Stability In Organic Solvents Research Articles

Further Characterization of Lipase B from Ustilago maydis Expressed in Pichia pastoris: a Member of the Candida antarctica Lipase B-like Superfamily.

Lipases from the basidiomycete fungus Ustilago maydis are promising but underexplored biocatalysts due to their high homology with Candida antarctica lipases. This study provides a comprehensive characterization of a recombinant CALB-like lipase from U. maydis, expressed in Pichia pastoris (rUMLB), and compares its properties with those of the well-studied recombinant lipase B from C. antarctica (rCALB). Biochemical analyses included evaluations of optimal pH, temperature, triglyceride (TG) preference for short- and medium-chain acyl groups, phospholipase and amidase activities, enantiopreference, thermostability, stability in organic solvents, and response to NaCl concentrations. rUMLB, a glycosylated enzyme with a molecular weight of 38.6kDa, exhibited cold-active behavior at 0°C and preferred hydrolysis of partially soluble short-chain fatty acid TGs, like rCALB. In addition, rUMLB was also capable of hydrolyzing insoluble long-chain triglycerides like rCALB. The half-life at 50°C for rCALB was approximately 1.6 times greater than that of UMLB, which has fewer surface-exposed proline residues. Both enzymes displayed strong (R)-enantiopreference on (R)-glycidyl butyrate, (R)-ethyl hydroxy butyrate, and (R)-methyl hydroxy valerate enantiomers with increased activity in non-polar solvents. However, rUMLB was more sensitive to polar solvents. Notably, rUMLB was activated at high NaCl concentrations, as previously reported for rCALB. rUMLB showed amidase activity on capsaicinoids similar to rCALB; however, rUMLB uniquely demonstrated significant phospholipase activity toward natural phospholipids, a feature not observed in rCALB. The analysis of the cavity adjacent to the active site in the UMLB model and CALB structure revealed slightly larger area, volume, and hydrophobicity values for UMLB. These comparative insights highlight the functional diversity within the CALB-type lipase family, underscoring the potential of UMLB as a versatile biocatalyst and providing valuable information for biotechnological applications and for understanding enzyme structure-function relationships within the CALB superfamily.

Characterization of a novel subfamily 1.4 lipase from Bacillus licheniformis IBRL-CHS2: Cloning and expression optimization.

This study focuses on a novel lipase from Bacillus licheniformis IBRL-CHS2. The lipase gene was cloned into the pGEM-T Easy vector, and its sequences were registered in GenBank (KU984433 and AOT80658). It was identified as a member of the bacterial lipase subfamily 1.4. The pCold I vector and E. coli BL21 (DE3) host were utilized for expression, with the best results obtained by removing the enzyme's signal peptide. Optimal conditions were found to be 15°C for 24 h, using 0.2 mM Isopropyl β-D-1-thiogalactopyranoside (IPTG). The His-tagged lipase was purified 13-fold with a 68% recovery and a specific activity of 331.3 U/mg using affinity purification. The lipase demonstrated optimal activity at 35°C and pH 7. It remained stable after 24 h in 25% (v/v) organic solvents such as isooctane, n-hexane, dimethyl sulfoxide (DMSO), and methanol, which enhanced its activity. Chloroform and diethyl ether inhibited the lipase. The enzyme exhibited the highest affinity for p-nitrophenol laurate (C12:0) with a Km of 0.36 mM and a Vmax of 357 μmol min-1 mg-1. Among natural oils, it performed best with coconut oil and worst with olive oil. The lipase was stable in the presence of 1 mM and 5 mM Ca2⁺, K⁺, Na⁺, Mg2⁺, and Ba2⁺, but its activity decreased with Zn2⁺ and Al3⁺. Non-ionic surfactants like Triton X-100, Nonidet P40, Tween 20, and Tween 40 boosted activity, while Sodium Dodecyl Sulfate (SDS) inhibited it. This lipase's unique properties, particularly its stability in organic solvents, make it suitable for applications in organic synthesis and various industries.

Exploring the enhanced bioactivity and reactivity of novel Fe(III) and Co(II) complexes incorporating sulfadiazine tetradentate ligand: Structural, DFT, molecular docking, and biological applications

This current work presented the synthesis, characterization and bio-evaluation of new Fe(III) (FePSD), and Co(II) (CoPSD) complexes based on N-[4-amino-5-cyano-6-(methylthio)pyridin-2-yl]-3-oxobutanamide in pyridine afford N-(4-amino-5-cyano-6-(methylthio) pyridin-2-yl)-3-oxo-2-([4-(pyrimidin-2-ylsulfamoyl) phenyl]hydrazono) butanamide (PSD). Interestingly, the FePSD and CoPSD complexes exhibit notable stability and solubility in organic solvents, with molar conductivity values of 79.35 Ω−1 cm2 mol−1 for FePSD and 8.89 Ω−1 cm2 mol−1 for CoPSD, indicating a 1:1 electrolytic nature for FePSD and non-electrolytic behavior for CoPSD. FTIR analysis confirmed metal–ligand interactions, as shifts in key bands were observed, while UV–Vis spectra and magnetic moment measurements supported octahedral geometries for both complexes. DFT calculations provided insights into the electronic structure, revealing that CoPSD has higher reactivity and electrophilicity, while FePSD showed moderate reactivity. Thermal and mass spectral analyses further characterized their stoichiometry and stability. The antibacterial and antifungal activities were evaluated against a range of Gram-positive and Gram-negative bacteria and fungal strains. The FePSD and CoPSD complexes demonstrated significantly enhanced antimicrobial efficacy compared to the parent ligand, as evidenced by larger inhibition zones, higher activity indices, and lower minimum inhibition concentrations (MIC). CoPSD exhibited superior antibacterial and antifungal activity compared to FePSD, nearing the effectiveness of standard antibiotics and antifungal drugs. Additionally, the anti-inflammatory potential of these compounds was assessed using the egg albumin denaturation method. Both FePSD and CoPSD showed remarkable inhibition of protein denaturation, surpassing the parent ligand and even outperforming the standard drug Ibuprofen at higher concentrations. The enhancement in biological activity is attributed to the metal chelation effect, which improves cell membrane permeability and reactive oxygen species (ROS) generation. Molecular docking studies further elucidated the binding interactions of PSD, FePSD, and CoPSD with target proteins, revealing stronger hydrophobic interactions and hydrogen bonding in the metal complexes, correlating with their superior biological activity. These findings highlight the potential of FePSD and CoPSD as promising antimicrobial and anti-inflammatory agents.

A zinc–diketopyrrolopyrrole coordination layer as a fluorescent sensor for selective detection of caffeic acid

A novel diketopyrrolopyrrole (DPP)-derived dicarboxylic acid named 2,2′-(1,4-dioxo-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-2,5(1H,4H)-diyl)diacetic acid (H2TDPPAc) has been designed for the fabrication of luminescent coordination polymers (CPs). Reactions of Zn(NO3)2∙6H2O and H2TDPPAc in DMF/H2O under hydro(solvo)thermal conditions afforded a zinc–diketopyrrolopyrrole CP, [Zn(TDPPAc)(H2O)2]n (1). Single-crystal X-ray diffraction analysis indicates that 1 exhibits a 2D layer structure adopting a topological (4,4) rhombus sql net. XRPD patterns reveal that 1 has high chemical stability in H2O and various organic solvents. Moreover, 1 is also structurally stable in the pH 1–11 aqueous solutions, possessing good acid and base resistances. Luminescence studies show that 1 is almost luminescence silent in solid-state but emits remarkable ligand-centered (LC) yellow-orange fluorescence in suspension-phase of H2O with two strong emission bands at 556 and 594 nm (λex = 350 nm). Fluorescence sensing explorations indicate that 1 is an excellent fluorescence sensor to discriminatively detect caffeic acid (CA) with high sensitivity and selectivity, excellent anti-interference ability, and low limit of detection (LOD) as well as good recyclability. The remarkable fluorescence quenching response toward CA sensing is most likely attributed to the competition of absorption energy.

Thermodynamic Assessment of Sacrificial Oxidant Potential, H2O/O2 Potential, and Rate-Overpotential Relationship to Examine Catalytic Water Oxidation in Nonaqueous Solvents.

The water oxidation reaction (WOR), which is pivotal to storing energy in chemical bonds, requires a catalyst to overcome its inherent kinetic barrier. In bulk solutions, sacrificial oxidants (SOs) can regenerate the catalysts to ensure that the homogeneous WOR can be operated with long-term consistent performance. To implement this strategy for organic WOR systems, we modified four common SOs with tetra-n-butylammonium ([NBu4]+)─[NBu4]2[Ce(NO3)6], [NBu4][IO4], [NBu4][HSO5], and [NBu4]2[S2O8]─and examined their chemical stability and electrochemical behaviors in various organic solvents. We also derived the organic-solvent-associated redox potential of H2O/O2 in organic media (EH2O/O2(org)) using open-circuit potential measurements of the H+/H2 redox couple and the related thermochemical cycle. Our findings indicate that the EH2O/O2(org) varies with solvent identity and can be adjusted by changing the [H2O], [acid], and [base] levels; thus, the SO should be carefully selected for WOR, because the innate redox potentials of SOs are not always higher than EH2O/O2(org) under the studied conditions. Lastly, we obtained catalyst-performance-related insights via a rate-overpotential free-energy relationship by calculating the overpotentials of previously studied WOR systems in organic media.

Lignin as a bioderived modular surfactant and intercalant for Ti3C2Tx MXene stabilization and tunable functions

Controlled tailoring of atomically thin MXene interlayer spacings by surfactant/intercalants (e.g., polymers, ligands, small molecules) is important to maximize their potential for application. However, challenges persist in achieving precise spacing tunability in a well-defined stacking, combining long-term stability and dispersibility in various solvents. Here, we discovered that lignin can be used as surfactants/intercalants of Ti3C2Tx MXenes. The resulting MXene@lignin complexes exhibit superior colloidal stability and oxidation resistance in both water and different organic solvents. More important, we reveal a dynamic interaction between MXene and lignin that enables a wide-range fine interlayer distance tuning at a sub-nanometer scale. Such dynamic interaction is sparse in the reported organic surfactants/intercalants containing single types of functional groups. We also demonstrate the tunability of electrical conductivity, infrared emissivity, and electromagnetic interference shielding effectiveness. Our approach offers a starting point to explore the potential of MXene-biomacromolecule composites for electronics and photonics applications.

Gamma irradiation-induced degradation of hexachlorobenzene in methanol: Kinetics, mechanism and dehalogenation pathway

Hexachlorobenzene (HCB), a persistent organic pollutant (POP) and organochlorine compound (OCC), poses significant environmental and health risks due to its high stability and solubility in fats, oils, and organic solvents. This study investigates the degradation of HCB in methanol using gamma irradiation with a60Co source. A 2 × 10−4 M solution of HCB in methanol was prepared and irradiated at a dose rate of 1.74 Gy/s. The degradation process was monitored using Gas Chromatography-Mass Spectrometry (GC-MS), with optimized parameters for effective separation and analysis of byproducts.The results demonstrated a 100% degradation of HCB at an absorbed dose of approximately 51 kGy. The degradation pathway involved successive dechlorination, forming various chlorinated benzene (CB) byproducts such as pentachlorobenzene (PCB), tetrachlorobenzenes (TeCB), trichlorobenzenes (TCB), dichlorobenzenes (DCB), and ultimately benzene.Ion chromatography (IC) analysis revealed a dose-dependent increase in Cl⁻ concentrations, confirming the efficiency of dechlorination. A chlorine mass balance was performed to evaluate the distribution of chlorine during the degradation process, tracking Cl⁻ ions, CBs, and residual HCB. As the dose increases, the chlorine content in residual HCB decreases significantly, with none remaining at 50.2 kGy and beyond. At 169.5 kGy, nearly all chlorine (99.96%) is unaccounted for, suggesting that it has likely been released as gaseous byproducts, such as Cl₂ or other volatile chlorinated compounds.The formation of solvated electrons and hydrogen radicals initiated the dechlorination process, as evidenced by the identified reaction mechanisms. Kinetic analysis indicated that the degradation followed pseudo-first-order kinetics, with a rate constant of 5 × 10−4 s−1. The study also outlines a dose-dependent trend in radiation chemical yields (G values), initially increasing to a peak of 7.3 × 10−2 molecules per 100 eV at 12.6 kGy and subsequently decreasing to as low as 5.4 × 10−4 at 50.2 kGy.This study highlights the effectiveness of gamma irradiation for the complete degradation of HCB in methanol, offering a promising method for the remediation of POPs-contaminated environments. The proposed mechanism and kinetic properties provide a comprehensive understanding of the radiolytic degradation process, paving the way for further applications in environmental cleanup technologies.

Synergistic C2H2 Binding Sites in Hydrogen-Bonded Supramolecular Framework for One-Step C2H4 Purification from Ternary C2 Mixture.

Purification of C2H4 from the ternary C2 hydrocarbon mixture in one step is of critical significance but still extremely challenging according to its intermediate physical properties between C2H6 and C2H2. Hydrogen-bonded organic frameworks (HOFs) stabilized by supramolecular interactions are emerging as a new kind of adsorbents that facilitate green separation. However, it remains a problem to efficiently realize the one-step C2H4 purification from C2H6/C2H4/C2H2 mixture because of the low C2H2/C2H4 selectivity. We herein report a robust microporous HOF (termed as HOF-TDCPB) with dense O atoms and aromatic rings distributed on the pore surface which provide C2H6 and C2H2 preferred environment simultaneously. Dynamic breakthrough experiments indicate that HOF-TDCPB can not only obtain high-purity C2H4 from binary C2 mixture, but also firstly realize one-step C2H4 purification from ternary C2H6/C2H4/C2H2 mixture, with the C2H4 productivity of 3.2 L/kg (>99.999 %) for one breakthrough cycle. Furthermore, HOF-TDCPB displays outstanding stability in air, organic solvents and water, which endow it excellent cycle performance even under high-humidity conditions. Theoretical calculations indicate that multiple O sites on pore channels can create synergistic binding sites for C2H2, thus affording overall stronger multipoint interactions.

Synergistic C2H2 Binding Sites in Hydrogen‐Bonded Supramolecular Framework for One‐Step C2H4 Purification from Ternary C2 Mixture

AbstractPurification of C2H4 from the ternary C2 hydrocarbon mixture in one step is of critical significance but still extremely challenging according to its intermediate physical properties between C2H6 and C2H2. Hydrogen‐bonded organic frameworks (HOFs) stabilized by supramolecular interactions are emerging as a new kind of adsorbents that facilitate green separation. However, it remains a problem to efficiently realize the one‐step C2H4 purification from C2H6/C2H4/C2H2 mixture because of the low C2H2/C2H4 selectivity. We herein report a robust microporous HOF (termed as HOF‐TDCPB) with dense O atoms and aromatic rings distributed on the pore surface which provide C2H6 and C2H2 preferred environment simultaneously. Dynamic breakthrough experiments indicate that HOF‐TDCPB can not only obtain high‐purity C2H4 from binary C2 mixture, but also firstly realize one‐step C2H4 purification from ternary C2H6/C2H4/C2H2 mixture, with the C2H4 productivity of 3.2 L/kg (>99.999 %) for one breakthrough cycle. Furthermore, HOF‐TDCPB displays outstanding stability in air, organic solvents and water, which endow it excellent cycle performance even under high‐humidity conditions. Theoretical calculations indicate that multiple O sites on pore channels can create synergistic binding sites for C2H2, thus affording overall stronger multipoint interactions.

Reaction Time Induced a Two-Step Dissolution and Recrystallization Structural Transformation with Three Eu Metal-Organic Frameworks: Crystal Structures and Multiresponsive Fluorescence Detection.

Under solvothermal conditions, three 3D lanthanide metal-organic frameworks (Ln-MOFs): [Eu(H2DHTA)1.5(DMF)2]·DMF (1), [Eu(H2DHTA)0.5(DHTA)0.5(DMF)(H2O)]·2H2O (2), and Eu(HCOO)3 (3) (H4DHTA = 2,5-dihydroxyterephthalic acid) have been synthesized by different reaction times. Interestingly, induced by reaction time, compounds 1-3 underwent a two-step dissolution and recrystallization structural transformation (DRST) reaction. Investigations on the DRST processes were carried out, and the transformation pathway was deduced, which was verified by XRD analyses. Notably, compound 2 demonstrates pronounced luminescence as well as high stability in water and other organic solvents. The fluorescent detection of furan antibiotics can serve as turn-off effects, and glutamic acid (Glu), aspartic acid (Asp), and riboflavin (VB2) can serve as the turn-on effect. To explain the enhancing and quenching mechanisms, XRD, UV-visible absorption spectroscopy, electrochemistry, IR spectra, theoretical calculation, fluorescence lifetimes, and XPS were discussed. Additionally, MOF-coated test strips were utilized to detect these analytes, exhibiting excellent agreement with fluorescence spectroscopy. This work provides an example for more effective designs to employ Ln-MOFs as multiresponsive fluorescent sensors for detection of environmental pollutants in aqueous solution.

Facile fabrication of robust and tight PIMs-based TFC hollow fiber membranes with a semi-interpenetrating polymer network via liquid phase cross-linking for organic solvent nanofiltration

Resource recovery and reuse are essential for sustainable development, particularly for high-value resources such as homogeneous (photo)catalysts, active pharmaceutical ingredients, and high-value natural compounds, which can offer economic benefits. Recently, organic solvent nanofiltration (OSN) for resource recovery has gained significant attention owing to its advantages including low energy consumption and seamless integration with other processes. Polymers of intrinsic microporosity (PIMs) have great potential as membrane materials for OSN, owing to their excellent pore properties and solution processability. However, swelling and dissolution of PIMs in organic solvents can impede the filtration performance of PIMs-based OSN membranes. In this study, we fabricated thin-film composite hollow fiber membranes for OSN based on PIMs with improved organic solvent stability using a semi-interpenetrating polymer network (semi-IPN) formed by cross-linking Matrimid with 1,6-hexanediamine within the PIMs through the liquid phase cross-linking method. Semi-IPNs mitigate swelling and tighten the pores of PIMs-based membranes, enabling excellent filtration and molecular separation performance. Furthermore, the fabricated PIMs with a semi-IPN membrane exhibited excellent rejection performance (>96 %) for homogeneous photocatalysts, allowing successful concentration and recovery via OSN. Therefore, PIMs-based membranes with a semi-IPN hold great promise as OSN membranes for the recovery of valuable resources.

Structural insights into polyethylene terephthalate (PET)-degrading archaeal lipase enzyme: An insilico approach

Biodegradation 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.

Anti-counterfeiting labels with controllable and anti-interference coding information based on core–shell Ag@SiO2 nanomaterials for ink printing

The core–shell structured Ag@SiO2 nanomaterial integrated with surface-enhanced Raman scattering (SERS) spectroscopy promises a critical application in anti-counterfeiting. Security labels have been fabricated based on Ag@SiO2 embedded with Raman reporters. The Ag@SiO2 nanomaterial shows good stability and excellent anti-interference property for anti-counterfeiting. Multiple kinds of Raman probe molecules have been anchored in the Ag@SiO2 labels to provide specific and abundant encoding information. The flexible encoding security information could be controlled conveniently by adjusting probe molecules, which not only enrich the SERS information but also improve the level of anti-counterfeiting. Furthermore, the Ag@SiO2 shown excellent stability in organic solvent, and successfully used in ink for the anti-counterfeiting application.

Isomeric organic ligands directing octamolybdates-linked Copper(II) functionalized complexes as active catalysts in electrochemistry and desulfurization

Two remarkable octamolybdates-based copper-organic complexes, namely, [Cu7(L)4(H2O)7(β-H2Mo8O26)]·7H2O (POM 1) and [Cu6(HX)4(β-Mo8O26)(H2O)6]·3H2O (POM 2) (H3L = 2-(pyridine-4-yl)-1H-imidazole-4,5-dicarboxylic acid; H3X = 2-(pyridine-3-yl)-1H-imidazole-4,5-dicarboxylic acid), were successfully assembled using two isomeric organic ligands under hydrothermal conditions. The two-dimensional metal-organic layers of POMs 1 and 2 were converted into three-dimensional frameworks by hexadentate β-H2Mo8O262− and tetradentate β-Mo8O264− clusters, respectively. The electrocatalytic properties of POM 1 were investigated, revealing its ability to catalyze the reduction of BrO3−, NO2− and H2O2 and the oxidation of ascorbic acid. Notably, POMs 1 and 2 demonstrated exceptional stability in organic solvents and exhibited excellent catalytic performance in oxidative desulfurization. When employed as catalysts for thioanisole oxidation, the conversion rates reached 94.5% after 150 min for POMs 1 and 99.9% after 120 min for POMs 2. In addition, their catalytic performances in model oil remained largely unchanged after five recycling cycles.

Polyfunctional Arylamine Based Nanofiltration Membranes with Enhanced Aggressive Organic Solvents Resistance.

Organic solvent nanofiltration (OSN) membranes with high separation performance and excellent stability in aggressive organic solvents are urgently desired for chemical separation. Herein, we utilized a polyfunctional arylamine tetra-(4-aminophenyl) ethylene (TAPE) to prepare a highly cross-linked polyamide membrane with a low molecular weight cut-off (MWCO) of 312 Da. Owing to its propeller-like conformation, TAPE formed micropores within the polyamide membrane and provided fast solvent transport channels. Importantly, the rigid conjugated skeleton and high connectivity between micropores effectively prevented the expansion of the polyamide matrix in aggressive organic solvents. The membrane maintained high separation performance even immersed in N,N-dimethylformamide for 90 days. Based on the aggregation-induced emission (AIE) effect of TAPE, the formation of polyamide membrane can be visually monitored by fluorescence imaging technology, which achieved visual guidance for membrane fabrication. This work provides a vital foundation for utilizing polyfunctional monomers in the interfacial polymerization reaction to prepare high-performance OSN membranes.

Organic-organic interfacial polymerization for the ultrathin polyamide organic solvent nanofiltration membranes

There is an increasing demand for advanced membranes that exhibit both high perm-selectivity and good stability in organic solvents, particularly for organic solvent nanofiltration (OSN). Traditional methods of synthesizing thin films using conventional interfacial polymerization (CIP) have been limited by the use of water-soluble monomers, which has hindered the development of high-performance membranes. To address this issue, a new method called organic-organic interfacial polymerization (OOIP) has been proposed. This method allows for the use of aromatic amines that are not water-soluble in the fabrication of ultrathin polyamide (PA) (<40 nm) thin film composite (TFC) membranes. By investigating five different organic solvents (tetrahydrofuran, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide) with varying water content as the organic phase for a water-insoluble benzidine monomer, two diffusion models of monomers were identified that resulted in different membrane structures and degrees of network crosslinking. The ultrathin PA membranes produced using tetrahydrofuran-H2O and N,N-dimethylformamide-H2O, along with solvent activation, demonstrated high methanol permeances of 11.4 L m−2 h−1 bar−1 and 6.0 L m−2 h−1 bar−1, respectively, while maintaining exceptional rejections of over 99.0 % for small molecules with molecular weights greater than 452 g mol−1. The OOIP method is scalable and reproducible, making it suitable for large-scale membrane production. This innovative approach shows great potential for advancing OSN technology and providing efficient and cost-effective separation solutions for various industries.

Role of covalent crosslinking and 2D nanomaterials in the fabrication of advanced organic solvent nanofiltration membranes: A review of fabrication strategies, recent advances, and challenges

Organic solvent nanofiltration (OSN) membranes have gained significant attention owing to their pivotal role in various industrial applications, including pharmaceuticals, fine chemicals, and manufacturing. This review provides a comprehensive overview of the recent advances in OSN membrane technology, focusing on membrane materials, fabrication techniques, and strategies for tuning the chemistry, structure, and performance of OSN membranes. Initially, the fundamental principles underlying OSN are described, highlighting the critical parameters influencing membrane selectivity, permeability, and stability in organic solvents. It also focuses on the importance of covalent crosslinking in the design and fabrication of dense polyamide membranes. Subsequently, the design and synthesis of novel membrane materials are discussed, including polymeric, inorganic, and hybrid membranes. The use of 2D nanomaterials is summarized, with an emphasis on their structural characteristics and tailored properties for solvent separation applications. We further explored the innovative fabrication strategies, such as interfacial polymerization, modification of ultrafiltration supports, and tuning of the active layer chemistry by incorporating the membrane structure with porous nanofillers. This review also discusses the inhomogeneity issues between inorganic nanofillers and organic matrices of membranes as well as the strategies to overcome these limitations through proper functionalization. Finally, we identified emerging trends and prospects in OSN membrane research, encompassing sustainability, scalability, and integration with other membrane processes, to address existing challenges and discover new opportunities for efficient solvent separation in diverse industrial sectors.

A solvent-free processed low-temperature tolerant adhesive

Ultra-low temperature resistant adhesive is highly desired yet scarce for material adhesion for the potential usage in Arctic/Antarctic or outer space exploration. Here we develop a solvent-free processed low-temperature tolerant adhesive with excellent adhesion strength and organic solvent stability, wide tolerable temperature range (i.e. −196 to 55 °C), long-lasting adhesion effect ( > 60 days, −196 °C) that exceeds the classic commercial hot melt adhesives. Furthermore, combine experimental results with theoretical calculations, the strong interaction energy between polyoxometalate and polymer is the main factor for the low-temperature tolerant adhesive, possessing enhanced cohesion strength, suppressed polymer crystallization and volumetric contraction. Notably, manufacturing at scale can be easily achieved by the facile scale-up solvent-free processing, showing much potential towards practical application in Arctic/Antarctic or planetary exploration.

Enhancing Chymotrypsin Activity and Stability of Capillary Immobilized Enzyme Microreactors Using Zeolitic Imidazolate Frameworks as Encapsulation Materials.

Open-tubular immobilized enzyme microreactors (OT-IMERs) are some of the most widely used enzyme reaction devices due to the advantages of simple preparation and fast sample processing. However, the traditional approaches for OT-IMERs preparation had some defects such as limited enzyme loading amount, susceptibility to complex sample interference, and less stability. Here, we report a strategy for the preparation of highly active and stable OT-IMERs, in which the single-stranded DNA-enzyme composites were immobilized in capillaries and then encapsulated in situ in the capillaries via zeolitic imidazolate frameworks (ZIF-L). The phosphate groups of the DNA adjusted the surface potential of the enzyme to negative values, which could attract cations, such as Zn2+, to promote the formation of ZIF-L for enzyme encapsulation. Using chymotrypsin (ChT) as a model enzyme, the prepared ChT@ZIF-L-IMER has higher activity and better affinity than the free enzyme and ChT-IMER. Moreover, the thermal stability, pH stability, and organic solvent stability of ChT@ZIF-L-IMER were much higher than those of free enzyme and ChT-IMER. Furthermore, the activity of ChT@ZIF-L-IMER was much higher than that of ChT-IMER after ten consecutive reactions. To demonstrate the versatility of this preparation method, we replaced ChT with glucose oxidase (GOx). The stability of GOx@ZIF-L-IMER was also experimentally demonstrated to be superior to that of GOx and GOx-IMER. Finally, ChT@ZIF-L-IMER was used for proteolytic digestion analysis. The results showed that ChT@ZIF-L-IMER had a short digestion time and high digestive efficiency compared with the free enzyme. The present study broadened the synthesis method of OT-IMERs, effectively integrating the advantages of metal-organic frameworks and IMER, and the prepared OT-IMERs significantly improved enzyme stability. All of the results indicated that the IMER prepared by this method had a broad application prospect in capillary electrophoresis-based high-performance enzyme analysis.

Polyamide thin-film composite membranes with enhanced interfacial stability for durable organic solvent nanofiltration

Polyamide thin-film composite (TFC) membranes present a promising option for organic solvent nanofiltration (OSN) due to their superior advantages in facile fabrication and high separation efficiency. However, existing TFC-based OSN membranes are heavily limited by their weak interfacial stability in organic solvents, because many solvent-resistant porous supports are hydrophobic and have poor interfacial compatibility to polyamide. Herein, we report a polyamide TFC membrane with enhanced interfacial stability and durable OSN performance, by multifunctional surface modification and in-situ interfacial polymerization on a hydrophobic and solvent-resistant polypropylene substrate. Distinct from nascent ones, the polypropylene substrates modified by tannic acid/aminopropyltriethoxysilane coating possess excellent hydrophilicity and more functional groups, in which the former allows for the in-situ synthesis of integral polyamide layers via interfacial polymerization and the latter greatly enhances the binding strength between the polyamide layer and PP substrate by 30 times. With this method, the TFC membranes exhibit excellent thermal stability in 80 °C dimethylformamide solution. Meanwhile, the TFC membranes display high ethanol permeance (9.2 L m−2 h−1 bar−1) and acid fuchsin rejection (98.5 %), outperforming the performance of most OSN membranes reported. This straightforward method, robust structural stability, and extraordinary performance make the TFC membranes a step closer to commercial OSN membranes.