a ciliate, associated with and without the endosymbiotic Chlorella variabilis, we investigated the isolated crystals using a light microscope and analyzed their length and solubility. A negligible number of crystals was found in P. bursaria cells harboring symbiotic algae. The average crystal length in alga-free and algae-reduced cells was about 6.8 μm and 14.4 μm, respectively. The crystals of alga-free cells were spherical, whereas those of algae-reduced cells were angular in shape. The crystals of alga-free cells immediately dissolved in acids and bases, but not in water or organic solvents, and were stable at – 20 °C for more than 3 weeks. This study, for the first time, reveals that the characteristics of crystals present in the cytoplasm of P. bursaria vary greatly depending on the amount of symbiotic algae. [ABSTRACT FROM AUTHOR]

Mole fraction solubilities are reported for (2-nitrophenyl)acetic acid dissolved in 1-pentanol, 1-heptanol, 1-octanol, 2-butanol, 3-methyl-1-butanol, 2-pentanol, 4-methyl-2-pentanol, cyclopentanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 1,4-dioxane, methyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, pentyl acetate, methyl butyrate, dimethyl adipate and propanenitrile at 298.15 K. Solubilities were determined using a spectrophotometric method of chemical analysis. Experiment-based Abraham model solute descriptors are calculated for the molecular, monomeric form of (2-nitrophenyl)acetic acid by combining our experimental values with the published solubility data obtained from the published paper by Zhou and co-workers. The calculated solute descriptors describe the observed solubility data to within an overall standard deviation of 0.10 log units. [ABSTRACT FROM AUTHOR]

Asphaltene deposition poses a significant threat to the safe production of crude oil as it tends to occur in forming porous media, wellbores, pipelines, and refining equipment. It is also responsible for the high viscosity of crude oil, making it challenging to recover heavy crude oil. This study investigates the impact of aliphatic chain length on asphaltene aggregation and the molecular properties of organic solvents and dispersants interacting with asphaltenes. To achieve this, two model asphaltenes, M1 and C5Pe, were used in molecular dynamics simulations using radial distribution function, root means square displacement, diffusion coefficient, solubility parameter, cohesion energy density, and interaction energy as characterization parameters. The simulations revealed that the aggregation onset of C5Pe and M1 occurs at 2–5 Å at room temperature and pressure, and π–π stacking is the primary mode of aggregation, with the presence of heteroatomic groups providing additional forces for stable aggregation. Additionally, it was found that the π–π interactions weakened with the increase of the side chain length. The study also investigated the molecular behavior of asphaltenes in six organic solvents and found that M1 was more soluble in aromatic solvents than C5Pe, and undesirable solvents could induce asphaltene aggregation. Furthermore, the effect of five dispersants on asphaltene aggregation was explored, with PIBSI, BEHP, B-DBSA, CTAB, and benzoic acid showing decreasing dispersing ability in that order at lower concentrations. However, at higher concentrations, the effect of some dispersants diminishes and triggers self-aggregation behavior. [ABSTRACT FROM AUTHOR]

Three types of 9,9-bis(4-hydroxyphenyl)fluorene-based diols reacted with 4,4′-difluorobenzophenone via nucleophilic substitution polymerization to afford the corresponding aromatic poly(ether ketone)s. The resulting polyketones have excellent solubility in typical organic solvents, such as THF, CHCl3, and NMP. They also have good thermal stability above 400 °C (Td10). In particular, the surface tension of the polyketone, which has four C4F9 groups per repeating unit, is 18.7 mN/m, which is equal to that of PTFE. The introduction of propylene linkers and many C4F9 groups per repeating unit was effective at improving water/oil repellency. [ABSTRACT FROM AUTHOR]

Microfibrillated cellulose (MFC) and hydroxypropyl methylcellulose (HPMC) were employed as gelling agents in hydroalcoholic solutions. However, a limited number of studies have explored the interactions between MFC and cellulose derivatives in organic solvents. Most of these studies have primarily focused on either the interactions between MFC and polymers in aqueous solutions. To investigate their collaborative effect, phase diagrams were constructed by varying the concentration of the constituent elements, confirming phase separation, and identifying liquid-like and gel-like properties through oscillatory rheological measurements. Oscillatory amplitude, frequency, oscillatory swing temperature and viscosity were performed. Additionally, aerogels were fabricated with and without ethanol for microscopic analysis. It was demonstrated that ethanol significantly influences the rheological characteristics of MFC and MFC + HPMC dispersions, resulting in an increase in the elastic modulus (G'), decreased thixotropic behavior, and increased stability. Tests were also conducted with urea, a strongly chaotropic agent, providing evidence of the types of interactions governing the systems, and demonstrating that intermolecular hydrogen bond interactions play a predominant role. [ABSTRACT FROM AUTHOR]

Carob plant extracts contain a variety of secondary metabolites (SM) with potential health benefits. Factors such as the extraction method and the geographical origin of the plant influence the extraction yield and quality of SM extracts. This study aims to increase the percentage of aqueous fraction in the solvent used to extract SM from carob pulp from distinct regions of Morocco (Ghafsai and Tainest). At the same time, it seeks to maximize the total phenolic content (TPC) in the extracts, minimize degradation, and preserve their integrity. A preliminary screening was conducted to assess the extraction efficiency of pure aqueous and organic solvents, revealing that water, methanol, and ethanol were the most effective solvents. The mixture response surface design methodology was then applied to investigate the synergistic effect of these solvents on the extraction of Total Phenolic Content (TPC). The results from the mixture design methodology (MDM) demonstrated that the optimal solvent system was a water/methanol/ethanol blend (50:30:20 v/v/v), yielding TPC concentrations of up to 55.47 ± 0.01 and 41.85 ± 0.04 mg GAE/g from carob samples collected in Ghafsai and Tainest, respectively. These extracts also exhibited notable IC50 values (DPPH: 328.18 ± 0.21 and 879.06 ± 0.15, ABTS: 65.71 ± 0.2 and 128.05 ± 0.17, FRAP: 328.18 ± 0.21 and 879.06 ± 0.15 µg/mL for Tainest and Ghafsai samples, respectively). This study underscores the synergistic effect of the solvent mixture on TPC extraction and the influence of interregional variation on SM contents. Overall, this study advocates for the promotion and increased utilization of water as a green solvent in SM extraction from plant material, aiming to mitigate toxicity and risks associated with high proportions of organic solvents used in the extraction process. [ABSTRACT FROM AUTHOR]

Auricularia auricula melanin has a variety of biological activities, but its application is limited because melanin is not easily soluble in water and most organic solvents. In this study, Auricularia auricula melanin was modified using arginine and analyzed for its structure, physicochemical properties, as well as antioxidant and antibacterial activities. It was found that the water solubility of melanin modified by arginine was 11.6 mg/mL. Arg-melanin is stable under cold dark conditions. Structural analysis by UV, IR and NMR revealed that Auricularia auricula melanin was mainly eumelanin. Arg-melanin exhibited scavenging activities of 75.4%, 76.7%, and 77.6% against DPPH radicals, OH radicals, and O2−, respectively, which were 9.6%, 42.2%, and 31.2% higher than those of melanin. The MICs of melanin and Arg-melanin were 2.5 mg/mL and 1.5 mg/mL against S. aureus, and 3 mg/mL against E. coli. The MIC and MBC values were identical. As the concentration of melanin increased, the strain exhibited greater growth inhibition and more nucleic acid leakage. Arginine modification of melanin can improve its water solubility, and can enhance the antioxidant and bacteriostatic activity of melanin, which provides a theoretical basis for the application of melanin in the field of food and medicine. [ABSTRACT FROM AUTHOR]

Purpose: The formalin-ethyl acetate (FEA) concentration method is commonly used in routine clinical practice to detect parasite eggs in feces. This procedure involves extraction of oil with the organic solvent ethyl acetate (EA), which reduces fecal sediment and provides a cleaner background for microscopic analysis. However, clinically, some sediment failed to float after EA treatment. Methods: Hexane, commonly used in the food oil extraction from oilseeds did not float the feces. Gas chromatography–mass spectrometry (GC–MS) analysis showed that neither the amount of the oil nor the classes of the oil determined was differed whether hexane or EA was used to float the feces. Oil red, Bodipy and Calcofluor staining showed that the unabsorbed oil droplets in the fecal sediment were trapped within the leaf structure. HCl or acetic acid was added to see if the acid residue could dissolve the cellulose of the leaf to promote the bulk float. Results: Our result showed that the fecal bulk contained the loosened mesophyll cell wall. The addition of acid residues improved fecal bulk float. The proximity of cellulose fiber to EA, but not hexane, may enhance the efficacy of oil extraction from cellulose. Conclusion: This is the first report that the interaction of cellulose with ethyl acetate in fecal solution has an effect on bulk float. This study improves the understanding of fecal bulk flotation and may assist in the visualization of parasite eggs in clinical practice with non-floating fecal samples in the FEA concentration method. [ABSTRACT FROM AUTHOR]

5‐Hydroxymethylfurfural (HMF) was transformed into 2,5‐diformylfuran (DFF) with nitric acid as the oxidant. The initial HMF content was as high as 12.5 wt %, and water was the sole solvent. This is an intensely exothermic reaction along with the emission of NO2 gas. A high DFF yield of 83.2 % was achieved if the oxidation ability of nitric acid matched with the requirement of target oxidation reaction while mismatched those of side reactions by regulating the initial concentration of nitric acid (59.5 wt %) and reaction temperature (50–60 °C). The oxidation reaction of HMF, overoxidation of HMF, and skeleton‐cracking reaction of FDCA preferred concentrated HNO3, hot HNO3, and concentrated or hot HNO3, respectively. After liquid‐liquid extraction, filtration, and column chromatography, light‐yellow DFF powders with purity of 92.1 wt % and isolated yield of 40.2 % were obtained and confirmed by NMR, FTIR, UV‐Vis, and elemental analysis. HMF was the dominant impurity due to its affinity to DFF. In addition, chromogenic substances were obtained as a byproduct, and they were potential pH indicators. These chromogenic substances had highly conjugated molecular structures, and they were generated via successive β‐protonation‐based ring‐opening reaction of HMF, aldol reaction, and dehydration reaction. [ABSTRACT FROM AUTHOR]

The present study outlines the approach that was employed for cloning, expression, and characterization of the recombinant pullulanase enzyme from Bacillus cereus ATCC 14579 into Escherichia coli BL21(DE3) using pET‐25b (+) expression vector. The recombinant pullulanase enzyme was purified using ammonium sulfate precipitation and immobilized metal ion affinity chromatography (IMAC). The molecular mass of the purified pullulanase enzyme was measured using sodium dodecyl sulfate‐polyacrylamide gel electrophoresis (SDS‐PAGE) as 95 kDa. The purified recombinant pullulanase enzyme demonstrated significant thermal stability, maintaining its structural integrity and functionality at temperatures as high as 90°C over a period of 4 h. The inclusion of divalent metal ions, specifically Ca2+ and Mg2+, had a positive effect on the activity of the pullulanase enzyme. Conversely, the presence of Co2+ and EDTA (Ethylene Diamine Tetra Acetic acid) resulted in suppression of the enzyme activity. The purified pullulanase enzyme demonstrated remarkable resistance when exposed to organic solvents. The enzyme activity was notably decreased in the presence of SDS (Sodium Dodecyl Sulfate) while β‐mercaptoethanol and tween‐60 did not substantially affect the enzyme activity and stability which suggest its potential applicability in the detergent sector. This discovery indicates a potential approach to improve the effectiveness of currently available detergents in the marketplace. [ABSTRACT FROM AUTHOR]

Highlights The preparation of functionalised graphene often involves consuming significant amounts of organic solvents, complicated steps, and expensive equipment. This study presented a simple, low‐cost, and efficient method for preparing well‐dispersed functionalised graphene. This method involved the microwave heating of commercial graphene precursors and ball milling of grafted expanded graphite, resulting in a short and straightforward preparation process without requiring large amounts of organic solvents. This process enabled the preparation of few‐layer graphene with a thickness of only 3.5 ± 0.5 nm. During this process, the majority of the surface oxygen‐containing groups were replaced by polyetheramine (D2000) at a grafting rate of up to 5.14%, which improved the interface adhesion strength between the graphene and the epoxy resin. The fabricated altered graphene notably enhanced the mechanical characteristics of the epoxy resin., that is, the toughening effect reached up to 171% with a graphene content of only 0.3 wt%, while the Young's modulus and tensile strength values increased by 54% and 39%, respectively. This process is cost‐effective, easy to operate, and highly efficient, making it suitable for the large‐scale production of well‐dispersed functionalised graphene. Pioneers mechanical chemical energy in graphene, a new materials science direction. First ball milling on microwave graphene, merging milling benefits with graphene. Ball milling cuts D2000 grafting time on graphene, boosting efficiency. Reduces organic solvent use, cutting costs and environmental effects. Ball milling lowers costs and impacts, aiding graphene material commercia‐lization. [ABSTRACT FROM AUTHOR]

Organic frameworks face a trade‐off between the framework stability and the bond dynamics, which necessitates the development of innovative linkages that can generate stable frameworks without hindering efficient synthesis. Although iodine(I)‐based halogen‐bonded organic frameworks (XOFs) have been developed, constructing XOFs based on bromine(I) is desirable yet challenging due to the high sensitivity of bromine(I) species. In this work, we present the inaugural construction of stable bromine(I)‐bridged two‐dimensional (2D) halogen‐bonded organic frameworks, XOF(Br)−TPy−BF4/OTf, based on sensitive [N⋅⋅⋅Br⋅⋅⋅N]+ halogen bonds. The formation of XOF(Br)−TPy−BF4/OTf was monitored by 1H NMR, XPS, IR, SEM, TEM, HR‐TEM, SEAD. Their framework structures were established by the results from PXRD, theoretical simulations and SAXS. More importantly, XOF(Br) displayed excellent chemical and thermal stabilities. They exhibited stable two‐dimensional framework structures in various organic solvents and aqueous media, even over a wide pH range (pH 3–12), while the corresponding model compounds BrPy2BF4/OTf decomposed quickly even in the presence of minimal water. Furthermore, the influence of the counterions were investigated by replacing BF4 with OTf, which improved the stability of XOF(Br). This characteristic enabled XOF(Br) to serve as an efficient oxidizing reagent in aqueous environments, in contrast with the sensitivity of BrPy2BF4/OTf, which performed well only in organic media. This study not only deepens our fundamental understanding of organic frameworks but also opens new avenues for the development and application of multifunctional XOFs. [ABSTRACT FROM AUTHOR]

Here, we successfully synthesized four structurally analogous, self‐assembled chiral molecular tubes with relatively high yields. This achievement involved the condensation of six equivalents of enantiomerically pure trans‐cyclohexane‐1,2‐diamine (trans‐CHDA) and three equivalents of the corresponding tetraformyl precursor. Each precursor was equipped with a luminescent linker terminated by two m‐phthalaldehyde units. Even though these tetraformyl precursors are barely soluble in almost all organic solvents, the molecular tubes are highly soluble in nonpolar solvents such as chloroform, allowing us to fully characterize them in solution. The stereo‐chirality of the chiral bisamino building blocks endows the frameworks of molecular tubes with planar chirality. As a consequence, all of these molecular tubes exhibit circularly polarized luminescence (CPL) with relatively large dissymmetry values |glum| up to 7×10−3, providing an efficient method for synthesizing CPL‐active materials. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) are promising next‐generation crystalline porous materials with exceptional structural, chemical, and application diversity. Since their discovery, the reticular tunability and physiochemical properties of MOFs have been studied and carefully manipulated to make them suitable for a wide variety of applications. After decades of research, these materials are moving from the benchtop to commercial, industrial‐scale production. Although MOFs are now widely explored, the overall environmental impacts of these emerging materials are still underexplored. In this work, the first example of overall assessment of ten industrially produced and widely explored MOFs considering 18 diverse environmental impact categories such as global warming potential, fossil resource scarcity, water consumption, ecotoxicity, etc. via cradle‐to‐gate life cycle assessment is presented. Importantly, this study presents a comprehensive comparison between different synthetic methods of each MOF and compiles the environmental impacts associated only with the individual “synthesis” or “washing” steps. This study highlights the critical importance of using of green solvents over organic to reduce the overall environmental footprint. By identifying the synthetic drawbacks associated with different methods, this work provides a blueprint for the sustainable design and required future development of MOF synthesis. [ABSTRACT FROM AUTHOR]

Catalysis has been at the forefront of the developments that has revolutionised synthesis and provided the impetus in the discovery of platform technologies for efficient C−C or C−X bond formation. Current environmental situation however, demands a change in strategy with catalysis being promoted more in solvents that are benign (Water) and for that the development of hydrophilic ligands (especially phosphines) is a necessity which could promote catalytic reactions in water, allow recyclability of the catalytic solutions and make it possible to isolate products using column‐free techniques that involve lesser usage of hazardous organic solvents. In this review, we therefore critically analyse such catalytic processes providing examples that do follow the above‐mentioned parameter. [ABSTRACT FROM AUTHOR]

The extraction of targets from biological samples for immunoassays using organic solvents, such as methanol, is often necessary. However, high concentrations of organic solvents in extracts invariably lead to instability of the employed antibody, resulting in poor performance of the immunoassay. Evaluating the tolerance ability and exploring the molecular mechanisms of antibody tolerance in organic solvents are essential for the development of robust immunoassays. In this work, 25 monoclonal antibodies and methanol are utilized as models to address these questions. A novel protocol is initially established to precisely and rapidly determine antibody tolerance in methanol, identifying two distinct methanol effect patterns. Through a detailed investigation of the structural basis, a novel hypothesis regarding methanol effect patterns is proposed, termed "folding‐aggregation," which is subsequently validated through molecular dynamics simulations. Furthermore, the investigation of sequence basis reveals significant differences in residue types within the complementarity‐determining regions and ligand‐binding residues, distinguishing the two antibody methanol effect patterns. Moreover, the methanol effect patterns of the antibodies are defined by germline antibodies. This work represents the first exploration of antibody methanol effect patterns and associated molecular mechanisms, with potential implications for the discovery and engineering of tolerant antibodies for the development of robust immunoassays. [ABSTRACT FROM AUTHOR]

To overcome the challenges associated with the toxicity of the majority of organic solvents for the liquid phase synthesis of solid electrolytes toward the human body and environment, we demonstrate the synthesis of tin-based sulphide electrolytes using water, which is the most environmentally friendly solvent. ortho-Thiostannate, i.e., Li4SnS4, was obtained from a mixture of Li2S, Sn, and S using aqueous solution synthesis. Furthermore, Li10SnP2S12, a superionic conductor, was obtained by mixing an aqueous solution of Li4SnS4 and tetrahydrofuran suspension of Li3PS4, which exhibited the highest ionic conductivity (5.9 × 10−3 S cm−1 at 25 °C) in liquid-phase synthesis. This study successfully demonstrates that water can be efficiently used to synthesize sulphide electrolytes instead of conventional organic solvents. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are gaining rapid prominence in numerous biocatalysis processes due to their green characteristics, biodegradability, low cost, and simple preparation compared to harsh organic solvents and toxic ionic liquids. However, natural enzymes tend to show activity reduction, even inactivation in the presence of many DESs. Here, we present the first rational design approach to achieve enzymes resistant to both DESs and high temperatures. Using the interaction pattern between DESs and BSLA (Bacillus subtilis lipase A, our model enzyme) derived from all-atom molecular dynamics (MD) simulations, we formulated a solvation-guided engineering strategy. This was established after assessing 33 structural, solvation, and energy observables. We rationally designed and experimentally tested 36 single substitutions, of which 28 (a 77.78% success rate) exhibited improvements in at least two DES cosolvents: choline chloride (ChCl) : acetamide, tetrabutylphosphonium bromide (TBPB) : ethylene glycol (EG), and ChCl : EG. Additionally, through stepwise recombination, we identified two robust BSLA variants, D64H/R107L/E171Y and D64H/R142L, showing stability improvements of up to 4.4-fold and 3.2-fold in three DESs and at 50 °C, respectively. Further MD studies demonstrated that (i) the restricted overall structure but fine-tuned local flexibility and (ii) increased water but decreased DES molecules at substituted sites are two main factors contributing to the enhanced multiple DES resistance. Overall, solvation-guided engineering offers an efficient and rational approach for designing lipases tolerant to DES cosolvents and elevated temperatures, with a considerable potential for adaptation to other enzymes. [ABSTRACT FROM AUTHOR]

A super-lightweight, bidirectionally ordered, three-dimensional porous hybrid graphene aerogel (HGA) was prepared and evaluated. The preparing parameters involved obtaining a uniform suspension through mechanical stirring for 3 h, followed by ultrasonic dispersion for 30 min, maintaining pH at 9. The suspension then underwent liquid nitrogen pre-freezing, vacuum freeze-drying for 48 h and hydrazine hydrate vapor reduction at 90 ℃ for 24 h. Furthermore, the microstructure, the adsorption and reusability properties of HGA were evaluated. The results demonstrated that HGA could adsorb organic solvents up to 159 times its own weight and effectively separate oil from water. The HGA exhibited excellent mechanical properties, releasing 98% of its shape with a 30% compression ratio under a stress 2653 times its own weight. Additionally, after 10 adsorption-combustion cycles, the adsorption capacity decreased by only 3.67%, and the mass retention rate exceeded 90%, indicating good reusability and flame-retardant properties. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DES) represent a promising class of green solvents, offering particular utility in the extraction and development of new formulations of natural compounds such as ferulic acid (FA). The experimental phase of the study undertook a systematic investigation of the solubility of FA in DES, comprising choline chloride or betaine as hydrogen bond acceptors and six different polyols as hydrogen bond donors. The results demonstrated that solvents based on choline chloride were more effective than those based on betaine. The optimal ratio of hydrogen bond acceptors to donors was found to be 1:2 molar. The addition of water to the DES resulted in a notable enhancement in the solubility of FA. Among the polyols tested, triethylene glycol was the most effective. Hence, DES composed of choline chloride and triethylene glycol (TEG) (1:2) with added water in a 0.3 molar ration is suggested as an efficient alternative to traditional organic solvents like DMSO. In the second part of this report, the affinities of FA in saturated solutions were computed for solute-solute and all solute-solvent pairs. It was found that self-association of FA leads to a cyclic structure of the C 2 8 type, common among carboxylic acids, which is the strongest type of FA affinity. On the other hand, among all hetero-molecular bi-complexes, the most stable is the FA-TEG pair, which is an interesting congruency with the high solubility of FA in TEG containing liquids. Finally, this work combined COSMO-RS modeling with machine learning for the development of a model predicting ferulic acid solubility in a wide range of solvents, including not only DES but also classical neat and binary mixtures. A machine learning protocol developed a highly accurate model for predicting FA solubility, significantly outperforming the COSMO-RS approach. Based on the obtained results, it is recommended to use the support vector regressor (SVR) for screening new dissolution media as it is not only accurate but also has sound generalization to new systems. [ABSTRACT FROM AUTHOR]

In this study, we focused on the fluorous affinity acting among fluorine compounds, and then developed a new separation medium and evaluated their performance. We prepared the stationary phases for a column using silica gel‐modified alkyl fluoride and investigated the characteristics of fluorous affinity by comparing them with a typical stationary phase, which does not contain fluorine, using high‐performance liquid chromatography (HPLC). In HPLC measurements, we confirmed that while all non‐fluorine compounds were not retained, retention of fluorine compounds increased as the number of fluorine increased with the stationary phase. It also revealed that the strength of fluorous affinity changes depending on the types of the organic solvent; the more polar the solvent, the stronger the effect. Additionally, the stationary phase was employed to compare the efficiency of our column with that of a commercially available column, Fluofix‐II. The retention selectivity was almost the same, but the absolute retention strength was slightly higher on our column, indicating that the column is available for practical use. [ABSTRACT FROM AUTHOR]

Solvothermal synthesis is the predominant method for creating new structured covalent organic frameworks (COFs), yet it grapples with challenges in controlling shape and morphology. This issue is attributed to the unregulated solvent‐feeding process, which results in rapid polymerization and uncontrolled phase separation. Consequently, a two‐step solvent‐feeding process is reported for the solvothermal shaping of imine‐linked COF monoliths with hierarchical porosity. The synthesis conditions for COF powders reported in existing literature are directly utilized without extensive optimization; however, solvents are divided into two segments prior to feeding. A minor segment of solvents is employed to dissolve monomers, which polymerize in situ to form amorphous monoliths. Subsequently, the remaining organic solvent, along with an acetic acid aqueous solution, is added for crystallization. The versatility of this two‐step feeding process in producing COF monoliths is illustrated. The high‐quality COF monoliths demonstrate benzene uptakes ranging from 6.0 to 16.8 mmol g−1 at 298 K. This study confirms that the two‐step solvent feeding process can be effectively integrated with the conventional solvothermal method to enhance the solution‐processability of COFs. It is anticipated that this modified solvothermal approach can readily shape COFs to meet practical application requirements. [ABSTRACT FROM AUTHOR]

[Display omitted] The formation of soft colloidal crystals, which are nonclose-packed ordered arrays of colloidal particles suspended in a solvent, is dictated by a single physical factor that yields a fixed threshold at order–disorder boundaries for different experimental conditions such as ion concentration, solvent type, and particle size. Identifying the determinant factor and its threshold value should enable the prediction of the critical concentrations of colloidal particles to form soft colloidal crystals. Soft colloidal crystals were fabricated using a series of monohydric alcohols as dispersion media and reflectance spectra were measured to locate order–disorder boundaries. The interaction forces acting between particles were also measured by employing atomic force microscopy. The interparticle forces at the order–disorder boundaries exhibited a universal threshold that was independent of the solvent types including alcohols and water. Therefore, the determinant factor for the formation of soft colloidal crystals was determined to be the force acting between the particles. Furthermore, a priori calculation of this critical force and consequently the critical particle concentration in colloidal systems was demonstrated by referring to the pressure at the liquid-to-solid transition in a hard sphere system (Alder transition). [ABSTRACT FROM AUTHOR]

The industrial separation of hydrocarbons relies on distillation. Organic solvent nanofiltration can provide an energy-efficient alternative. We prepared high performance organosiloxane membranes for fractionation of heavy aromatics. They achieved a high permeance up to 0.13 L m−2 h−1 bar−1, with a rejection rate of 88.7% for hydrocarbons with five aromatic rings. [ABSTRACT FROM AUTHOR]

This paper reports a new sustainable protocol for the microwave‐assisted catalytic conversion of levulinic acid into N‐substituted pyrrolidones over tailor‐made mono (Pd, Au) or bimetallic (PdAu) catalysts supported on either highly mesoporous silica (HMS) or titania‐doped HMS, exploiting the advantages of dielectric heating. MW‐assisted reductive aminations of levulinic acid with several amines were first optimized in batch mode under hydrogen pressure (5 bar) in solvent‐free conditions. Good‐to‐excellent yields were recorded at 150 °C in 90 min over the PdTiHMS and PdAuTiHMS, that proved recyclable and almost completely stable after six reaction cycles. Aiming to scale‐up this protocol, a MW‐assisted flow reactor was used in combination with different green solvents. Cyclopentyl methyl ether (CPME) provided a 99 % yield of N‐(4‐methoxyphenyl) pyrrolidin‐2‐one at 150 °C over PdTiHMS. The described MW‐assisted flow synthesis proves to be a safe procedure suitable for further industrial applications, while averting the use of toxic organic solvents. [ABSTRACT FROM AUTHOR]

Protonated and methylated bis‐acridinium tweezers built around a 2,6‐diphenylpyridyl and an electron enriched 2,6‐di(p‐anisyl)pyridyl spacer have been synthesized. These tweezers can self‐assemble in their corresponding homodimers and the associated thermodynamic parameters have been probed in organic solvents. The switching properties of the tweezers have been exploited in biphasic transfer experiments showing the shift of the equilibria towards the homodimers. Moreover, the thermodynamic parameters of the formation of the reduced methylated homodimers investigated by electrochemical experiments revealed the dissociation of the dimers. Thus, in addition to solvent and temperature, the pH and redox responsiveness of the acridinium units of the tweezers make it possible to modulate to a larger extent the monomer‐dimer equilibria. [ABSTRACT FROM AUTHOR]

Due to the mismatched aggregation behavior and limited compatibility between the donor and acceptor, it is a challenge for the active layer of organic solar cells (OSCs) to spontaneously realize well‐developed morphology in nonhalogenated solvents. In this contribution, an aggregation regulation strategy for acceptors with strong aggregation is developed via thiophene‐substituted alkyl chain engineering to fabricate high‐performance nonhalogenated solvent‐processed OSCs without an additive or post‐treatment. With the replacement of alkyl chains with steric conjugated thiophene‐substituted alkyl chains, the resulting acceptor (namely BTP‐2T, BTP‐T, and BTP‐T‐BO) shows reduced aggregation to match the polymer donor D18‐Cl using toluene as a processing solvent, enabling ordered molecular arrangement and uniform phase separation morphology. Especially, the combined modification of the asymmetric thiophene‐substituted inner chain and branched outer side chains for BTP‐T‐BO enables the formation of a superior nanoscale bi‐continuous interpenetrating network along with ordered and compact molecular packing in the D18‐Cl:BTP‐T‐BO blend. As a result, an excellent PCE of 18.05% is achieved in the D18‐Cl:BTP‐T‐BO‐based device using toluene as the processing solvent without any extra treatment, which is the highest value for nonhalogenated solvent‐processed OSCs without any extra treatment. [ABSTRACT FROM AUTHOR]