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Background:: Dihydroquinazolinone derivatives are an important family of fused heterocyclic shows a wide range of biological, medicinal and pharmacological properties such as anti-tumor, anti-biotic, diuretic, analgesic, antihypertonic, anti-pyretic, anti-depressant, anti-histamine and vasodilation activities. Introduction:: So far some acid catalysts, e.g.; p-toluenesulfonic acid, silica sulfuric acid, zinc(II) perfluorooctanoate, gallium(III) triflate, ionic liquid, Al(H2PO4)3, I2, montmorillonite K-10, Amberlyst-15, Al/Al2O3 and Fe3O4 nanoparticles, have been reported to accomplish this three component reaction. Some of these methods have drawbacks such as toxic solvents and catalysts, long reaction time, the use of expensive catalysts and adverse yields. Method:: A mixture of benzaldehydes (1mmol), isatoic anhydride (1 mmol), Glycine (1 mmol) and OImDSA (2 mL) were stirred at room temperature for the required reaction times (1-2 h). The progress of the reaction was monitored by TLC (EtOAc: petroleum ether 1:2). After completion of reaction, as indicated by TLC, the ionic liquid was separated by extraction with 2×15 mL of water. The solid residue was separated by recrystallization from EtOH. The pure products were collected in 86-97% yields. Results:: Herein, in order to achieve a more efficient synthesis method, to deplete side effects, reduce reaction steps, increase efficiency and curtail reaction time, and also to continue our research on the synthesis of heterocyclic and pharmaceutical compounds. We wish to report the mild synthesis of some derivatives of 2-aryl-quinazolin-4(1H)-ones from isatoic anhydride and Glycine using OImDSA Conclusion:: In conclusion, we have developed a simple, green and efficient protocol for the synthesis of 2-aryl-quinazolin- 4(1H)-ones using OImDSA as an efficient and new procedure. Simplicity, easy practice, integrated with inexpensive, environmentally friendly and reusable ionic liquid are notable attributes of this new method. To the best of our knowledge, this is the first report for the synthesis of a new library of quinazolin-4(1H)-ones derived from Glycine as a natural substrate based on green chemistry conditions.

Ionic liquids (ILs) have been used in solvents for proteins in many applications, including biotechnology, pharmaceutics, and medicine due to their tunable physicochemical and biological properties. Protein aggregation is often undesirable, and predominantly occurs during bioprocesses, while the aggregation process can be reversible or irreversible and the aggregates formed can be native/non-native and soluble/insoluble. Recent studies have clearly identified key properties of ILs and IL-water mixtures related to protein performance, suggesting the use of the tailorable properties of ILs to inhibit protein aggregation, to promote protein crystallization, and to control protein aggregation pathways. This review discusses the critical properties of IL and IL-water mixtures and presents the latest understanding of the protein aggregation pathways and the development of IL systems that affect or control the protein aggregation process. Through this feature article, we hope to inspire further advances in understanding and new approaches to controlling protein behavior to optimize bioprocesses.

An efficient method for prediction in the capture of SO2 from flue gas by imidazolium ionic liquids was reported, where the concentration of SO2 is 2000 ppm. On the basis of quantitative calculations through a combination of Langmuir simulation, theoretical calculation and quantum chemical method, SO2 absorption and desorption performance from flue gas by twelve kinds of imidazolium ionic liquids with different anions were designed and predicted. Then, among them, five kinds of imidazolium ionic liquids were chosen and prepared to investigate their behavior of SO2 absorption capacity, desorption residue, and available absorption capacity. The results indicated that the experimental values were in good agreement with the predicted values. Thus, an ideal ionic liquid [Emim][Tetz] was obtained through the predictive method for the capture of SO2 of 2000 ppm, which showed high available absorption capacity of 0.24 g SO2 per g ionic liquid and excellent reversibility.

The simultaneous introduction of two new functionalities into the same polymeric substrate under mild reaction conditions is an interesting and important topic. Herein, dual-functional polydimethylsiloxane (PDMS) surfaces with antibacterial and antifouling properties were conveniently developed

Strain-sensitive and conductive hydrogels have attracted extensive research interest due to their potential applications in various fields, such as healthcare monitoring, human–machine interfaces and soft robots. However, low electrical signal transmission and poor tensile properties still limit the application of flexible sensing hydrogels in large amplitude and high frequency motion. In this study, a novel ionic liquid segmental polyelectrolyte hydrogel consisting of acrylic acid (AAc), 1-vinyl-3-butylimidazolium bromide (VBIMBr) and aluminum ion (Al3+) was prepared by molecular design and polymer synthesis. The cationic groups and amphiphilicity of ionic liquid chain segments effectively improve the tensile behavior of the polyelectrolyte hydrogel, with a maximum tensile strength of 0.16 MPa and a maximum breaking strain of 604%. The introduction of ionic liquid segments increased the current carrying concentration of polyelectrolyte hydrogel, and the conductivity reached the initial 4.8 times (12.5 S/m), which is a necessary condition for detecting various amplitude and high frequency limb movements. The flexible electronic sensor prepared by this polyelectrolyte hydrogel efficiently detects the movement of different parts of the human body stably and sensitively, even in extreme environment (−20 °C). These outstanding advantages demonstrate the great potential of this hydrogel in healthcare monitoring and wearable flexible strain sensors.

In this work, a simple but effective method based on Gamma-ray initiated polymerization was reported for the first time through direct irradiation of CNCs and ionic liquid monomer to obtain poly (ionic liquids) functionalized CNCs (IL@CNCs). The adsorptive removal of Congo red (CR) from aqueous solution by IL@CNCs was also examined and the influence of contact time, pH values, initial concentrations and temperature on adsorption behavior was investigated in detail. Under the same adsorption conditions, the adsorption capacity was increased from 59.72 mg/g (CNCs) to 195.83 mg/g (IL@CNCs). The results of the adsorption isotherm and adsorption kinetics showed that the experimental data were more suitable to be described by the Freundlich isotherm adsorption model and the pseudo-second-order model. The adsorption process of CR on the surface of the adsorbent was endothermic and spontaneous. When the aqueous solution was acidic, it was more conducive to the adsorption of CR. At 100% breakthrough, the value of adsorption capacity is 199.95 mg/g and the value of partition coefficient is 9.64. Moreover, the adsorption capacity is expected to be further improved through adjustment of polymerization parameters and this method can also be used for preparation other poly (ionic liquids) modified composites.

Organic cations are essential components of locally concentrated ionic liquid electrolytes (LCILEs), but receive little attention. Herein, we demonstrate their significant influence on the electrochemical performance of lithium metal batteries via a comparison study of two LCILEs employing either 1‑butyl‑1-methylpyrrolidinium cation (Pyr14+) or 1-ethyl-3-methylimidazolium cation (Emim+). It is demonstrated that the structure of the organic cation in LCILEs has only a limited effect on the Li+- bis(fluorosulfonyl)imide anion (FSI−) coordination. Nonetheless, the coordination of FSI− with the organic cations is different. The less coordination of FSI− to Emim+ than to Pyr14+ results in the lower viscosity and faster Li+ transport in the Emim+-based electrolyte (EmiBE) than the Pyr14+-based electrolyte (PyrBE). Additionally, the chemical composition of the solid-electrolyte interphase (SEI) formed on lithium metal is affected by the organic cations. A more stable SEI growing in the presence of Emim+ leads to a higher lithium plating/stripping Coulombic efficiency (99.2%). As a result, Li/EmiBE/LiNi0.8Mn0.1Co0.1O2 cells exhibit a capacity of 185 mAh g−1 at 1C discharge (2 mA cm−2) and capacity retention of 96% after 200 cycles. Under the same conditions, PyrBE-based cells show only 34 mAh g−1 capacity with 39.6% retention.

A novel ionic liquid (IL) functionalized with thiodiglycol amic acid containing a soft S donor was synthesized for the effective and efficient extraction of platinum group metals (Ru, Rh, and Pd) from aqueous nitric acid solutions, such as high-level radioactive liquid waste (HLLW). The IL enabled rapid extraction of Pd(II) with an extraction ratio of approximately 100%. The extractions of Ru(III) and Rh(III) by the IL were slower than that of Pd(II), but the rates were accelerated by temperature elevation. The extractions of Ru(III) and Rh(III) at 50 °C reached equilibrium within 4 and 8 h, respectively, with the extraction ratios of over 90% without assisting agents or other methods for the extraction system. Furthermore, the IL could extract more than 90% of Ru(III), Rh(III), and Pd(II) from the simulated HLLW within 2 h at 50 °C.

The application of ion liquids (ILs) as green solvents has attracted the attention of the scientific community. However, ILs may play the role of toxins. Even though ionic liquids may assist to minimise air pollution, but their discharge into aquatic ecosystems might result in significant water pollution due to their potential toxicity and inaccessibility to biodegradation. Recently, more attention has been paid to the toxicity of ILs on plants, bacteria, and humans. Here, a quantitative structure-toxicity relationship study (QSTR) based on the Monte Carlo method of CORAL software has been applied to estimate the logarithm of the half-maximal effective concentration of toxicity of ILs against leukemia rat cell line IPC-81 (logEC50). A hybrid optimal descriptor is used to build QSTR models for a large set of 304 diverse ILs including ammonium, imidazolium, morpholinium, phosphonium, piperidinium, pyridinium, pyrrolidinium, quinolinium, sulfonium, and protic ILs. The SMILES notations of Ils are utilized to compute the descriptor correlation weight (DCW). Four splits are made from the whole dataset and each split is randomly divided into four sets (training subsets and validation set). The index of ideality of correlation (IIC) is applied to evaluate the authenticity and robustness of the QSTR models. A QSTR model with statistical parameters R2=0.85, CCC =0.92, Q2=0.84, and MAE =0.25 for the validation set of the best split is considered as a prime model. The outliers and promoters of increase/decrease of logEC50 are extracted and the mechanistic interpretation of effective descriptors for the model is also offered.HighlightsGlobal SMILES-based QSAR model was developed to predict the toxicity of ILs.The CORAL software is used to model the ILs toxicity on IPC-81 leukemia rat cell lineIIC is tested as a criterion of predictive potential.The toxicological effects of ILs are discussed based on the proposed model.

Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology.

Cryopreservation has facilitated considerable advances in both medical technology and scientific research. However, further developments have been limited by the relatively low number of effective cryoprotective agents. Even after fifty years of research, most protocols rely on the same two toxic agents, i.e. dimethylsulfoxide or glycerol. Ionic liquids are a class of promising solvents which are known glass formers and may offer a less-toxic alternative. The research presented here investigates ten protic ionic liquids as potential cryoprotective agents. The liquids are screened for key properties including cellular toxicity, permeability and thermal behaviour. The most promising, ethylammonium acetate, was then tested as a cryoprotective agent on a model cell line and was found to be as effective as the common cryoprotectant, dimethylsulfoxide. This work reports the first use of a protic ionic liquid as an effective cryoprotective agent for a mammalian cell line. This will inform the development of a suite of potential new ionic liquid-based cryoprotectants that could potentially allow the cryopreservation of new cell types.

The advance of space technology is deeply affected by the breakthrough of high-performance fuels. Hypergolic ionic liquids (HILs) are one of the most potential fuels for bipropellant systems. However, high viscosity value and low specific impulse of traditional N-based HILs limit their application. Recently, boron-based HILs with low viscosity become the new candidates, and their derivatives are also found to promote the hypergolicity as additives in HILs. Here, the synthesis, physical chemical properties and thermal performance of boron-based HILs and HIL-additive system are reviewed.

In the current work, we present a broad analysis of cytotoxicity toward normal (kidney and lung) and cancer (lung, liver, and cervix) cells of ionic liquids (ILs) with imidazolium cations and cyano-based or bis(trifluoromethylsulfonyl)imide anions. Additionally, we verify if ILs might be candidates for new potential virucidal agents. We observed the highest biological activity for 1-methyl-3- octylimidazolium bis(trifluoromethylsulfonyl)imide, whereas the least toxic was 1-ethyl-3-methylimidazolium thiocyanate. We found that all investigated ILs revealed a lack of antiviral activity against viruses: human parainfluenza virus type 3 (HPIV-3), human adenovirus 5 (AdV5), human herpesvirus 1 (HSV-1), and human herpesvirus 5 (HCMV) in nontoxic concentrations.

Ionic liquids (ILs) have received attention for many years due to them being very promising as green solvent substitutes, but they are not fully understood, especially their behavior dissolved in other solvents, for example, water. Thus, the goal of this contribution is to show insight into the different IL-water mixtures interaction. In this way, two protic ILs (PILs), ethylammonium nitrate (EAN) and 1-methylimidazolium acetate (MIA), mixed with water were investigated. To study the PILs-water interaction, the unique spectroscopical behavior in water of the molecular probe 4-aminophthalimide (4-AP) was used. 4-AP emission spectra show hypsochromic shifting by changing the excitation wavelength and, using time-resolved spectroscopy, can be detected by a blue shifting with time. Also, the water mixture of an aprotic IL, 1-methyl-3-butylimidazolium tetrafluoroborate (bmimBF4), and three alcohols, methanol (MeOH), 2-propanol (2-PrOH), and t-butanol (t-BOH), were investigated for comparison. Our results show that the water-ILs interaction is dominated by the size of the IL components, in particular, the cation size. Thus, in MIA-water and bmimBF4-water mixtures, 4-AP is mostly solvated by the IL, even at a low IL molar fraction, as in the t-BOH-water mixture. This finding is especially interesting when ILs-water mixtures are used as a solvent in an organic reaction, where it may call attention to water probably not being the solvent that is interacting with the reactants.

Ionic liquids are used in different processes owing to their low vapor pressure, large viscosity range, chemical and thermal stability, and superior conductance even without water. These features make them flexible and tunable, indicating their possible use as substitutes for commonly used compounds in many processes. The objective of this study was to evaluate the properties of aqueous binary solutions for three different ionic liquids (ILs): dibutylammonium acetate, dibutylammonium propanoate, and dibutylammonium butanoate. The measured properties were density, speed of sound, and conductivity, and their isentropic compressibility and thermal expansion coefficient were calculated based on these properties. The temperature range used for measurements was 293.15–323.15 K. Mathematical models were used for each ionic liquid + water mixture to fit the density and speed of sound data. The increase in the alkyl chain leads to a tendency to decrease the values of density, speed of sound, and conductivity of the solutions. However, decreasing the dilution in water, the density, the conductivity and the speed of sound initially increase and then decrease, exhibiting a maximum in the initial water concentration range which indicates the formation of aggregates. Critical micellar concentrations at 298 K were determined through conductivity data. Enhancing the temperature leads to a decrease on density and sound velocity. Supplementary Information The online version contains supplementary material available at 10.1007/s43153-021-00174-7.

Nonaqueous electrolytes are used in various electrochemical devices as their electrochemical potential window is wider than that of aqueous electrolytes. Electrochemical reactions significantly change depending on the combination of nonaqueous solvent and salt and the dissolved state of the metal ions or redox species in the solvent. Room-temperature ionic liquids (RTILs), a type of nonaqueous solvent, have unique physicochemical properties such as negligible vapor pressure and non-flammability. Their application as reaction media for a variety of reactions, including electrochemical reactions has attracted significant interest, as they enable reactions that cannot proceed in water or organic solvents. We have been researching materials synthesis and energy devices using RTILs and organic electrolytes. Herein, we comprehensively review our research on the electrodeposition of metals, preparation of metal nanoparticles, and secondary batteries using nonaqueous electrolytes.

International audience; Background: - Nitrous oxide (N2O), as a potent greenhouse gas, is increasingly becoming a major multidisciplinary concern in recent years. Therefore, the removal of N2O using powerful green solvents such as ionic liquids (ILs) has turned into an attractive way to reduce the amount of N2O in the atmosphere. Methods: -The aim of this study was to establish rigorous models that can predict the solubility of N2O in various ILs. To achieve this, three advanced soft-computing methods, viz. cascaded forward neural network (CFNN), radial basis function neural network (RBFNN), and gene expression programming (GEP) were trained and tested using comprehensive experimental measurements. Significant Findings: - The obtained results demonstrated that the newly implemented models can predict the solubility of N2O in ILs with high accuracy. Besides, it was found that the CFNN model optimized using Levenberg-Marquardt (LM) algorithm was the best predictive paradigm (R2=0.9994 and RMSE=0.0047). Lastly, the Leverage technique was carried out, and the statistical validity of the newly implemented model was documented as more than 96% of data were located in the applicability realm of this paradigm.

This study revealed that mixed chitin esters with long fatty and bulky acyl substituents were efficiently synthesized by acylation using acyl chlorides in the presence of pyridine and N,N-dimethyl-4-aminopyridine in an ionic liquid, 1-allyl-3-methylimidazolium bromide (AMIMBr), at 100 °C for 24 h. A stearoyl group was selected as the first substituent, which was combined with different long fatty and bulky acyl groups as the second substituents. In addition to IR analysis of the products, which suggested progress of the acylation, 1H NMR measurement was allowed for structural confirmation for high degrees of substitution (DSs) of the desired derivatives in CDCl3/CF3CO2H solvents. Crystalline structures and thermal property of the products were evaluated by powder X-ray diffraction and differential scanning calorimetry measurements, respectively. All the products showed film formability by casting from solutions in chloroform or chloroform/trifluoroacetic acid solvents. The occurrence of halogen exchange between acyl chlorides and AMIMBr in the present system was speculated to produce highly reactive acyl bromides in situ, which efficiently reacted with hydroxy groups in chitin to obtain high DS products.

Wearable strain and temperature sensors are desired for human-machine interfaces, health monitoring, and human motion monitoring. Herein, the fibrous mat with aligned nanofibers of ionic liquid (IL)/thermoplastic polyurethane (TPU) ionogels is fabricated via an electrospinning technique. The resultant fibrous mat is cut into a rectangle specimen and electrodes are loaded along the direction perpendicular to the nanofiber orientation to design a high-performance multimodal sensor based on an ionic conducting mechanism. As a strain sensor, the obtained sensor exhibits a wide strain working range (0-200%), a fast response and recovery (119 ms), a low detection limit (0.1%), and good reproducibility because of the reversible and deformable ionic conductive pathways of the sensor. Moreover, the sensor also exhibits excellent temperature-sensing behaviors, including a monotonic thermal response, high sensitivity (2.75% °C-1), high accuracy (0.1 °C), a fast response time (2.46 s), and remarkable repeatability, attributable to the negative temperature coefficient behavior of the IL/TPU fibrous mat. More interestingly, the IL/TPU fibrous sensor possesses good breathability, which is desired for wearable electronics. Because of these excellent sensing capabilities in strain and temperature, the sensor can not only monitor tiny and large human motions but also detect respiration and proximity, exhibiting enormous potential in wearable electronics.

The emerging application risks of traditional ionic liquids (ILs) toward the ecosystem have changed the perception regarding their greenness. This resulted in the exploration of their more biocompatible alternatives known as biocompatible ILs (BioILs). Here, we have investigated the impact of two such biocompatible cholinium amino acid-based ILs on the structural behavior of model homogeneous DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) lipid bilayer using all-atom molecular dynamics simulation technique. Two classic cholinium-amino acid-based ILs, cholinium glycinate ([Ch][Gly]) and cholinium phenylalaninate ([Ch][Phe]), which differ only by the side chain lengths and hydrophobicity of the anions, have been utilized in the present work. Simultaneous analysis of the bilayer structural properties reveals that the existence of [Ch][Gly] BioIL above a particular concentration induces phase transition from fluid phase to gel phase in the DMPC lipid bilayer. Such a freezing of lipid bilayer upon the exposure to concentrated aqueous solution of [Ch][Gly] BioIL indicates the harmfulness of this BioIL toward the cell membranes majorly containing DMPC lipids, as the cell freezing can negatively affect its stability and functionality. Despite having a more hydrophobic amino acid side chain of [Phe]- anion in [Ch][Phe], in the case of bilayer-[Ch][Phe] systems we observe the minimal impact of [Ch][Phe] BioIL on the DMPC bilayer properties up to 10 mol % concentration. In the presence of these BioIL, we observe the thickening of the bilayer and accumulation of the cations and anions of the BioILs at the interface of DMPC lipid heads and tails. The transfer free-energy profile of a [Phe]- anion from aqueous phase to membrane center also indicates the anion partitioning at lipid head-tail interface and its inability to penetrate in the lipid membrane tail region. In contrast, the free-energy profile for a [Gly]- anion offers a very high energy barrier to the insertion of [Gly]- into the membrane interior, leading to accumulation of [Gly]- anions at the lipid head-water region.

Interactions between ionic liquids and biomolecules are of great interest due to the intrinsic properties of ionic liquids and the flexibility allowed by mixing and matching cations and anions to create unique ionic liquids. A number of ionic liquid–biomolecule studies have focused on interactions with proteins, including industrially relevant enzymes. One of these, laccase from Trametes versicolor, is a naturally derived enzyme used in the breakdown of phenolic compounds in a wide variety of industries, especially useful in breakdown of lignocellulosic materials. Here, a combination of experiments and molecular dynamics (MD) simulations was used to investigate the interactions of ionic liquids with laccase. Enzyme kinetics assays indicated that ionic liquids composed of tetramethylguanidine (TMG) and either serine or threonine caused significant reduction in enzymatic activity, while kinetics was not impacted by TMG-Asp or TMG-Glu ionic liquids. Similarly, intrinsic fluorescence of laccase in the presence of TMG-Ser and TMG-Thr exhibited a shift in spectral properties consistent with structural destabilization, but again TMG-Asp and TMG-Glu had no impact. MD simulations of laccase and ABTS with/without TMG-Ser ionic liquid provided insight into the deactivation mechanism of laccase. The simulations indicated that TMG-Ser disrupts laccase’s electron transfer mechanism.

International audience; For the first time, the possibility of obtaining porous germanium from both single-crystal and polycrystalline starting materials using environmentally friendly (in contrast to the commonly used HF and HCl) imidazolium ionic liquids (IL) was shown. It was demonstrated that pore formation depended significantly on the viscosity of the IL, on the etching current density and etching time, and on defects and imperfections of the substrate surface. By varying these parameters, the rates of two competing processes - formation and growth of pores and electropolishing - could be adjusted, consequently allowing germanium with a various structured surface, including a porous surface. In particular, using a more viscous IL (for example, [BMIM][PF6] versus [BMIM][BF4]) made it possible to reduce the rate of dissolution of the germanium dioxide surface layer; as a result, the formation and growth of pores became a dominant process. At the same time, the dissolution rate of the already formed porous layer (electropolishing) increased with the etching current density and the number of defects and imperfections of the germanium surface.

The knowledge of water solubility in ionic liquids (ILs) is an important property with an impact on the design of many physical and chemical processes, like the purification of organic compounds or the establishment of decontamination procedures. The development of methods to predict or establish solubility trends in ILs is, therefore, extremely relevant, as it may avoid expensive and time-consuming experimental procedures. In this work, we compare results of water solubility in ILs predicted by a quantitative structure-property relationship (QSPR) model with trends found using aggregation studies in molecular dynamics (MD) simulation results. This study was performed for ILs combining the cations 1-butyl-1-methylpyrrolidinium and 1-butyl-1-methylmorpholinium, with the anions bis(pentafluoroethylsulfonyl)imide (BETI-), trifluoromethanesulfonate (TF-), and tetrafluoroborate (BF4-). Both methods indicated that, at 298.15 K, the water solubility in ILs was almost independent of the investigated cations. However, if the IL is composed of a hydrophobic anion, a slight increase in the mixability of the IL with water may be observed if the cation can form H-bonds. The QSPR model indicated that the hydrophobic BETI- anion leads to solubilities (xH2O ∼ 0.33), approximately half of those predicted when the cations are combined with TF- and BF4- anions (xH2O ∼ 0.60). The MD results suggested that this difference is essentially related to the ability of the water molecules to interact with the anion. This interaction involves the formation of networks of molecules, where H2O is completely solvated by anions. These structures make the formation of interactions between water molecules difficult, which are responsible for their segregation from solution and, therefore, to liquid-liquid phase separation. For the investigated ILs, the MD data also suggest that the solubility trends are inversely proportional to the number of "isolated" anions relative to ···AN-H2O-AN-H2O··· networks.

Hydrophobicity of natural organic matter (NOM) is one of its fundamental properties that influence the environmental fate of pollutants and the performance of many water treatment unit processes. In this study, a high-throughput method was developed for NOM hydrophobicity measurement based on the phase separation technique in the 96-well format. It measures the partition coefficients of NOM (KATPS,IL) in an ionic liquid (IL)-based aqueous two-phase system (ATPS). The ATPS was made of 1-butyl-3-methylimidazole bromide solution and a salt solution containing potassium phosphate monobasic and potassium phosphate dibasic. The partition of NOM in IL-based ATPS is mainly affected by its hydrophobicity. log KATPS,IL linearly correlated with the commonly used NOM hydrophobicity scales, including (O + N)/C, O/C, and aromatic carbons. KATPS,IL provided a more accurate assessment of NOM hydrophobicity than spectroscopic indices. Furthermore, KATPS,IL can predict the organic carbon-water partition coefficients for hydrophobic organic chemical sorption to NOM based on the two-phase system model. The high-throughput KATPS,IL measurement and the two-phase system model can be applied to real surface water samples. Our results suggest that the proposed high-throughput method has great potential to be applied to monitor NOM hydrophobicity for environmental risk assessment and water treatment purposes.

Exploring efficient and robust antibacterial materials is crucially important for human health and ecological security. Compared with intrinsically antibacterial materials, materials modified with antibacterial agents either by chemical or physical modification can simultaneously maintain basic functions and antibacterial properties. In particular, physical modification with antiseptic sprays is quite suitable for large-size objects in our daily life but restricted by high volatility of the antibacterial agents or poor adhesion strength between the antibacterial agents and the targeted objects. In this paper, we report a poly(ionic liquid) (PIL-Cn)-based efficient and robust antiseptic spray that exhibits long-term antibacterial properties against both Gram-positive and Gram-negative bacteria on diverse substrates, including glass, PE, and cotton. It is believed that this work will provide an alternative for current antiseptic sprays for usage in our daily life and hospitals.

Tunable aryl alkyl ionic liquids (TAAILs) based on the imidazolium cation were first reported in 2009. Since then, a series of TAAILs with different properties due to the electron‐donating or ‐withdrawing effect of the substituents at the aryl ring has been developed. Herein, a wide variety of those ionic liquids (ILs) is presented in terms of their cation structure. The authors synthesized ILs containing the bromide or bis(trifluoromethane)sulfonimide anion and 1‐aryl‐3‐alkyl imidazolium cations with various substituents in the ortho and/ or para position of the phenyl ring and alkyl chains of different lengths varying from butyl to dodecyl. The differences of their physical properties (melting point, thermal decomposition, viscosity, electro‐chemical window) of these ILs are reported according to their structure., Different 1‐aryl‐3‐alkyl imidazolium ionic liquids (tunable aryl alkyl ionic liquids, TAAILs) with electron withdrawing and electron donating substituents on the phenyl ring of the cation, various alkyl chain lengths and the bis(trifluoromethane)sulfonimide (LiNTf2) anion have been prepared. Their physical properties, such as melting points, thermal decomposition, viscosity and electrochemical window, are described to give a broad overview of this class of organic salts.

Ionic liquids (ILs) have been widely used in biomedical and pharmaceutical fields as solvents or permeation enhancers. Recently, more and more researchers focused on optimizing the physicochemical properties of active pharmaceutical ingredient (API) by ILs technology. Converting APIs into ILs (API-ILs) has shown great potential for drug delivery by eliminating polymorphism, tailoring solubility, improving thermal stability, increasing dissolution, controlling drug release, modulating the surfactant properties, enhancing permeability of APIs and modulating cytotoxicity on tumor cells. In addition, API-ILs are also used in various formulations as active ingredients, such as solutions, emulsions, even tablets or nanoparticles. This paper aims to review current status of API-ILs, including the rational and design, preparation and characterization, the improvement on the physicochemical characteristics of APIs, the compatibility of API-ILs with various formulations, and the future prospects of API-ILs in biomedical and pharmaceutical fields.

Development of new plant protection strategies has become an urgent matter in modern agriculture, in view of the evidently proved negative effect of currently used active ingredients of pesticides. In recent years, much effort has been made to eliminate the use of pesticides established to be toxic to pollinators.In this study, we present a group of new bifunctional ionic liquids based on dodine (N-dodecylguanidine) cation whose physical and biological properties have been modified relative to those of the commercially available N-dodecylguanidine acetate. The decreased level of residue of active substances in plant tissues reduces their availability to pollinators, which increases the safety of their use. Moreover, lower environmental impact in combination with high antifungal activity and an additional biological function, that is the systemic acquired resistance induction, are in line with the goals of sustainable agriculture.The presented approach shows the possibility of derivatization of commonly used fungicide into the form of bifunctional salts whose physical and biological properties can be easily modified. The paper reports successful design and synthesis of new sustainable and green chemicals for the modern agriculture, being less toxic to the environment and human health but still effective against pathogens. © 2021 Society of Chemical Industry.

Six hydrophobic magnetic guanidinium ionic liquids (HMILs) were designed and prepared for the extraction of DNA. The physical and thermal properties of the HMILs were characterized using vibrating sample magnetometry, density meter, rotational rheometer, Karl Fischer moisture, Fourier transform infrared spectrometry, and thermogravimetric analysis. Single-stranded DNA and duplex DNA extracted by HMILs can be rapidly collected by a magnet. Three assisted extraction methods, including vortex extraction, mechanical shaking extraction, and ultrasonic extraction, were introduced to extract DNA with HMILs and the extraction efficiencies were evaluated using NanoDrop. Influencing factors of the DNA extraction were comprehensively evaluated, involving the HMIL volume, extraction time, pH, and extraction temperature. The HMIL-based extraction method can well extract DNA from complex matrices and Escherichia coli cell lysates.

The study highlights the effect of acid- and base-rich conditions on the proton dynamics of diethylmethylammonium poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide, [DEMA][PSTFSI], a polymerized protic ionic liquid designed as a polymer electrolyte for nonhumidified polymer electrolyte membrane fuel cells. Different proportions of triflic acid (HTf) and diethylmethylamine (DEMA) were added to the pristine polymer. The thermal analysis of the mixtures revealed that the addition of the base increases the glassy/amorphous nature of the polymer; however, HTf plasticizes the polymer and lowers the Tg value, so that it falls outside of the differential scanning calorimetry-studied temperature range. 50 mol % doping of the HTf contents increases the conductivity upto 0.952 mS cm-1, and 50 mol % DEMA mixture has a conductivity of 0.169 mS cm-1 at 100 °C. Vogel-Tamman-Fulcher fitting of the ionic conductivities of the doped systems suggested that the ionic conductivities are completely decoupled from segmental motion of the polymer. A combination of Fourier transform infrared and static NMR studies demonstrated that HTf-added polymer composites show conduction via Grotthuss and vehicular mechanisms, while DEMA-added polymer composites show predominantly a Grotthuss mechanism by developing the aggregates of proton and added base.

Silver(I) ions undergo selective olefin complexation and have been utilized in various olefin/paraffin separation techniques such as argentation chromatography and facilitated transport membranes. Ionic liquids (ILs) are solvents known for their low vapor pressure, high thermal stability, low melting points, and ability to promote a favorable solvation environment for silver(I) ion-olefin interactions. To develop highly selective separation systems, a fundamental understanding of analyte partitioning to the stationary phase and the thermodynamic driving forces behind solvation is required. In this study, a chromatographic model treating silver(I) ions as a pseudophase is constructed and employed for the first time to investigate the olefin separation mechanism in silver(I) salt/IL mixtures. Stationary phases containing varying amounts of noncoordinated silver(I) salt ([Ag+][NTf2-]) dissolved in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C10MIM+][NTf2-]) IL are utilized to determine the partition coefficients of various analytes including alkanes, alkenes, alkynes, aromatics, aldehyde, esters, and ketones. As ligand coordination to silver(I) ions is known to lower its olefin complexation capability, this study also examines two different types of coordinated silver(I) ion pseudophases, namely, monocoordinated silver(I) salt ([Ag+(1-decyl-2-methylimidazole, DMIM)][NTf2-]) and dicoordinated silver(I) salt ([Ag+(1-methylimidazole, MIM)(DMIM)][NTf2-]). The extent of olefin partitioning to the coordinated silver(I) ion pseudophases over the carrier gas and IL decreased by up to two orders of magnitude. Values for enthalpy, entropy, and free energy of solvation were determined for the three silver(I) ion-containing systems. Olefin retention was observed to be enthalpically dominated, while ligand coordination to the silver(I) ion pseudophase resulted in variations for both enthalpic and entropic contributions to the free energy of solvation. The developed model can be used to study chemical changes that occur in silver(I) ions over time as well as identify optimal silver(I) salt/IL mixtures that yield high olefin selectivity.

Neodymium (Nd) is one of the most essential rare-earth metals due to its outstanding properties and crucial role in green energy technologies such as wind turbines and electric vehicles. Some of the key uses includes permanent magnets present in technological applications such as mobile phones and hard disk drives, and in nickel metal hydride batteries. Nd demand is continually growing, but reserves are severely limited, which has put its continued availability at risk. Nd recovery from end-of-life products is one of the most interesting ways to tackle the availability challenge. This perspective concentrates on the different methods to recover Nd from permanent magnets and rechargeable batteries, covering the most developed processes, hydrometallurgy and pyrometallurgy, and with a special focus on electrodeposition using highly electrochemical stable media (e.g., ionic liquids). Among all the ionic liquid chemistries, only phosphonium ionic liquids have been studied in-depth, exploring the impact of temperature, electrodeposition potential, salt concentration, additives (e.g., water) and solvation on the electrodeposition quality and quantity. Finally, the importance of investigating new ionic liquid chemistries, as well as the effect of other metal impurities in the ionic liquid on the deposit composition or the stability of the ionic liquids are discussed. This points to important directions for future work in the field to achieve the important goal of efficient and selective Nd recovery to overcome the increasingly critical supply problems.

We developed a new hybrid material resulting from an innovative supramolecular tripartite association between an ionic liquid covalently immobilized on primary β-cyclodextrins rim and an anionic water-soluble polymer. Two hydrophilic ternary complexes based on native and permethylated β-cyclodextrins substituted with an ionic liquid and immobilized on poly(styrene sulfonate) (CD-IL+PSS− and CD(OMe)IL+PSS−) were obtained by simple dialysis with a cyclodextrin maximal grafting rate of 25% and 20% on the polymer, respectively. These polyelectrolytes are based on electrostatic interactions between the opposite charges of the imidazolium cation of the ionic liquid and the poly(styrene sulfonate) anion. The inclusion properties of the free cavities of the cyclodextrins and the synergic effect of the polymeric matrix were studied with three reference guests such as phenolphthalein, p-nitrophenol, and 2-anilinonaphthalene-6-sulfonic acid using UV-visible, fluorescent, and NMR spectroscopies. The support has been applied successfully in dialysis device to extract and concentrated aromatic model molecule. This simple and flexible synthetic strategy opens the way to new hybrid materials useful for fast and low-cost ecofriendly extraction techniques relevant for green analytical chemistry.

Persulfate oxidation technology is widely used in wastewater treatment, but there are still many disadvantages, such as high energy consumption, side reaction and narrow pH applicability. Copper oxides can activate persulfate steadily with higher efficiency. In this paper, a novel preparation method of shape-controlled cuprous oxide (Cu2O) nanoparticles featured with high catalytic performance was explored. It was found that adding ionic liquid 1-butyl-3-methylimidazolium bromide ([BMIM]Br) during preparation of Cu2O can improve the degradation rate of diclofenac (DCF). Cu2O nanoparticles possess good stability in consecutive cycling tests, which was confirmed by X-ray photoelectron spectroscopy. The possible mechanism of Cu2O activating persulfate at different initial pH conditions was discussed based on electron paramagnetic resonance spin-trapping experiment. It was found that DCF was efficiently degraded in the Cu2O/peroxydisulfate (PDS) system within a broad pH range from 5 to 11. It proved via a quenching experiment that the activation process of PDS mainly occurs on the surface layer of Cu2O nanoparticles. As a result, shape-controlled Cu2O nanoparticles prepared by ionic liquid are expected to be used for in situ chemical oxidation, which is an effective oxidation processes to degrade DCF remaining in surface water and ground water. HIGHLIGHTS This study provides a novel preparation method of shape-controlled cuprous oxide (Cu2O) particles featured with high catalytic performance to degrade diclofenac (DCF).; It overcomes the disadvantages of degradation of organic pollutants by the traditional Fe in situ chemical oxidation system to some extent, such as being unrecyclable and having a narrow application range of pH value.

Developing renewable energy technology is an effective way to address the global warming and air pollution problems derived from depleting fossil fuels. Due to the high theoretical capacity (3860 mAh g−1) and low electrochemical potential of lithium metal anode, lithium metal batteries (LMBs) have attracted tremendous research attention with the scalable application and vigorous deployment of electric vehicles. Unfortunately, the further commercialization of Li metal anode is hindered by the random growth of Li dendrites during the lithium plating/stripping processes, leading to the continuous consumption of active Li and the puncture on the separator. Just recently, Ma's group proposed a new approach to systematically investigate the relationship between functional groups and Li dendrite generation during the Li plating/stripping processes. The proposed new approach could be of an effective tool to gain new insights into functional groups in the electrolyte additives and Li dendrites formation, highly valuable for the rational structural design of highperformance Li metal electrode materials.

The utilization of sugarcane bagasse (SB) in fermentation requires pretreatment processes to render fermentable components available to microorganisms. Pretreatment by using ionic liquids (ILs) is considered promising but the high cost is an impediment in its adoption, therefore, a mixture of IL pretreated and untreated SB was utilized to obtain bacterial multienzyme under solid-state fermentation (SSF). Bacillus aestuarii UE25, a thermophilic strain was utilized for that purpose. Fermentation conditions were optimized by adopting a central composite design. The model showed a good correlation between the predicted and the experimental values for amylase, xylanase, endoglucanase, and β-glucosidase. Volumetric and specific productivity of xylanase (4580 IU ml-1 h-1 , 244.25 IU mg-1 substrate, and 50 IU mg-1 protein) were higher than the other enzymes. Changes in lignin content and reduced cellulose crystallinity due to IL pretreatment, followed by fermentation, were visualized by scanning electron microscopy, Fourier transform infrared spectroscopy, and Nuclear magnetic resonance. The strategy adopted by utilizing a mixture of IL pretreated and untreated SB under SSF proved promising to obtain high titers of different enzymes simultaneously. Since the bacterial strain used is thermophilic, therefore, the multienzyme can find its application in commercial processes which are carried out at high temperatures.

Since injection administration for diabetes is invasive, it is important to develop an effective transdermal method for insulin. However, transdermal delivery remains challenging owing to the strong barrier function of the stratum corneum (SC) of the skin. Here, we developed ionic liquid (IL)-in-oil microemulsion formulations (MEFs) for transdermal insulin delivery using choline-fatty acids ([Chl][FAs])-comprising three different FAs (C18:0, C18:1, and C18:2)-as biocompatible surface-active ILs (SAILs). The MEFs were successfully developed using [Chl][FAs] as surfactants, sorbitan monolaurate (Span-20) as a cosurfactant, choline propionate IL as an internal polar phase, and isopropyl myristate as a continuous oil phase. Ternary phase behavior, dynamic light scattering, and transmission electron microscopy studies revealed that MEFs were thermodynamically stable with nanoparticle size. The MEFs significantly enhanced the transdermal permeation of insulin via the intercellular route by compromising the tight lamellar structure of SC lipids through a fluidity-enhancing mechanism. In vivo transdermal administration of low insulin doses (50 IU/kg) to diabetic mice showed that MEFs reduced blood glucose levels (BGLs) significantly compared with a commercial surfactant-based formulation by increasing the bioavailability of insulin in the systemic circulation and sustained the insulin level for a much longer period (half-life > 24 h) than subcutaneous injection (half-life 1.32 h). When [Chl][C18:2] SAIL-based MEF was transdermally administered, it reduced the BGL by 56% of its initial value. The MEFs were biocompatible and nontoxic (cell viability > 90%). They remained stable at room temperature for 3 months and their biological activity was retained for 4 months at 4 °C. We believe SAIL-based MEFs will alter current approaches to insulin therapy and may be a potential transdermal nanocarrier for protein and peptide delivery.

Ionic liquids (ILs) are synthetic solvents used as replacements for volatile organic solvents. Human exposure occurs through dermal or oral routes. In rodents, several ILs were reported to induce dermal toxicity, irritation, and sensitization. Due to the potential for occupational exposure, and industrial use as nonvolatile solvents, 1-ethyl-3-methylimidazolium chloride (EMIM, 6.25% to 50% v/v), 1-butyl-3-methylimidazolium chloride (BMIM, 3.12% to 12.5% v/v), 1-butyl-1-methylpyrrolidinium chloride (BMPY, 0.825% to 6.25% v/v), and N-butylpyridinium chloride (NBuPY, 0.825% to 12.5% v/v) were nominated to the National Toxicology Program and evaluated for skin sensitization. The test compound was applied to the ears of female BALB/c mice daily for 3 days in a primary irritancy (IRR)/local lymph node assay (LLNA). Sensitization was assessed in vitro in the direct peptide reactivity assay (DPRA), KeratinoSens™ assay, and human cell line activation test (h-CLAT). In the LLNA, the butylated ILs, BMIM, and BMPY were more potent than NBuPY (butylated) or EMIM (ethylated), which was neither an irritant nor a sensitizer. NBuPY induced skin irritation in vivo at ≥3.12% (p ≤ 0.01), and sensitization in vitro in the KeratinoSens™ assay and h-CLAT, but was negative for sensitization in vivo and in the DPRA. Although SI3 was not achieved, dermal treatment with 12.5% BMIM or 6.25% BMPY increased (p ≤ 0.01) lymph node cell proliferation in the LLNA. In vitro, BMIM was positive for sensitization in the h-CLAT, and BMPY was positive in the h-CLAT and KeratinoSens™ assay; both were negative in the DPRA. Integrated data analyses, weighted toward in vivo data, suggested that BMIM and BMPY may induce weak to mild sensitization.

This study highlights the role of time-dependent hydrolysis of ionic liquid anion, [BF4]-, of ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate, [C2mim][BF4], which results in ever-changing pH conditions. Such pH changes along with the ionic interactions bring conformational changes in bovine serum albumin (BSA), leading to the formation of amyloid fibers at 37 °C without external control of pH or addition of electrolyte. The fibrillation of BSA occurs spontaneously with the addition of IL; however, the highest growth rate has been observed in aqueous solution of 10% IL (v/v %) among investigated systems. Thioflavin T (ThT) fluorescence emission has been employed to monitor the growth and development of β-sheet content in amyloid fibrils. The structural alterations in BSA have also been investigated using intrinsic fluorescence measurements. Circular dichroism (CD) measurements confirmed the formation of amyloid fibrils. Transmission electron microscopy (TEM) has been explored to establish the morphologies of BSA fibrils at different intervals of time, whereas atomic force microscopy (AFM) has established the helically twisted nature of grown amyloid fibrils. The docking studies have been utilized to understand the insertion of IL ions in different domains of BSA, which along with decreased pH cause the unfolding and growth of BSA into amyloid fibrils. It is expected that the results obtained from this study would help to understand the impact of IL containing [BF4]- anion on protein stability and aggregation along with providing a new platform to control the formation of amyloid fibrils and other biomaterials driven via ionic interactions and alterations in pH.

Chemical reactivity, kinetics, degradation pathways and mechanisms, and ecotoxicity of the oxidation of 1-vinyl-3-ethylimidazolium bromide ([VEIm]Br), the most common alternative to organic solvents, by Fe(VI) (HFeO4-) were studied by lab experiments and theoretical calculations. Results show that Fe(VI) can efficiently remove VEIm through the dioxygen transfer-hydrolysis mechanism, which has not been reported yet. The reactivity of VEIm toward Fe(VI) mainly depends on the double bonds in the side chain of VEIm. The second-order rate constant for VEIm was 629.45 M-1 s-1 at pH 7.0 and 25 °C. Typical water constituents, except for SO32-, Cl-, and Cu2+, had no obvious effects on the oxidation. The oxidation products were determined by high-performance liquid chromatography hybrid quadrupole time-of-flight mass spectrometry, which proves that there were interactions between the oxidation intermediates of the anion and cation parts of [VEIm]Br during the degradation process. The structures of related products and oxidation mechanisms were further rationalized by theoretical calculations. The ecotoxicity of products from the three oxidation pathways all showed a trend of increase after the initial decrease. We hope that the findings of this work can give researchers some new inspirations on Fe(VI) degradation of other alkene-containing contaminants.

A new recyclable basic ionic liquid was introduced as an efficient catalyst for aldol condensation and transesterification reactions under environmentally friendly conditions. The catalyst was prepared based on methyl imidazolium moieties bearing hydroxide counter anions via the Hofmann elimination on a 1,3,5‐triazine framework. The ionic liquid with two functionalities including anion stabilizer and high basicity, was used as an efficient catalyst for aldol condensation as well as transesterification reaction of a variety of alkyl benzoates. All reactions were performed in the absence of any external reagent, co‐catalyst, or solvent, in line with environmental protection. The kinetics isotope effect (KIE) was conducted for the transesterification reaction to elucidate the mechanism and rate determining step (RDS). It worth noted that, the homogeneous catalyst could be recycled from the reaction mixture and reused for several consecutive runs with insignificant drop of basicity and conversion., A homogenous recyclable ionic liquid with high basicity has been developed for metal‐ and solvent‐free aldol condensation and transesterification reaction.

We synthesized new imidazolium‐based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2F5)4]−. Phenyl and phenyl derivatives (2‐Me, 4‐OMe, 2,4‐F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C2F5)4] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2‐Me‐substituted gallate‐TAAILs slowly decompose over several weeks, whereas all other gallate‐TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66–162 cP, the gallate‐TAAILs are promising candidates as electrolytes in electrochemical applications., New gallate‐TAAILs (imidazolium‐based tunable aryl alkyl ionic liquids) containing the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2F5)4]‐, are promising candidates as electrolytes in electrochemical applications. Phenyl and phenyl derivatives (2‐Me, 4‐OMe, 2,4‐F) in combination with different alkyl chain lengths from 1–12 carbon atoms were investigated with regard to their viscosity, conductivity and electrochemical window and compared to EMIM and BMIM standard cations. Contrary to the gallate‐TAAIls, the EMIM and BMIM gallates show electrochemical instability.

By simulating butan-2-ol dissolved in the chiral ionic liquid 1-ethyl-3-methylimidazolium (S)-alaninate, we investigate the chiral recognition of butan-2-ol in the ionic liquid. The hydrogen bonding between the chiral anion and both enantiomers of butan-2-ol is similar; however, both chiral molecules (anion and alcohol) induce an asymmetry in the achiral cation which leads to a more favorable environment for the alcohol in the heterochiral system as compared to the homochiral system and hence provides an energetic stabilization of the former.

This study explores the transport properties of bis(trifluoromethylsulfonyl)imide-based ionic liquids with a naturally derived (1R,2S,5R)-(−)-menthol moiety in the cationic part. In particular, we investigated the dependence of the dynamic viscosity and electrical conductivity as functions of the alkyl chain length. An important finding of this study is that both properties show nonmonotonic behavior with respect to the alkyl chain length. The nonmonotonic dependency is an obstacle for establishing the relationships between the structure and transport properties of homologues. To overcome this difficulty, we recommend fast property screening using a theoretical model that we developed, which allows for efficient viscosity prediction by means of the group contribution method. As demonstrated in this study, the model allows for reliable predictions of viscosity in the studied series with an overall relative deviation of less than 8%.

In this work, a simple, reliable, and fast capillary electrophoretic method was developed and validated for the simultaneous determination of 12 polyphenolic compounds, the most frequently found in carob's pulp and seeds. The present work deals with the development of a novel dual electrophoretic system based on the combined use of β-CD and ionic liquid (IL) as buffer additives. A baseline separation of the target analytes was achieved in less than 10 min by using a BGE consisting of 35 mM borate along with 15 mM β-CD and 3 mM l-alanine tert butyl ester lactate (l-AlaC4 Lac) IL as buffer additives at pH 9.5, a temperature of 25°C, and an applied voltage of 30 kV. The application of the developed electrophoretic method to real samples enabled the identification and quantification of the main phenolic constituents of both ripe and unripe carob pulp extracts. The results revealed the predominance of gallic acid in both ripe (183.92 μg/g carob pulp) and unripe (205.10 μg/g carob pulp) carob pulp and highlighted the great influence of the ripening stage on carobs polyphenolic composition, with unripe pods being more enriched in polyphenols (total phenolics detected: 912.58 and 283.13 μg/g unripe and ripe carob pulp).

Solutions of two types of cellulose in the ionic liquid 1-butyl-3-methyl-imidazolium acetate (BmimAc) have been analyzed using rheology and fast-field cycling nuclear magnetic resonance (NMR) spectroscopy, in order to analyze the macroscopic (bulk) and microscopic environments, respectively. The degree of polymerization (DP) was observed to have a significant effect on both the overlap (c*) and entanglement (ce) concentrations and the intrinsic viscosity ([η]). For microcrystalline cellulose (MCC)/BmimAc solutions, [η] = 116 mL g-1, which is comparable to that of MCC/1-ethyl-3-methyl-imidazolium acetate (EmimAc) solutions, while [η] = 350 mL g-1 for the commercial cellulose (higher DP). Self-diffusion coefficients (D) obtained via the model-independent approach were found to decrease with cellulose concentration and increase with temperature, which can in part be explained by the changes in viscosity; however, ion interactions on a local level are also important. Both Stokes-Einstein and Stokes-Einstein-Debye analyses were carried out to directly compare rheological and relaxometry analyses. It was found that polymer entanglements affect the microscopic environment to a much lesser extent than for the macroscopic environment. Finally, the temperature dependencies of η, D, and relaxation time (T1) could be well described by Arrhenius relationships, and thus, activation energies (Ea) for flow, diffusion, and relaxation were determined. We demonstrate that temperature and cellulose concentration have different effects on short- and long-range interactions.

Lithium metal batteries are gaining increasing attention due to their potential for significantly higher theoretical energy density than conventional lithium ion batteries. Here, we present a novel mechanochemical modification method for lithium metal anodes, involving roll-pressing the lithium metal foil in contact with ionic liquid-based solutions, enabling the formation of an artificial solid electrolyte interphase with favorable properties such as an improved lithium ion transport and, most importantly, the suppression of dendrite growth, allowing homogeneous electrodeposition/-dissolution using conventional and highly conductive room temperature alkyl carbonate-based electrolytes. As a result, stable cycling in symmetrical Li∥Li cells is achieved even at a high current density of 10 mA cm–2. Furthermore, the rate capability and the capacity retention in NMC∥Li cells are significantly improved.

The large electrochemical and cycling stability of “water‐in‐salt” systems have rendered promising prospective electrolytes for batteries. The impact of addition of water on the properties of ionic liquids has already been addressed in several publications. In this contribution, we focus on the changes in the state of water. Therefore, we investigated the protic ionic liquid N‐butyl‐pyrrolidinium bis(trifluoromethanesulfonyl)imide with varying water content at different temperatures with the aid of molecular dynamics simulations. It is revealed that at very low concentrations, the water is well dispersed and best characterized as shared solvent molecules. At higher concentrations, the water forms larger aggregates and is increasingly approaching a bulk‐like state. While the librational and rotational dynamics of the water molecules become faster with increasing concentration, the translational dynamics are found to become slower. Further, all dynamics are found to be faster if the temperature increases. The trends of these findings are well in line with the experimental measured conductivities., From single molecules to bulk liquid: The state of water in a protic ionic liquid at different concentration is investigated by the aid of molecular dynamics simulations. At a low concentration, the water shows the behavior of free molecules. With increasing concentration, the formation of clusters can be observed. Finally, at concentrations near the phase separation the behavior approaches that of the bulk liquid.

The ionoSolv process is one of the most promising technologies for biomass pretreatment in a biorefinery context. In order to evaluate the transition of the ionoSolv pretreatment of biomass from bench-scale experiments to commercial scale, there is a need to get better insight in process intensification. In this work, the effects of biomass loading, particle size, pulp washing protocols and 100-fold scale up for the pretreatment of the grassy biomass Miscanthus giganteus with the IL triethylammonium hydrogen sulfate, [TEA][HSO4], are presented as a necessary step in that direction. At the bench scale, increasing biomass loading from 10 to 50 wt% reduced glucose yields from 68 to 23% due to re-precipitation of lignin onto the pulp surface. Omitting the pulp air-drying step maintained saccharification yields at 66% at 50 wt% loading due to reduced fiber hornification. 100-fold scale-up (from 10 mL to 1 L) improved the efficacy of ionoSolv pretreatment and increasing loadings from 10 to 20 wt% reduced lignin reprecipitation and led to higher glucose yields due to the improved heat and mass transfer caused by efficient slurry mixing in the reactor. Pretreatment of particle sizes of 1–3 mm was more effective than fine powders (0.18–0.85 mm) giving higher glucose yields due to reduced surface area available for lignin re-precipitation while reducing grinding energy needs. Stirred ionoSolv pretreatment showed great potential for industrialization and further process intensification after optimization of the pretreatment conditions (temperature, residence time, stirring speed), particle size and biomass loading. Pulp washing protocols need further improvement to reduce the incidence of lignin precipitation and the water requirements of lignin washing.

The development of biocompatible ionic liquids is needed in order to explore their vastly underutilized pharmaceutical potential. US10912834 patent discloses ionic liquids comprising macromolecular biological anions and alkylated cations, which provides enhanced dermal delivery and cell internalization of the large biological anions. The studies of ex vivo permeation through excised pig skin indicated significantly higher skin penetration of percent dose and enhanced drug internalization was achieved using these ionic liquids. Although, the patent advances an infant field of biological macromolecule-based ionic liquids, the evaluation of these claimed ionic liquids relies only on the in vivo cytotoxicity data and ex vivo skin permeation behavior. Exhaustive studies, including dermatokinetic evaluation and long-term animal toxicity experiments, should be performed in order to unravel the potential of the aforementioned ionic liquids.