Imidazolium-based Ionic Liquids Research Articles

Impact of ionic liquids on the thermal properties of polymer composites

Abstract The integration of ionic liquids and polymer composites has become a promising way to improve their thermal properties, representing a notable advancement in the development of advanced materials for specific applications. Their thermal properties heavily influence the suitability of polymer composites for particular applications. It is imperative to understand and manipulate the thermal behavior of these composites to optimize their performance across various fields. In this mini-review, diverse polymer matrices and fillers utilized in polymer composites containing ionic liquids are categorized. Additionally, various ionic liquids employed in studies related to the thermal properties of polymer composites are identified. The impact of ionic liquids on the thermal properties of these composites is also briefly reviewed. The knowledge illustrated in this review enriches the understanding of the types of polymer matrices and fillers used in conjunction with ionic liquids, as well as their thermal properties. In a nutshell, imidazolium-based ionic liquids with tetrafluoroborate, bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, halides, and hydrogen sulfate anions have the impact of improving the glass transition temperature, melting temperature, degradation temperature, and thermal conductivity of thermoplastic, thermosetting, and elastomer composites.

Optimizing Gluten Extraction Using Eco-friendly Imidazolium-Based Ionic Liquids: Exploring the Impact of Cation Side Chains and Anions.

Gluten is a well-known food allergen globally, and it can induce immune responses in celiac- and nonceliac gluten-sensitive patients. The gliadin proteins from gluten have a special amino acid sequence that make it hydrophobic. One way to deal with gluten allergies is to provide a gluten-free diet. The hydrophobic characteristic of gliadin makes gliadin detection more difficult. An analyst needs to use an organic solvent or multiple processes to denature gluten for extraction. Although organic solvents can rapidly extract gluten in a sample, organic solvent also denatures the antibody and induces false biotest results without buffer dilute, and the accuracy will reduce with buffer dilute. An ionic liquid (IL) is a highly modifiable green chemical organic salt. The imidazolium has a cationic structure and is modified with different lengths (C = 0, 1, 3, 5, 7, 9, and 12) of carbon side chains with organic and inorganic anions [methanesulfonate (MSO), Cl-, F-, NO3-, HSO4-, and H2PO4-] to make different kinds of ILs for testing the solubility of gliadin. Different IL/water ratios were used to test the solubility of gluten. We measured the solubility of gliadin in different imidazolium ILs, and the kinetic curve of gliadin dissolved in 1% [C5DMIM][MSO]aq was conducted. We also used circular dichroism spectroscopy and an enzyme-linked immunosorbent assay to measure the gliadin structure and the effect of binding with an antibody after 1% [C5DMIM][MSO]aq treatment. An 2,3-bis-(2-methoxy-4- nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide (XTT) assay was used to test the toxicity of [C5DMIM][MSO]aq in N2a cells. In our research, 1% [C5DMIM][MSO]aq produced a good solubility of gluten, and it could dissolve more than 3000 ppm of gluten in 5 min. [C5DMIM][MSO]aq did not break down the gluten structure and did not restrict antibody binding to gluten, and more importantly, [C5DMIM][MSO] did not exhibit cell toxicity. In this report, we showed that [C5DMIM][MSO] could be a good extraction solution applied for gluten detection.

Surface modification of poly (ethylene terephthalate) using imidazolium-based ionic liquids

Ionic liquids (ILs), with their unique characteristics, are widely known as new alternatives for solvents and catalysts used in various chemical reactions. Due to their extensive range of applications and environmental compatibility, they are suitable options for treating fibrous substrates. In this regard, this paper focuses on investigating the possibility of poly (ethylene terephthalate) surface modification via imidazolium-based ILs. Surface modification was carried out under different process conditions by varying the temperature and the catalyst. The possibility of treating samples in the IL solution for the second time was also examined. Moreover, the effect of the modification on the dyeing of polyester with disperse dye without carrier at 100 °C was studied. The samples’ wettability properties were investigated through several test methods by measuring vertical wicking height, wetting time, drop contact angle, surface resistivity and absorption of methylene blue dye. The chemical and physical changes of the modified samples were also evaluated via scanning electron microscopy images, Fourier-transform infrared spectroscopy (FTIR) spectra and mechanical tests. Results demonstrate that treatment with [BMIM]Cl and [BMIM]Br induces morphological changes on the fibre surface, creating grooves and voids. FTIR analysis and Methylene blue staining test confirm the formation of hydroxyl and carboxyl groups, enhancing the fabric's hydrophilicity and dyeability. Wettability tests reveal that increased water absorption leads to reduced electrical resistivity. Mechanical tests indicate a slight reduction in tensile strength attributed to surface roughness.

In vitro antifungal activity, cytotoxicity and binding analysis of imidazolium based ionic liquids with fluconazole: DFT and spectroscopic study

Fungal infections represent a significant challenge in various living organisms, including humans, animals, and plants. Fungi are versatile organisms capable of thriving in diverse environments, which contributes to their widespread presence and potential to cause infections. Recently, imidazolium-based ionic liquids emerged as good antimicrobial agent in either monomeric or polymeric form. Therefore, herein, we have reporting the in-vitro antifungal activity, cytotoxicity, and binding analysis of 1-decyl-3-methylimidazolium chloride, [C10Mim][Cl] and 1-hexyl-3-methylimidazolium chloride, [C6Mim][Cl] ionic liquids with fluconazole (Flz). The antifungal activity of ILs and ILs with Flz against candidiasis species (C. albicans) in terms of minimum inhibitory concentration (MIC) was assessed. The antifungal activity results showed that [C10Mim][Cl]-Flz exhibit good antifungal activity then [C10Mim][Cl] and Flz alone. The cytotoxicity of ILs with Flz was checked against human embryonic kidney (HEK293) cell line regarding cell viability and result showed minute cytotoxicity of the combinations at higher concentrations. Further, the binding of ILs with Flz was also studied using various techniques such as UV–visible, fluorescence, Fourier-transform infrared (FTIR) spectroscopy, isothermal titration calorimetry (ITC), and conductivity method. It was found that [C10Mim][Cl] shows more binding affinity then [C6Mim][Cl] with Flz. In-silico molecular docking analysis of Flz-[C10Mim][Cl] complex show a higher binding affinity with CYP51 which in turn enhanced its ability to inhibit the ergosterol biosynthesis as compared to alone [C10Mim][Cl] and Flz. The classical density functional theory (DFT) model was also utilized which further supports the spectroscopic results.

Graphene Oxide/Melamine/Ionic liquid membranes for selective CO2 separation

Highly permeable and selective membranes with long-term stability are needed to reduce operating and capital costs of industrial gas-separation units. In this study, we fabricate new membranes made of melamine (M)- and imidazolium-based ionic liquid (IL)-modified graphene oxide (GO) deposited on a porous support and buried with a polydimethylsiloxane (PDMS) layer. The CO2/N2 and CO2/CH4 ideal selectivities of the composite membranes are respectively 65 % and 70 % higher than those of the membranes containing only the IL. This significant improvement in ideal selectivity is attributed to synergic effects of nanochannels created by GO, fixed facilitated transport provided by the IL and numerous amine groups in the melamine structure, and the increased polarity of the membrane caused by the presence of the IL. The composite membrane has a pure CO2 permeance of 47 GPU with a high CO2/N2 ideal selectivity of 109 and a satisfactory CO2/CH4 ideal selectivity of 39. The composite membrane maintains stable performance over a 60-hour operation, highlighting its long-term reliability. The outstanding performance, coupled with the ease of fabrication, underscores the potential of these composite membranes for practical and efficient CO2 removal from both natural and flue gas streams in real-world applications.

Degradation of imidazolium-based ionic liquids by UV photolysis and pulsed corona discharge: The effect of persulfates addition

Ionic liquids (ILs) are salts with exceptional properties important for future development, although potentially hazardous for humans and aquatic life due to their high aqueous solubility and toxicity. Biodegradation of ILs depends on the anion nature and cation structure: many ILs are not readily degraded during conventional wastewater treatment, thus requiring alternative cost-effective and energy-efficient solutions. In this research, the degradation of aqueous imidazolium-based ILs by pulsed corona discharge (PCD) and UV photolysis combined with persulfates was studied, using peroxymonosulfate (PMS) and peroxydisulfate (PDS) as extrinsic oxidants. 1-Ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-methyl-3-octylimidazolium chloride ([Omim][Cl]), and 1-ethyl-3-methylimidazolium bromide ([Emim][Br]) were chosen as imidazolium-based ILs with different alkyl chain lengths and anions in oxidation experiments under variable operation factors - pH, concentrations of persulfates, pulse repetition frequency in PCD. Pulsed corona discharge has previously shown high energy efficiency in the degradation of micropollutants but has not yet been applied to ionic liquids. The experimental results showed the ability of PCD, PCD/oxidant and UV/oxidant combinations to completely degrade the ILs with the degradation rates in descending order [Emim][Cl] > [Omim][Cl] > [Emim][Br], indicating an impact of both the alkyl chain length and the type of anion on the oxidation rate. The strong activation of persulfates was observed in UV/oxidant combinations, whereas PCD demonstrated the effect of persulfates addition between slight acceleration and moderate deceleration of oxidation dependent on the concentration of extrinsic oxidants. The addition of the sulfate radicals’ scavenger, however, showed the presence of those in all combinations indicating a certain replacement of PCD-generated reactive oxygen species with secondary reactants formed from persulfates. The unassisted PCD and UV/PDS combination demonstrated similar energy efficiencies of about 54 and 26 mmol kWh−1 for [Emim][Cl] and [Emim][Br] degradation, respectively, while for [Omim][Cl] the UV/PDS combination showed energy efficiency 1.42 times higher than unassisted PCD.

Lionomers versus Zn-Ionomer: A new route for the preparation of microcellular foams

In this work, LIonomers based on maleic anhydride-grafted polypropylene (PPgMA) are successfully designed. These LIonomers are developed from the addition of two imidazolium-based ionic liquids (ImILs) to PPgMA: one unreactive ImIL, i.e. 1-ethyl-3-methylimidazolium diethyl phosphate (E+DEP), and one reactive ImIL, i.e. 1-aminoethyl-3-methylimidazolium bromide (AE+Br). Thus, the effect of the ImIL nature on LIonomers properties was highlighted and those ones compared to conventional Zn-Ionomer. Firstly, NMR and FTIR spectroscopies have revealed the existence of ionic-polar/ionic interactions and/or the creation of chemical bonds depending on the chemical nature of ImILs. These various interactions in polymer blends lead to the different multiscale structurations, i.e. a dual assembling of ionic species (including multiplets and large clusters) and homogeneous morphologies on the blends with E+DEP and AE+Br compared to the phase separation of ions occurring for conventional Zn-Ionomer. The rheological properties have highlighted the presence of such interactions between maleic anhydride groups and cations or anions for the imidazolium IL-based LIonomers, similar to the interactions of Zn2+ with anions pairs within Zn-Ionomers. Thanks to the existence of maleic anhydride/ImIL interactions and the generation of β-crystalline form as well as the various ionic-rich phases, an outstanding compromise between stiffness and stretchability was achieved from LIonomers. In addition, considering supercritical carbon dioxide (scCO2) as physical foaming agent, the foamability of PPgMA has been considerably improved thanks to the ionic networks formed by ionic liquids compared to Zn2+ acetate addition. Finally, the foam morphology and the compressive behavior were investigated as a function of the cation/anion combination of ILs or Zn2+Ac addition.

Elucidating the stabilization mechanism of a K+-depleted c-MYC DNA G-quadruplex in hydrophobic imidazolium-based ionic liquids using spectroscopy coupled with molecular dynamics simulations

Stabilizing native nucleic acid structures is critical for developing nucleic acid-based therapeutics, which have enormous potential in biomedicine for disease prevention, disease treatment and diagnostics. Imidazolium chloride ionic liquids (ImCl ILs) can increase the thermal stability of G-Quadruplex DNA structures. Generally, G-Quadruplex DNA requires K+ (or sometimes Na+) to stabilize their structures via coordination of the guanine bases. In this work we investigated the ability of ImCl ILs to stabilize G-Quadruplex DNA without K+ present. Temperature-dependent CD spectroscopy showed that the ImCl ILs that can form micelles in aqueous solution ([OMIM]Cl and [DMIM]Cl) increase the thermal stability of G-Quadruplex DNA without K+, while the ImCl ILs that do not form micelles ([EMIM]Cl, [BMIM]Cl, and [HMIM]Cl) do not stabilize the structure. Notably, [OMIM]Cl and [DMIM]Cl only stabilize G-Quadruplex DNA at concentrations above their CMC values; at concentrations equal to their CMC values these ILs actually destabilize the structure. MD simulations were performed to elucidate the mechanism of thermal stabilization. Simulations are consistent with experimental results as [DMIM]Cl micelles keep the G-Quadruplex structure stable without K+ present. These results show how ILs can encapsulate and stabilize DNA, which can help guide the development of new strategies for stabilizing DNA and RNA structures at room temperature.

Molecular mechanism for the interaction of natural products with ionic liquids: Insights from MD and DFT study

Ionic liquids (ILs) as a class of green sustainable solvents, have been widely studied and used for the extraction, separation, recovery, and catalytic conversion of natural products (NPs). It is well known that elucidating the dynamic interaction behavior and mechanism of NPs in ILs can help rationally design efficient IL solvent systems at the molecular level. However, the interaction mechanism of rutin molecules and ILs is still unclear. In this contribution, an exhaustive theoretical study of dynamic interaction behavior and mechanism of rutin in six imidazolium-based IL systems is presented for the first time by combining molecular dynamics (MD) simulations with density functional theory (DFT) calculations. Meanwhile, the synergistic effect of cation and anion on rutin-IL complexes stability is deeply investigated by the frontier molecular orbital (FMO), electrostatic potential (ESP), radial distribution functions (RDF), averaged non-covalent interaction (aNCI) and non-covalent interaction (NCI). The final result provides a comprehensive molecular mechanism of interaction between rutin and ILs. The combination of various nonbonded forces (such as H-bond, van der Waals, repulsion and cation-π stacking) between molecules determines the stability of rutin-IL complexes. In addition, the structure, size and functional groups of ILs play a decisive role in promoting the formation of nonbonded forces. Our work shows that avoiding substituents with steric hindrance and electron-withdrawing effect in anions, considering the symmetry of the alkyl chain of imidazolium cations, and enhancing the cooperation between anions and cations is a promising pathway to develop a new and efficient ILs solvent systems for the NPs extraction, recovery, separation, detection, and catalytic conversion.

Vapor–Liquid Equilibrium for Acetonitrile + Ethanol with Imidazole-Based Ionic Liquids as Entrainers at 101.3 kPa

Vapor–Liquid Equilibrium for Acetonitrile + Ethanol with Imidazole-Based Ionic Liquids as Entrainers at 101.3 kPa

ISFME extraction of As species from some real water samples using an imidazolium-based task-specific ionic liquid (TSIL): Synthesis and characterization

ABSTRACT To determine of arsenic species in real water samples using electrothermal atomic absorption spectrometry, a high-performance in-situ solvent formation microextraction technique has been developed using homogenous liquid – liquid microextraction concepts. The developed method was based on the use of a synthesized imidazolium-based ionic liquid (IL) modified with ammonium pyrrolidine dithiocarbamate as a task-specific ionic liquid (TSIL), which was chelated with As(III) and then converted to a hydrophobic IL using ammonium hexafluorophosphate in anion exchange reactions. As(V) was reduced to As(III), using a satisfied reducing agent, and the total amount of As was analyzed using ETAAS. TSIL acts simultaneously as an extracting solvent and a chelating agent. The characterization of the synthesized TSIL was performed using13CNMR and FTIR analyses. When optimal conditions were met, linear dynamic ranges of 0.5–50 µg/L and 0.5–20 µg/L were obtained in the determination of As(III) and total As, respectively. The limits of detection (LOD) and quantitation (LOQ) were determined to be 0.021 µg/Land 0.064 µg/L for the determination of As(III) (for concentration 20 µg/L), respectively, and the standard deviation (RSD%, n = 7) was 2.0%. To evaluate the validity of the method, it was successfully applied for As species determination in different real water samples.

Pyrrolidium- and Imidazolium-Based Ionic Liquids and Electrolytes with Flexible Oligoether Anions.

A new class of fluorine-free ionic liquids (ILs) and electrolytes based on aliphatic flexible oligoether anions, 2-(2-methoxyethoxy)acetate (MEA) and 2-[2-(2-methoxyethoxy)ethoxy]acetate (MEEA), coupled with pyrrolidinium and imidazolium cations is introduced. For the ILs with MEEA anions, Li+ conducting electrolytes are created by doping the ILs with 30 mol % of LiMEEA. The structural flexibility of the oligoether functionality in the anion results in glass transition temperatures (Tg) as low as -60 °C for the neat ILs and the electrolytes. The imidazolium-based ILs and electrolytes reveal better thermal stabilities but higher Tg and lower electrochemical stabilities than the corresponding pyrrolidinium-based analogues. All neat ILs show comparable transport properties for the cations and these decrease by the addition of lithium salt - the pyrrolidinium-based electrolyte being affected the most.

Construction of poly (ionic liquid)-derived gold/silver alloy@nitrogen-doped carbon shell and its application for ratiometric electrochemical detection of nitric oxide

A nitrogen-doped carbon shell loaded with a gold and silver alloy (Au/Ag@NCS) was constructed for highly sensitive electrochemical detection of NO. The Au/Ag@NCS material was prepared by use of SiO2 particles as a template to polymerize imidazolium-based ionic liquids loaded with gold and silver salts, and subsequent carbonization treatment and template removal. The hollow structure of the carbon material acted as a carrier for electrochemical sensing, offering high specific surface area, large pore capacity, robust electron conductivity, and excellent mechanical stability. The inclusion of gold in the composite enhanced its catalytic and sensing capabilities, while silver oxidation was employed as a reference signal for accurate detection. By utilization of the Au/Ag@NCS-modified electrode, a wide detection range from 0.5 nM to 1.05 μM with a low detection limit of 0.32 nM was achieved for NO detection. The electrochemical sensor also exhibited high selectivity and excellent stability. The fabricated sensor was further utilized to explore the release of NO from breast cancer cells, revealing that the electrochemical platform could be regarded as an important method to study the daily tests of NO in clinical application.

Selective extraction of cellulose from xylose residue using ionic liquids/DMSO: COSMO-RS prediction and experimental verification

Efficiently dissolving and separating cellulose from xylose residue is beneficial to realize the high added-value of lignocellulosic waste. In this work, theoretical prediction by using COSMO-RS and practical experiments were combined to investigate the extraction selectivity of ionic liquids (ILs) for cellulose and lignin. Two imidazolium-based ILs, 1-ethyl-3-methylimidazolium diethylphosphate ([Emim]DEP) and 1-allyl-3-methylimidazolium chloride ([Amim]Cl), were screened out from 425 ILs. These ILs were subsequently mixed with dimethyl sulfoxide (DMSO) to dissolve and separate cellulose from xylose residue. The cellulose extraction efficiency of [Emim]DEP/DMSO were optimized by regulating the content of xylose residue, dissolution temperature and time. As the cellulose content was 1.2 wt%, the dissolution temperature of 80 °C, and the dissolving time of 120 min, the cellulose extraction rate of xylose residue could reach as high as 99.3% in [Emim]DEP/DMSO, which is higher than that in [Amim]Cl/DMSO (95.4%). The higher cellulose and lower lignin dissolution capacities of [Emim]DEP indicated that [Emim]DEP was a promising solvent to realize the conversion and utilization of cellulose in agro-industrial residues. In addition, [Emim]DEP presents constant dissolution capacity even it was recycled for five times. Furthermore, the produced xylose residue cellulose film (XRCF) displayed a homogeneous and smooth morphology with a tensile strength of 55.9 MPa, which had great potential in packaging.

Toward an understanding of volumetric and isentropic compressibility behavior of imidazolium-based ionic liquids in aqueous polymer solutions

ABSTRACT A systematic experimental density and sound velocity measurement was carried out for imidazolium-based ionic liquids (ILs) in pure water and in aqueous solutions of 0.03 w/w of water-miscible polymers with different structures and molar masses at T= (288.15, 293.15, 298.15, 303.15 and 308.15) K and p = 84.5 kPa. The ILs under investigation are 1-butyl-3-methylimidazolium hydrogen sulphate ([C4mim][HSO4]) and 1-butyl-3-methylimidazolium bromide ([C4mim]Br). The effects of temperature, polymer type, and IL anion type on the various volumetric and compressibility properties, such as apparent molar volume, isentropic compressibility, apparent molar isentropic compressibility, and infinite dilution apparent molar properties for transfer of ILs from water to aqueous polymer solution were scrutinised. From the gathered results, ion-water interactions, ion-ion interactions at finite concentration, and water-structure breaking character for aqueous solutions of [C4mim][HSO4] are more considerable than aqueous solutions of [C4mim]Br. However, [C4mim]Br-polymer interactions are more favourable than interactions between [C4mim][HSO4] and the studied polymers.

Exploring the Effect of Different Anions and Cations on the Solubility of CO2 in Nitrile Imidazolium-Based Ionic Liquids with Sulfonated-Based Anions

Exploring the Effect of Different Anions and Cations on the Solubility of CO2 in Nitrile Imidazolium-Based Ionic Liquids with Sulfonated-Based Anions

A performance enhancement of dye-sensitized solar cells using pyrazolium-based ionic liquids electrolytes vs imidazolium-based ionic liquids electrolytes

Pyrazolium-based ionic liquids (ILs) having similar heteroaromatic ring structure as imidazolium are distinguishable by the position of the heteroatom (nitrogens) but are less delved into their properties and their capability in dye-sensitized solar cells (DSSCs). Herein, alkylpyrazolium and alkylimidazolium-based ionic liquids having iodide and triiodide anions were compared in terms of their properties namely viscosity, ionic conductivity, and performance as electrolytes in dye-sensitized solar cells (DSSCs). Furthermore, the effect of varying the concentration of the iodide and triiodide anions was also scrutinized. The DSSCs having pyrazolium-based ILs electrolytes showed considerably higher fill factor (FF) and short circuit current (Jsc) than the cells containing imidazolium-based ILs electrolytes attributable to the high ionic conductivities. The cells with butylpyrazolium [4-1-pz][I] and [4-1-pz][I3] ILs showed the highest power conversion efficiency of 4.76 % with an improvement of 62.4 % compared to corresponding imidazolium ILs electrolytes, owing to the high current density (Jsc). The concentration of the iodide and triiodide redox couple was found to affect the dye regeneration and recombination process as elucidated by electrochemical impedance spectra. The high concentration of triiodide has caused cell efficiency to decrease by more than 50 % with low Jsc, electron diffusion (Deff), and triiodide ions diffusion (DI3-) indicating poor mass transport. The best concentrations for iodide and triiodide found in this study are 0.45 M and 0.064 M, respectively. Hence, pyrazolium-based ILs have high potential to be used as electrolytes for DSSCs applications.

A Hierarchical Metal-Organic Framework Composite Aerogel Catalyst Containing Integrated Acid, Base, and Metal Sites for the One-Pot Catalytic Synthesis of Cyclic Carbonates.

Catalysis has played a decisive role in the development of unique chemical reactions to produce important chemicals. However, conventional stepwise synthetic routes that rely on individual catalysts to promote each step often suffer from ponderous processes for the isolation of intermediates that result in massive material losses and large economic expenditures. In addition, traditional powder forms of these catalysts suffer from poor processability and recoverability. Herein, we designed and prepared a hierarchical metal-organic framework (MOF) composite monolithic catalyst IL-Au@UiO-66-NH2/CMC that contains integrated acid (Zr4+), base (ionic liquid (IL)), and metal sites (Au nanoparticles (NPs)) to promote the one-pot preparation of cyclic carbonates from styrene derivatives and CO2. Highly dispersed Au NPs, IL 1-aminoethyl-3-methylimidazolium bromide ([C2NH2 MIM] [Br]), and MOF-positioned Lewis acid sites within this composite aerogel are separately responsible for catalyzing selective epoxidation of the styrene derivatives and the subsequent cycloaddition reaction of CO2 with intermediate styrene oxides. Importantly, inclusion of the imidazolium-based IL effectively modulates the size and chemical microenvironment of the Au NPs via electrostatic protection, leading to catalyst stability and its selective oxidation of styrene. Benefiting from the rapid mass transfer and high exposure of active sites within the pore-rich hierarchical nanostructure, IL-Au@UiO-66-NH2/CMC promotes high conversion (90.5%) of the styrene and selectivity (80.5%) for styrene carbonate (SC) formation in the one-pot process, a performance level that far exceeds those of related catalysts containing only Au NPs or IL (the selectivity of SC < 42%). Furthermore, the composite aerogel catalyst can be readily separated and recycled at least five times without a remarkable loss of activity and selectivity. The controllable integration of various active components in the hierarchical MOF composite aerogel herein should serve as the foundation for the design of multifunctional monolithic catalysts for other valuable tandem processes.

Anticancer activity features of imidazole-based ionic liquids and lysosomotropic detergents: in silico and in vitro studies.

Long-chain imidazole-based ionic liquids (compounds 2, 4, 9) and lysosomotropic detergents (compounds 7, 3, 8) with potent anticancer activity were synthesized. Their inhibitory activities against neuroblastoma and leukaemia cell lines were predicted by the new in silico QSAR models. The cytotoxic activities of the synthesized imidazole derivatives were investigated on the SK-N-DZ (human neuroblastoma) and K-562 (human chronic myeloid leukaemia) cell lines. Compounds 2 and 7 showed the highest in vitro cytotoxic effect on both cancer cell lines. The docking procedure of compounds 2 and 7 into the NAD+ coenzyme binding site of deacetylase Sirtuin-1 (SIRT-1) showed the formation of protein-ligand complexes with calculated binding energies of -8.0 and - 8.1kcal/mol, respectively. The interaction of SIRT1 with compounds 2, 7 and 9 and the interaction of Bromodomain-containing protein 4 (BRD4) with compounds 7 and 9 were also demonstrated by thermal shift assay. Compounds 2, 4, 7 and 9 inhibited SIRT1 deacetylase activity in the SIRT-Glo assay. Compounds 7 and 9 showed a moderate inhibitory activity against Aurora kinase A. In addition, compounds 3, 4, 8 and 9 inhibited the Janus kinase 2 activity. The results obtained showed that long-chain imidazole derivatives exhibited cytotoxic activities on K562 leukaemia and SK-N-DZ neuroblastoma cell lines. Furthermore, these compounds inhibited a panel of molecular targets involved in leukaemia and neuroblastoma tumorigenesis. All these results suggest that both long-chain imidazole-based ionic liquids and lysosomotropic detergents may be an effective alternative for the treatment of neuroblastoma and chronic myeloid leukemia and merit further investigation.

Computing Accurate True Self-Diffusion Coefficients and Shear Viscosities Using the OrthoBoXY Approach.

In a recent paper [Busch, J.; Paschek, D. J. Phys. Chem. B 2023, 127, 7983-7987], we have shown that for molecular dynamics (MD) simulations using orthorhombic periodic boundary conditions with "magic" box length ratios of Lz/Lx = Lz/Ly = 2.7933596497, the self-diffusion coefficients Dx and Dy in x- and y-directions are independent of the system size. They both represent the true self-diffusion coefficient D0 = (Dx + Dy)/2, while the shear viscosity can be calculated from diffusion coefficients in x-, y-, and z-directions, using η = kBT·8.1711245653/[3πLz(Dx + Dy - 2Dz)]. In this contribution, we test this "OrthoBoXY" approach by its application to a variety of different systems: liquid water, dimethyl ether, methanol, triglyme, water/methanol mixtures, water/triglyme mixtures, and imidazolium-based ionic liquids. The chosen systems range from small-sized molecular liquids to complex mixtures and ionic liquids, while spanning a viscosity range of almost 3 orders of magnitude. We assess the efficiency of the method for computing true self-diffusion and viscosity data and provide simple formulas for estimating the required MD simulation lengths and sizes for delivering reliable data with targeted uncertainty levels. Our analysis of the system size dependence of statistical uncertainties for both the viscosity and the self-diffusion coefficient leads us to the conclusion that it is preferable to extend the simulation length instead of increasing the system size. MD simulations consisting of 768 molecules or ion pairs seem to be perfectly adequate.