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In the search for pharmaceutically active compounds from natural products, it is crucial and challenging to develop separation or purification methods that target not only structurally similar compounds but also those with specific pharmaceutical functions. The adsorption-based method is widely employed in this field and holds potential for this application, given the diverse range of functional monomers that can be chosen based on structural or functional selectivity. In this work, an imidazolium ionic liquid (IL) modified paper membrane was synthesized via microwave reaction. Caffeic acid (CA), with potential interactions with imidazolium IL and a representative component of phenolic acids in Taraxaci Herba, was chosen as a target compound. After optimization of synthesis and extraction parameters, the resulting extraction membrane could be used to quantitatively analyze CA at ng/ml level, and to extract CA's analogues from the sample matrix. Cheminformatics confirmed the presence of structural and functional similarity among these extracted compounds. This study offers a novel approach to preparing a readily synthesized extraction membrane capable of isolating compounds with structural and functional analogies, as well as developing a membrane solid-phase extraction-based analytical method for natural products., (© 2024 John Wiley & Sons Ltd.)

Weighing paper-assisted magnetic ionic liquid headspace single-drop microextraction using microwave distillation followed by gas chromatography-mass spectrometry was successfully developed to determine the essential oil components in lavender. The magnetic ionic liquid 1-octyl-3-methylimidazolium tetrachloroferrate was successfully synthesized and used as the optimal extraction solvent. An aliquot of 9 μL of magnetic ionic liquid could be stably suspended on the weighing paper for long time extraction. The increase of the extractant volume resulted in a significantly enhanced in extracting efficiency of the weighing paper-assisted magnetic ionic liquid headspace single-drop microextraction than traditional headspace single-drop microextraction method. In this experiment, the optimal conditions were 1-octyl-3-methylimidazolium tetrachloroferrate as the extraction solvent, extraction time of 12 min, microwave power of 600 W, cyclohexane as back-extractant and sample amount of 30 mg. The developed method was successfully applied to analyze 16 lavender samples from three different harvest years. A total of 39 compounds in lavender were identified and the principal component analysis provided a clear separation between those lavender samples harvested in different years. The results indicated that the proposed weighing paper-assisted magnetic ionic liquid headspace single-drop microextraction is a novel, fast, simple and sensitive microextration technique for the determination of the essential oil components in lavender., (© 2020 Wiley-VCH GmbH.)

A new planar sorptive phase based on the simple immobilization of polymeric ionic liquids on paper is proposed. The sorptive phase can develop hydrophobic or mixed-mode (combining hydrophobic and ion exchange) interactions with the target analytes. The polymer is prepared by the Radziszewski reaction, which takes place in aqueous media, and it has been thoroughly characterized by different techniques including infrared spectroscopy, matrix-assisted laser desorption/ionization coupled to high-resolution mass spectrometry and proton nuclear magnetic resonance. Three different strategies aimed to immobilize the polymeric ionic liquid on paper have been evaluated. Among them, simple thermal curing at 120 °C was selected. The as-prepared paper has been evaluated for the extraction of several non-steroidal anti-inflammatory drugs from urine, the analytes being finally determined by liquid chromatography with tandem mass spectrometry. The method detection limits were 3.8, 7.2, 6.8, 9.4, 15.7, and 5.1 μg/L for indomethacin, diclofenac, tolmetin, ketoprofen, naproxen, and ibuprofen, respectively. Calibration models were linear (R 2  > 0.9949) up to 1000 μg/L. The intra-day precision, expressed as relative standard deviation and calculated at three different concentrations levels (limit of quantification, 250 μg/L, and 1000 μg/L), varied between 1.1 and 13%. The accuracy, calculated as relative recovery, was in the range from 72 to 95%, thus being considered appropriate. The easiness of polymeric ionic liquid paper synthesis and the multi-sample extraction protocol designed allows the processing of a high number of samples at the same time., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Cellulose extracted from printed paper wastes were selectively depolymerized under controlled conditions into cello-oligomers of controllable chain lengths via dissolution in an ionic liquid, 1-allyl-3-methylimidazolium chloride (AMIMCl), and in the presence of an acid catalyst, Amberlyst 15DRY. The depolymerization process was optimized against reaction temperature, concentration of acid catalyst, and reaction time. Despite rapid initial depolymerization process, the rate of cellulose depolymerization slowed down gradually upon prolonged reaction time, with 75.0 wt% yield of regenerated cello-oligomers (mean Viscosimetric Degree of Polymerization value of 81) obtained after 40 min. The depolymerization of cellulose fibers at 80 °C appeared to proceed via a second-order kinetic reaction with respect to the catalyst concentration of 0.23 mmol H3O(+). As such, the cellulose depolymerization process could afford some degree of control on the degree of polymerization or chain lengths of cello-oligomers formed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Iron gall inks have been known since Roman times, were widely used in the Medieval Age, and became the most used ink in the Renaissance period. They were still officially used by the German Government as recently as 1973. The two main constituents of the ink are tannic acid and ferrous sulfate (vitriol). The vitriol normally used was not very pure and likely contained a mixture of iron sulfate with traces of other metals, in particular, copper. Certain transition-metal ions contained in iron gall inks and their acidity are known to deteriorate paper. Therefore, stabilization treatments consist of deacidification and the addition of antioxidants. To this end, the use of tetraalkylammonium bromides was recently proposed. Here, it is shown that 1-butyl-2,3-dimethylimidazolium bromide both in aqueous and in alcoholic solution can prevent the oxidative deterioration of cellulose. Furthermore, it does not lead to the yellowing of paper nor does it significantly affect the colour of the ink.

A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O(2)) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The sensor looked like a piece of paper but possessed high sensitivity for O(2) in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors.

Cellulose-based aerogel (CBA) was prepared from waste newspaper (WNP) without any pretreatment using 1-allyl-3-methyimidazolium chloride (AmImCl) as a solvent via regeneration and an environmentally friendly freeze-drying method. After being treated with trimethylchlorosilane (TMCS) via a simple thermal chemical vapor deposition process, the resulting CBAs were rendered both hydrophobic and oleophilic. Successful silanization on the surface of the porous CBA was verified by a variety of techniques including scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and water contact angle (WCA) measurements. As a result, the silane-coated, interconnected CBAs not only exhibited good absorption performance for oils (e.g., waste engine oil), but also showed absorption capacity for organic solvents such as chloroform (with a representative weight gain ranging from 11 to 22 times of their own dry weight), making them diversified absorbents for potential applications including sewage purification., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Waste newspapers, composed of cellulose (>60wt%), lignin (∼15wt%), hemicellulose (∼10wt%) and other additives, are one kind of low-cost, easily collected and abundant resources. In order to get value-added products from this waste, in this work an attempt was made to directly convert waste newspapers into cellulose-based films by employing an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a solvent. Most of the organic substances in this waste were dissolved quickly in AmimCl under mild conditions, and then coagulated and dried. Although containing lignin, hemicellulose and inorganic additives, the regenerated cellulose-based films were smooth, compact and semi-transparent, and exhibited good mechanical properties. If the newspaper/AmimCl solution was filtered to remove undissolved inorganic substances, the regenerated films became transparent and had a tensile strength of 80MPa. Thus, this work provides a new, simple and highly efficient way to achieve a high-valued utilization of waste newspapers for packaging and wrapping., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Ionic liquids (ILs) become emerging environmental pollutants. Especially, alkyl imidazolium ILs commonly showed stimulation in toxicological studies and mechanisms remained to be explored. In the present study, alkyl imidazolium tetrafluoroborate ([amim]BF 4 ), with ethyl ([emim]), hexyl ([hmim]) and octyl ([omim]) as side-chains, were chosen as target ILs. Their toxicities on the reproduction and lifespan of Caenorhabditis elegans were explored with two types (A and B) exposure arrangements to mimic realistic intermittent multi-generational exposure scenarios. In type A scenario, there was an exposure every 4 generations with 12 generations in total, and in type B one, there was an exposure every two generations with 12 generations in total. Result showed that [emim]BF 4 caused inhibition on the reproduction in 8 generations in type A exposure but 6 ones in type B exposure. Meanwhile, [hmim]BF 4 showed inhibition in one generation and stimulation in 3 generations in type A exposure, but stimulation in 6 generations in type B exposure. Also, [omim]BF 4 showed stimulation in one generation in type B exposure. Collectively, the results demonstrated less frequencies of inhibition, or more frequencies of stimulation, in the exposure scenario with more frequent exposures. Further mechanism exploration was performed to measure the lipid storage and metabolism in the aspect of energy supply. Results showed that [emim]BF 4 , [hmim]BF 4 and [omim]BF 4 commonly stimulated the triglyceride (TG) levels across generations. They also disturbed the activities of glycerol-3-phosphate acyltransferase (GPAT) and acetyl CoA carboxylase (ACC) in lipogenesis, those of adipose triglyceride lipase (ATGL) and carnitine acyl transferase (CPT) in lipolysis, and also the contents of acetyl-CoA (ACA). Further data analysis indicated the energy allocation among life traits including reproduction, antioxidant responses and hormone regulations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Ionic liquids (ILs) have many beneficial properties that are extensively used in various fields. Despite their utility, the phytotoxic aspects of ILs are poorly known. This is especially true at the transcriptomic level and the role of nitric oxide (NO) in this process. Herein, we studied the mechanism by which endogenous NO reduces the toxicity of ILs in Arabidopsis. We examined the effects of two imidazolium-based ILs (IILs) on three Arabidopsis lines, each characterized by distinct endogenous NO levels, using a combination of physiological and transcriptomics methods. IILs impaired seed germination, seedling development, chlorophyll content, and redox homeostasis in Arabidopsis. Notably, 1,3-dibutyl imidazole bromide had greater toxicity than 1-butyl-3-methylimidazolium chloride. Nox1, a mutant with an elevated NO level, had enhanced resistance, while nia1nia2, a mutant with a diminished NO level, had increased susceptibility compared to the wild type. RNA sequencing results suggested that NO mitigates IILs-induced phytotoxicity by modulating the metabolism of chlorophyll and secondary metabolites, and by bolstering the antioxidant defense system. These findings illustrate the complex molecular networks that respond to IIL stress and reveal the potential of endogenous NO as a mitigating factor in plant stress physiology., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

1-octyl-3-methylimidazolium bromide ([C 8 mim]Br), one of the ionic liquids (ILs), has been used in various fields as an alternative green solvent of conventional organic solvents. Increased application and stabilization of imidazole ring structure lead to its release into the aquatic environment and long-term retention. Structure-activity relationship consideration suggested that ILs may be acetylcholinesterase inhibitors; however, neurotoxicity in vivo, especially the underlying mechanisms is rarely studied. In this study, the zebrafish were exposed to 2.5-10 mg/L [C 8 mim]Br for 28 days to comprehensively evaluate the neurotoxicity of ILs on adult zebrafish from the behavioral profiles and neurotransmitter systems for the first time. The results indicate that zebrafish exhibit suppressed spatial working memory and anxious behaviors. To assess the potential neurotoxic mechanisms underlying the behavioral responses of zebrafish, we measured the levels of neurotransmitters and precursors, key enzyme activities, and expression levels of relevant genes. Nissl staining showed significant neural cell death in zebrafish after 28-day [C 8 mim]Br exposure, with corresponding decreases in the levels of neurotransmitters (acetylcholine, glutamate, 5-hydroxytryptophan, gamma-aminobutyric acid, dopamine, and norepinephrine). Furthermore, these results were associated with mRNA expression levels of the disrupted neurotransmitter key genes (th, tph2, mao, slc6a3, ache, gad67). Overall, our study determined that [C 8 mim]Br caused potential mental disorders like anxiety and memory deterioration in zebrafish by impairing neurotransmitter systems, providing recommendations for the industrial production and application of [C 8 mim]Br., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A class of chemical with a potentially important perceived future contribution to the net zero carbon goal (as "green" solvents) is the methylimidazolium ionic liquids (MILs). These solvents are used in industrial processes such as biofuel production yet little is known about their environmental stability or toxicity in man although one MIL - 1-octyl-3-methylimidazolium (M8OI) - has been shown to activate the human estrogen receptor alpha (ERα). The stabilities of the chloride unsubstituted methylimidazolium (MI) and MILs possessing increasing alkyl chain lengths (2C, 1-ethyl-3-methylimidazolium (EMI); 4C, 1-butyl-3-methylimidazolium (BMI); 6C; 1-hexyl-3-methylimidazolium (HMI), 8C, M8OI; 10C, 1-decyl-3-methylimidazolium (DMI)) were examined in river water and a human liver model system. The MILs were also screened for their abilities to activate the human ERα in vitro and induce uterine growth in pre-pubertal rats in vivo. Short chain MILs (EMI, BMI and HMI) underwent negligible metabolism and mineralisation in river water; were not metabolised in a model of human liver metabolism; activated the human ERα in vitro and were estrogenic in vivo in rats. A structure-based computational approach predicted short chain MIL binding to both the estrogen binding site and an additional site on the human estrogen receptor alpha. Longer chain MILs (M8OI and DMI) were metabolised in river water and partially mineralised. Based on structure-activity considerations, some of these environmentally-derived metabolites may however, remain a hazard to the population. MILs therefore have the potential to become forever chemicals with adverse effects to both man, other animals and the environment in general., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Alkyl imidazolium ionic liquids (Cn[MIM]), initially heralded as eco-friendly green solvents for diverse industrial applications, have increasingly been recognized fortheir biodegradability challenges and multiple biotoxicity. Despite potential health risks, research into the effects of Cn[MIM] on human health remains scarce, particularly regarding their detection in biological serum samples. This study validated a matrix-matched calibration quantitative method that utilizes solid-phase extraction (SPE) coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The method was used to analyze the presence of 10 ionic liquids (ILs) with varying alkyl carbon chain lengths (C 2 -C 12 ) across 300 human serum samples. Efficient separation was achieved using optimized SPE conditions and a BEH C18 column with an appropriate mobile phase. Results demonstrated a strong linear relationship (0.05-100 ng/mL; R 2  = 0.995-0.999), with detection and quantification limits with detection and quantification limits ranging from 0.001 to 0.107 ng/mL and 0.003-0.355 ng/mL, respectively. Intraday and inter-day precisions were 0.85-6.99 % and 1.50-7.46 %, with recoveries between 82 and 113 %. The validated method detected C 6 MIM in 19 % of samples and C 8 MIM in 8.3 % of samples, with concentrations ranging from 0.02 to 111.70 μg/L and 0.09-16.99 μg/L, respectively, suggesting a potential risk of human exposure. This underscores the importance of robust detection methods in monitoring environmental and human health impacts of alkyl imidazolium compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Removing p-nitrophenol (PNP) from water resources is crucial due to its significant threat to the environment and human health. Herein, imidazolium ionic liquids with short/long alkyl chain ([C 2 VIm]Br and [C 8 VIm]Br) modified cellulose microspheres (MCC-[C 2 VIm]Br and MCC-[C 8 VIm]Br) were synthesized by radiation method. To examine the impact of adsorbent hydrophilicity on adsorption performance, batch and column experiments were conducted for PNP adsorption. The MCC-[C 2 VIm]Br and MCC-[C 8 VIm]Br, with an equivalent molar import amount of ionic liquids, exhibited maximum adsorption capacities of 190.84 mg/g and 191.20 mg/g for PNP, respectively, and the adsorption equilibrium was reached within 30 min. Both adsorbents displayed exceptional reusability. Integrating the findings from XPS and FTIR analyses, and AgNO 3 identification, the suggested adsorption mechanism posited that the adsorbents engaged with PNP through ion exchange, hydrogen bonds and π-π stacking. Remarkably, the hydrophobic MCC-[C 8 VIm]Br exhibited superior selectivity for PNP than the hydrophilic MCC-[C 2 VIm]Br, while had little effect on adsorption capacity and rate. MCC-[C 8 VIm]Br-2 with high grafting yield increased the adsorption capacity to 327.87 mg/g. Moreover, MCC-[C 8 VIm]Br-2 demonstrated efficient PNP removal from various real water samples, and column experiments illustrated its selective capture of PNP from groundwater. The promising adsorption performance indicates that MCC-[C 8 VIm]Br-2 holds potential for PNP removal from wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

In this paper, we have performed an all-atom molecular dynamics simulation to understand the structure and dynamics of Na + ions in water mixed Ionic liquids (Water in Ionic liquid). Two ionic liquid (IL) systems consist of (1) 1-butyl-3-methylimidazolium [BMIM] tetrafluoroborate [BF 4 ] and (2) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF 6 ] were considered in this work. We understand various inter - molecular structures and dynamic and thermodynamic behaviours of Na + ions in the water - mixed IL systems. The water (H 2 O) mole fractions (x) varied from 0.33 to 0.71. The neat ILs [BMIM][BF 4 ] and [BMIM][PF 6 ] pairwise radial distribution functions show a decrease with an increase in x. The [BMIM][PF 6 ] exhibits a strong coordination structure with Na + ions across the entire range of x values. The rdf between the pairs of Na + -[PF 6 ] presents a significant interaction compared to Na + and [BF 4 ]. The Na  +  ions manifested greater coordination with H 2 O In H 2 O-[BMIM][PF 6 ] compared to H 2 O-[BMIM][BF 4 ]. The self-diffusion coefficient (D) values of Na  +  ions increase with the rise in x in both ILs. The D values of Na  +  ions are 10-fold higher in [BMIM][BF 4 ] than [BMIM][PF 6 ]. The ionic conductivity values are higher for [BMIM][BF 4 ]. Overall, this paper unveils molecular-level insights for understanding the behavior of Na + ions in the water in ionic liquid systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

In this study, polymeric ionic liquids featuring different functional moieties were applied as sorbent coatings in direct-immersion solid-phase microextraction (DI-SPME) for the extraction of 2-methylimidazole (2-MI) and 4-methylimidazole (4-MI) from açaí-based food products followed by gas chromatography-mass spectrometry (GC-MS) analysis. The analytical method was optimized using a sequential experimental design. Variables used in GC-MS such as desorption time, as well as for SPME-DI, including extraction time, extraction temperature, incubation time of extraction, amount of NaCl in the extract, and stirring rate, were optimized. The fitness-for-purpose of the method was verified by the linearity of matrix-matched calibration curves (R 2  ≥ 0.9921), adequate recoveries (81.7-89.7 %), and precision (relative standard deviations ≤11.2 %). The method was applied to twenty-five samples of açaí-based food products. 4-MI was found in four samples whereas 2-MI was not detected above the limit of detection. The method was found to be suitable for quality control analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The dissolution of cellulose in double salt ionic liquids (DSILs) was studied in detail and compared with the dissolution in individual constituent ionic liquids (ILs). The DSILs, [C 4 mim](CH 3 CO 2 ) x Cl 1-x (x is the mole fraction of the single component ILs), were synthesized using acetate and chloride salts of 1-butyl-3-methylimidazolium. These DSILs were then used for the investigation of the solubility of cellulose in the whole mole fraction range. Commercial cellulose (CC) powder, kraft pulp (KP), and prehydrolysis kraft pulp (PHKP) of jute were chosen as cellulose sources. The solubility of cellulose increased with an increasing temperature for [C 4 mim](CH 3 CO 2 ) 0.6 Cl 0.4 and with increasing amount of [C 4 mim]Cl in DSILs. The maximum solubility of CC powder was 32.8 wt% in [C 4 mim](CH 3 CO 2 ) 0.6 Cl 0.4 at 100 °C, while for KP and PHKP, solubilities were 30.1 and 30.5 wt%, respectively under the identical condition. Cellulose could be regenerated from the DSILs using water as an antisolvent. Structure, morphology, and thermal stability of the regenerated cellulosic materials were analyzed. DSILs could be recycled >99 % without a discernible change in structure. This work demonstrates that DSILs display enhanced solubility over ILs system and have potential as a chemical processing methodology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

When ionic liquids (ILs) first came into use, we thought that they were safe. However, upon further investigation, researchers found that ILs are not harmless. In this study, the model soil organism, earthworms (Eisenia foetida), were used to study the acute toxicity of imidazole nitrate ionic liquids with varying chain lengths from 2 to 12. The experiment used two different methods, a filter paper contact test (48 h) and an artificial soil test (14 days), to determine the toxicity. These results demonstrated that the toxicity increased with the length of carbon chains until C 8 and that the cut-off effect occurred at 1-octyl-3-methyl imidazole nitrates.Then, the toxicity began to increase again. At the same time, the concentrations of [C 10 mim]NO 3 and [C 12 mim]NO 3 were determined by high performance liquid chromatography and demonstrated that ILs were stable throughout the experiment. The present study revealed the acute toxicity of ILs with varying chain lengths.

In this paper, a reinforced Biomass Gel Artificial Muscle (BGAM) was fabricated by natural polysaccharide of Sodium Alginate (SA) doped with an Ionic Liquid (IL) of 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIm][BF 4 ]). Micro-nano regulation effect and reinforcement mechanism of IL doping content on electromechanical response performance of BGAM were researched during a single cycle and repeated cycles. Then, a green fabrication process and a set of valid test methods for BGAM were proposed in detail. The experimental results showed that when IL doping content was 4 mL, the BGAM achieved optimal modification, with a porosity of 70.47%, where it internally adopted the porous polymer structure of ion channels. Additionally, specific capacitance of BGAM attained a maximum value of 126.98 mF/g, and the inner resistance and elastic modulus reached minimum values of 2.018 Ω and 1.871 MPa, separately. Thus, the optimal working life and output-force density values, namely, 1720 s and 13.072 mN/g, respectively, were also determined for the BGAM., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The paper presents the results of a study on the preparation of cellulose-based composite fibres (CEL) with graphene oxide addition (GO). Composite fibres (GO/CEL) were prepared via the wet spinning method from CEL solutions in 1-ethyl-3-methylimidazolium acetate (EMIMAc) that contained a nano-addition of GO dispersion in N,N-dimethylformamide (DMF). The GO contents of the composite fibres were 0, 0.21, 0.50, 0.98, and 1.97 % w w. The fibres were coagulated in two solvents: distilled water and methanol. The results demonstrated that the amount of GO additive and the type of coagulant significantly impact the physicochemical, mechanical and structural properties of the CEL and GO/CEL fibres. The use of distilled water in a coagulation bath causes a degree of crystallinity of 31.0-40.8 % (WAXS) and a shift in the thermal decomposition temperature (by approximately 19 °C) towards higher temperatures (TGA). The results demonstrate improvements in the mechanical properties of the GO/CEL fibres, which were at the level of 9.43-14.18 cN/tex. In addition, the GO/CEL fibres exhibit satisfactory GO dispersion throughout their volume., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Ionic liquids have been suggested as new engineering fluids, namely in the area of heat transfer, as alternatives to current biphenyl and diphenyl oxide, alkylated aromatics and dimethyl polysiloxane oils, which degrade above 200 °C and pose some environmental problems. Recently, we have proposed 1-ethyl-3-methylimidazolium methanesulfonate, [C 2 mim][CH 3 SO 3 ], as a new heat transfer fluid, because of its thermophysical and toxicological properties. However, there are some interesting points raised in this work, namely the possibility of the existence of liquid metastability below the melting point (303 K) or second order-disorder transitions ( l -type) before reaching the calorimetric freezing point. This paper analyses in more detail this zone of the phase diagram of the pure fluid, by reporting accurate thermal-conductivity measurements between 278 and 355 K with an estimated uncertainty of 2% at a 95% confidence level. A new value of the melting temperature is also reported, T melt = 307.8 ± 1 K. Results obtained support liquid metastability behaviour in the solid-phase region and permit the use of this ionic liquid at a heat transfer fluid at temperatures below its melting point. Thermal conductivity models based on Bridgman theory and estimation formulas were also used in this work, failing to predict the experimental data within its uncertainty.

The present study was designed to explore the hydrophobicity and concentration dependence of imidazolium based surface active ionic liquids (SAILs) effects on the structural-functional integrity of proteins. Specifically, we investigated the impact of SAILs viz. 1-octyl-3-methylimidazolium dodecylbenzenesulfonate ([OMIM][DBS]) and 1-dodecyl-3-methylimidazolium dodecylbenzenesulfonate ([DDMIM][DBS]) on activity, structure and stability of lysozyme. Activity measurements revealed that, in contrast to [DDMIM][DBS] that renders lysozyme either feebly active or inactive, [OMIM][DBS] significantly enhances the lysozyme activity in the concentration range of critical aggregation concentrations (CAC) to C s (SAIL saturation concentration of protein backbone) i.e., 0.5 mM-1.35 mM. Tensiometric results in agreement with turbidity measurements inferred significant composition and concentration dependence of the lysozyme-SAIL interactions. Spectroscopic investigations revealed that compared to destabilizing behaviour of [DDMIM][DBS], [OMIM][DBS] significantly enhances both conformational as well as thermal stability of lysozyme in the CAC to C s concentration regime. Altogether, results obtained do indicate that [OMIM][DBS], in the concentration regime of CAC to C s , serves as an efficient stabiliser with an ability to appreciably enhance the activity, thermal stability and overall conformational stability of lysozyme. We firmly believe that [OMIM][DBS], at least in the CAC to C s concentration ranges, can be exploited as a promising stabiliser and activity enhancer for numerous industrially important enzymes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

An imidazolium ionic-liquid-modified phenolic resin (ILPR) was synthesized using 3-aminophenol as a functional monomer, glyoxylic acid as a green cross-linker, and polyethylene glycol 6000 as a porogen. The obtained ILPR showed better extraction of benzoylurea plant hormones thidiazuron and forchlorfenuron than the unmodified phenolic resin because the imidazolium IL provides more interaction modes with the analytes. ILPR, as a tailored adsorbent for solid-phase extraction, was coupled with high-performance liquid chromatography (ILPR‒SPE‒HPLC) for the simultaneous determination of thidiazuron and forchlorfenuron in cucumbers. Good linearity of the ILPR‒SPE‒HPLC method was obtained, ranging from 0.0100 to 5.00 μg g -1 with a correlation coefficient (r) ≥ 0.9999. The recoveries of spiked samples ranged from 91.4% to 100.7% with a relative standard deviation of ≤ 6.0%., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Two analytical methodologies based on the combined use of hydroxypropyl-β-cyclodextrin and two different amino acid-based chiral ionic liquids (tetrabutylammonium-L-lysine or tetrabutylammonium-L-glutamic acid) in electrokinetic chromatography were developed in this work to perform the enantioselective determination of econazole and sulconazole in pharmaceutical formulations. The influence of different experimental variables such as buffer concentration, applied voltage, nature and concentration of the ionic liquid, temperature and injection time, on the enantiomeric separation was investigated. The combination of hydroxypropyl-β-cyclodextrin and tetrabutylammonium-L-lysine under the optimized conditions enabled to achieve the enantiomeric determination of both drugs with high enantiomeric resolution (3.5 for econazole and 2.4 for sulconazole). The analytical characteristics of the developed methodologies were evaluated in terms of linearity, precision, LOD, LOQ and recovery showing good performance for the determination of both drugs which were successfully quantitated in pharmaceutical formulations. This work reports the first analytical methodology enabling the enantiomeric determination of sulconazole in pharmaceutical formulations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Bacterial biofilm is an obstacle for wound healing because it can affect the epithelialization, development of granular cells, and other regular inflammatory procedures. It plays the role of safeguarding pathogens from antiseptics and antibiotics. In this respect, this research work aims to develop heteroatom (N, F, P/B) incorporated multi-walled carbon nanotubes (MWCNT), such as NFP-MWCNT and NFB-MWCNT, which can maximize the wound healing efficacy via destroying the wound pathogen and biofilms. NFP-MWCNT and NFB-MWCNT were obtained using self-assembling ionic liquids (ILs) such as BMIM-PF 6 and BMIM-BF 4 in an acid-functionalized MWCNT (A-MWCNT) suspension, followed by pyrolysis in a nitrogen atmosphere. The composite formation was established by FTIR, XRD, RAMAN, EDX mapping, and XPS spectroscopy. TEM and SEM analyses confirmed the bamboo stick-like morphology. During this reaction, IL molecules might be cross-linked with A-MWCNT via hydrogen bonding and ionic interaction, with further pyrolysis producing the defects with doping of N, F, P, or B elements. Finally, they were assessed for their antibiofilm activity against typical bacterial strains such as K. pneumoniae, P. aeruginosa, E. coli (Gram-negative), and B. subtilis (Gram-positive), using a quantitative estimation approach. The results revealed greater effectiveness of NFB-MWCNT and NFP-MWCNT, compared to pristine MWCNT. The antibiofilm activity of NFP-MWCNT and NFB-MWCNT was associated with their specific surface chemistry (due to the presence of N, F, P/B heteroatoms), and their nanosize. Moreover, the synthesized material was examined for its wound-healing ability in Wistar rats. The results proved that cells cultured on NFB-MWCNT and NFP-MWCNT displayed exceptional healing ability. The different electronegativity between the heteroatoms creates the surface charge that inhibits the biofilm formation, leading to healing the wounds together with the heteroatom mineral source for mouse fibroblast regeneration and granulation. This is the first study in which the role of different heteroatoms incorporated into MWCNT is examined in the context of antibiofilm-associated wound-healing ability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Cellulose nanocrystals were prepared using ionic liquids (ILs), 1-ethyl-3-methylimidazolium chloride [EMIM][Cl] and 1-propyl-3-methylimidazolium chloride [PMIM][Cl], from microcrystalline cellulose. The resultant samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The XRD results showed that nanocellulose obtained by treatment with both ILs preserved basic cellulose I structure, but crystallinity index of samples (except for Sigmacell treated with [EMIM][Cl]) was lower in comparison to the starting microcrystalline cellulose. The DLS results indicated noticeably smaller particle sizes of prepared cellulose for material treated with [PMIM][Cl] compared to cellulose samples hydrolyzed with [EMIM][Cl], which were prone to agglomeration. The obtained nanocellulose had a rod-like structure that was confirmed by electron microscopy analyses. Moreover, the results described in this paper indicate that cation type of ILs influences particle size and morphology of cellulose after treatment with ionic liquids.

Ionic liquids, a kind of emerging and persistent organic contaminants, always coexist with heavy metals in aquatic and terrestrial environments. However, the feasibility of phytoremediation to remove ionic liquids and heavy metals co-contaminants is still unclear. Thus, in this study, the hydroponic experiment was conducted to investigate the combined effect of 1-butyl-3-methylimidazolium bromide ([C 4 mim] + Br - ) and cadmium (Cd 2+ ) on growth and physiological indictors of perennial ryegrass, together with their uptake and translocation by plants. Results show that the exposure of ryegrass to [C 4 mim] + and Cd 2+ mixture significantly inhibited the biomass growth and affected the photosynthetic pigments contents in leaves. The increases of lipid peroxidation and catalase, peroxidase activity were also observed under the co-exposure experiments. The mixture toxicity of [C 4 mim] + and Cd 2+ to ryegrass growth showed an additive effect predicted by concentration addition and independent action. [C 4 mim] + uptake and acropetal translocation by ryegrass were significantly inhibited with dosing Cd 2+ . In contrast, [C 4 mim] + had no obvious effect on Cd 2+ uptake by ryegrass, while enhanced Cd 2+ translocation from roots to shoots occurred with increasing [C 4 mim] + dosages. These results indicate that the co-contamination of ionic liquids and heavy metals would affect their fates during phytoremediation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ionic liquids are a diverse range of charged chemicals with low volatility and often liquids at ambient temperatures. This characteristic has in part lead to them being considered environmentally-friendly replacements for existing volatile solvents. However, methylimidazolium ionic liquids are slow to break down in the environment and a recent study at Newcastle detected 1 octyl 3 methylimidazolium (M8OI) - an 8 carbon variant methylimidazolium ionic liquid - in soils in close proximity to a landfill site. The current M8OI toxicity database in cultured mammalian cells, in experimental animal studies and in model indicators of environmental impact are reviewed. Selected analytical data from the Newcastle study suggest the soils in close proximity to the landfill site, an urban soil lacking overt contamination, had variable levels of M8OI. The potential for M8OI - or a structurally related ionic liquid - to trigger primary biliary cholangitis (PBC), an autoimmune liver disease thought to be triggered by an unknown agent(s) in the environment, is reviewed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Herein, to research the toxic effect of ionic liquids (ILs) on earthworms and compare their different toxicities in different soils, 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim]BF 4 ) was selected as a test substance, Eisenia fetida was selected as the experimental indicator organism, and artificial and fluvo-aquic soils were selected as the media. The acute toxicity, reactive oxygen species (ROS) content, detoxification enzyme (GST) activity, anti-oxidant enzyme activities, lipid peroxidation oxidative and DNA damage in earthworms were all measured to evaluate the toxicity of [Bmim]BF 4 . The results showed that either in fluvo-aquic soil or artificial soil, [Bmim]BF 4 can stimulate the accumulation of ROS in earthworms, inducing activities of antioxidant enzymes and detoxification enzymes, inevitably causing lipid peroxidation and DNA damage in earthworms. The integrated biomarker response (IBR) indicated that the toxicity of [Bmim]BF 4 in fluvo-aquic soil was greater than that in artificial soil. This experiment is relevant to the reliability of artificial soil toxicity research, and maybe this paper can provide a more authentic understanding of traditional toxicity experiments., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ionic liquids (ILs) are ionic compounds with low melting points that can be designed to be used in an extensive set of commercial and industrial applications. However, the design of ILs is limited by the quantity and quality of the available data in the literature; therefore, the estimation of physicochemical properties of ILs by computational methods is a promising way of solving this problem, since it provides approximations of the real values, resulting in savings in both time and money. We studied two data sets of 281 and 134 liquids based on the molecule imidazole that were analyzed with QSPR techniques. This paper presents a software architecture that uses clustering techniques to improve the robustness of estimation models of the melting point of ILs. These results indicate an error of 6.25% in the previously unmodeled data set and an error of 4.43% in the second data set. We have an improvement with the second data set of 1.81% over the last results previously found.

In this study, the acute and subchronic toxicity of 1-alkyl-3-methyl imidazole bromide ionic liquids (ILs) [C n mim]Br (n = 2, 4, 6, 10, 12) was evaluated utilizing earthworms (Eisenia fetida) as a basis for their impact on terrestrial ecosystems. The filter paper tests and artificial soil tests were conducted as acute toxicity tests to investigate the LC 50 of ILs, while in subchronic toxicity tests, earthworms were exposed to ILs in artificial soil (5, 10, 20 and 40 mg kg -1 ) for 28 d. Reactive oxygen species (ROS), antioxidant enzymes, detoxifying enzymes and oxidative damage were measured to determine subchronic effects of ILs on E. fetida. The results showed that when the earthworms were exposed to these five ILs in acute toxicity experiments, [C 2 mim]Br had the lowest toxicity, as the alkyl length increased, the toxicity increased up to [C 10 mim]Br: a "cut-off effect" (decreased toxicity) was observed at [C 12 mim]Br. The results highlight the varying toxicity of ILs with different alkyl chains to E. fetida and provide valuable data for detailing the impact of ILs on ecological receptors., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this paper, Single and dual modification with etherification and Cross-linking of Zea mays starch were homogeneously carried out and in [BMIM]Cl ionic liquid media (IL), an excellent solvent for the starch modification using sodium monochloroacetic acid and sodium trimetaphosphate in different sequences. Characteristics analyzed indicated modification of starch which was further confirmed by determining a high degree of etherification (0.79) and Cross-linking (91.2%) could be achieved at short time scale in [BMIM]Cl, which is apparently due to the excellent dissolving capacity and catalytic effect of IL. Temperature showed a positive effect on swelling power and water solubility indexes of native and modified starches, however in Cross-linked starch the swelling power decreased. A considerable reduction in amylose content was noticed after modification except for Cross-linked starch. FT-IR and NMR analyses confirmed the modification of starch. Furthermore, the results of XRD and a SEM revealed that the crystallinity and the morphology of the native Zea mays starch was slightly changed throughout its modification in IL and was completely destroyed. Studies on the phase transitions associated with gelatinization using a DSC showed higher enthalpy values for Cross-linked starch and dual modified starches as compared to native and etherified starch., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Continuous-flow rhodium-catalysed hydroformylation of long chain alkenes has been achieved with selectivities to the desired linear aldehyde of 92% and minimum rhodium loss, using a xantphos-derived ligand attached to an imidazolium salt in a supercritical fluid–ionic liquid system. The effect of oxygen in the system can be ameliorated to some extent by adding a simple sulfonated triphenylphosphine to the catalytic solution. [ABSTRACT FROM AUTHOR]

Both softwood (southern yellow pine) and hardwood (red oak) can be completely dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) after mild grinding. Complete dissolution was achieved by heating the sample in an oil bath, although wood dissolution can be accelerated by microwave pulses or ultrasound irradiation. It has been shown that [C2mim]OAc is a better solvent for wood than 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) and that variables such as type of wood, initial wood load, particle size, etc.affect dissolution and dissolution rates; for example, red oak dissolves better and faster than southern yellow pine. Carbohydrate-free lignin and cellulose-rich materials can be obtained by using the proper reconstitution solvents (e.g., acetone/water 1 : 1 v/v) and approximately 26.1% and 34.9% reductions of lignin content in the reconstituted cellulose-rich materials (from pine and oak, respectively) have been achieved in one dissolution/reconstitution cycle. The regenerated cellulose-rich materials and lignin fractions were characterized and compared with the original wood samples and biopolymer standards. For pine, 59% of the holocellulose (i.e., the sum of cellulose and hemicellulose) in the original wood can be recovered in the cellulose-rich reconstituted material; whereas 31% and 38% of the original lignin is recovered, respectively, as carbohydrate-free lignin and as carbohydrate-bonded lignin in the cellulose-rich material. [ABSTRACT FROM AUTHOR]

A series of task-specific ionic liquids (TSILs) based on glycerylimidazolium cations have been prepared by reaction of 1-chloropropanediol, a compound obtainable from glycerol (a widely available and in-expensive waste product), with the appropriate base (1-H-imidazole, 1,2-dimethylimidazole and 1-methyl-1-H-imidazole). The reaction of 3-(1H-imidazol-1-yl)propane-1,2-diol with chloroalkanes, bromoalkanes and alkyl mesylates gave the corresponding salts which were characterized. The possibility to use these ILs in palladium catalyzed reactions was evaluated, evidencing good catalyst stability and a high recyclability. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) have generated considerable attention recently because of their cytotoxicity and application as antibiotics. However, the mechanism of how they damage cell membranes is not currently well understood. In this paper, the antibacterial activities of two imidazolium-based ILs, namely 1-butyl- 3-methylimidazolium tetrafluroborate ([BMIM][BF4]) and 1-ethyl- 3-methylimidazolium tetrafluroborate ([EMIM][BF4]) have been investigated. The activity of [BMIM][BF4] on gram negative bacteria E. coli is observed to be stronger compared with the short chained [EMIM][BF4]. To explain this observation, the effects of these ILs on the self-assembled structures of model cellular membranes have been investigated. The in-plane elasticity of a monolayer formed at air-water interface by 1,2-dipalmitoyl- sn-glycero- 3-phosphocholine (DPPC) lipids was reduced in the presence of the ILs. The x-ray reflectivity studies on polymer supported lipid bilayer have shown the bilayer to shrink and correspondingly exhibit an increase in electron density. The presence of a certain mol% of negatively charged lipid, 1,2-dipalmitoyl-rac-glycero-3-phospho-L-serine (DPPS), in DPPC mono- and bi-layers enhances the effect considerably., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Ionic liquids (ILs) immobilized on silica as a novel high-performance liquid chromatography (HPLC) stationary phase have attracted considerable attentions. However, it has not been applied to protein separation. In this paper, N-methylimidazolium IL-modified silica-based stationary phase (SilprMim) was prepared and investigated as a novel multi-interaction stationary phase with positive charges for protein separation. The results indicate that all of the basic proteins tested cannot be adsorbed on this novel stationary phase, whereas all of the acidic proteins tested can be retained, and the baseline separation of eight kinds of acidic protein standards can be achieved when being performed under reversed phase/ion-exchange chromatography (RPLC/IEC) mode. Compared with commonly used commercial C4 column, the novel stationary phase can show good selectivity and resolution to acidic proteins. The effects of acetonitrile and salt concentration, pH as well as the ligand structure on protein separation were investigated in detail. In addition, the mix-mode retention mechanism of proteins on the SilprMim column was also discussed using stoichiometric displacement theory for retention in LC (SDT-R). The result shows that the protein retention can be controlled mainly by the electrostatic and hydrophobic interactions between the proteins and the stationary phase. As a result, with such characteristics of multi-interaction mechanism and multi-modal separation, not only the selectivity to the acidic proteins can be enhanced, but also a better resolution can be achieved. The result demonstrates that the SilprMim mixed-mode chromatography (MMC) column has a promising application in the separation and analysis of acidic proteins from the complex samples., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper describes Quantitative Structure-Activity Relationships (QSAR) studies, molecular docking and in vitro antibacterial activity of several potent imidazolium-based ionic liquids (ILs) against S. aureus ATCC 25923 and its clinical isolate. Small set of 131 ILs was collected from the literature and uploaded in the OCHEM database. QSAR methodologies used Associative Neural Networks and Random Forests (WEKA-RF) methods. The predictive ability of the models was tested through cross-validation, giving cross-validated coefficients q 2  = 0.82-0.87 for regression models and overall prediction accuracies of 80-82.1% for classification models. The proposed QSAR models are freely available online on OCHEM server at https://ochem.eu/article/107364 and can be used for estimation of antibacterial activity of new imidazolium-based ILs. A series of synthesized 1,3-dialkylimidazolium ILs with predicted activity were evaluated in vitro. The high activity of 7 ILs against S. aureus strain and its clinical isolate was measured and thereafter analyzed by the molecular docking to prokaryotic homologue of a eukaryotic tubulin FtsZ., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This paper reports novel imidazole fluorescent poly(ionic liquid) nanoparticles (FPILNs) of poly(1-[(4-methyphenyl)methyl]-3-vinyl-imidazolium bromide (poly([MVI]Br) for selective and sensitive determination of pyrogallol. An imidazole ionic liquid of 1-[(4-methyphenyl)methyl]-3-vinyl-imidazolium bromide ([MVI]Br) was synthesized and used as the only monomer to obtain poly([MVI]Br) possessing phenyl fluorophores using a radical polymerization technique. The obtained poly([MVI]Br) can form nanoparticles in water. Scanning electron microscopy and dynamic light scattering results revealed majority of poly([MVI]Br) FPILNs with diameters ranging from 40 to 400nm. Although [MVI]Br showed weak fluorescence intensity, poly([MVI]Br) FPILNs exhibited strong fluorescence intensity with a quantum yield of 0.192, which is attributed to the presence of significant number of phenyl fluorophores and rigid construction. The selective and sensitive determination of pyrogallol was achieved through fluorescence quenching of poly([MVI]Br) FPILNs, and the quenching was attributed to the oxidation of poly([MVI]Br) FPILNs by O 2 ˙¯ produced by pyrogallol autoxidation. The poly([MVI]Br) FPILNs-based sensor demonstrated a good linear relationship between the extent of fluorescence quenching and the concentration of pyrogallol in a range of 0.05 - 10.0μM, achieving a detection limit of 0.01μM. Furthermore, the poly([MVI]Br) FPILNs-based assay detected pyrogallol in environmental water samples, suggesting its potential to be applied for practical purposes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Water-miscible alkylimidazolium ionic liquids (ILs) are "green" co-solvents for laccase catalysis, but generally inhibit enzyme activity. Here, we present novel insights into inhibition mechanisms by a combination of enzyme kinetics analysis and molecular simulation. Alkylimidazolium cations competitively bound to the T I Cu active pocket in the laccase through hydrophobic interactions. Cations with shorter alkyl chains (C₂~C₆) entered the channel inside the pocket, exhibiting a high compatibility with laccase (competitive inhibition constant K ic = 3.36~3.83 mM). Under the same conditions, [Omim]Cl (K ic = 2.15 mM) and [Dmim]Cl (K ic = 0.18 mM) with longer alkyl chains bound with Leu296 or Leu297 near the pocket edge and Leu429 around T I Cu, which resulted in stronger inhibition. Complexation with alkylimidazolium cations shifted the pH optima of laccase to the right by 0.5 unit, and might, thereby, lead to invalidation of the Hofmeister series of anions. EtSO₄ - showed higher biocompatibility than did Ac - or Cl - , probably due to its binding near the T I Cu and its hindering the entry of alkylimidazolium cations. In addition, all tested ILs accelerated the scavenging of 2, 2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radicals, which, however, did not play a determining role in the inhibition of laccase., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

In this paper; an imidazolium ionic liquid (IL) is used to functionalize multi-walled carbon nanotubes (MWNTs) by covalent bonding on the MWNT surface. The functionalization not only provides a hydrophilic surface for ion accessibility but also prevents the aggregation of MWNTs. The IL-functionalized MWNTs were then applied for the electrochemical determination of the dihydroxybenzene isomers hydroquinone (HQ); catechol (CC); and resorcinol (RC), exhibiting excellent recognition ability towards the three compounds. The linear calibration ranges for HQ; CC and RC are 0.9-150 μM; 0.9-150 μM and 1.9-145 μM and the detection limits are found to be 0.15 μM for HQ; 0.10 μM for CC and 0.38 μM for RC based on S/N of 3. The proposed electrochemical sensor was also found to be useful for the determination of the dihydroxybenzene isomers in Yellow River water with reliable recovery.

During the manufacturing of pharmaceutical compounds, solvent mixtures are commonly used, where the addition of a cosolvent allows for the tuning of the intermolecular interactions present in the system. Here we demonstrate how a similar effect can be accomplished using a room temperature ionic liquid. The pharmaceutical compound acetaminophen is studied in 21 common ionic liquids composed of a 1-n-alkyl-3-methylimidazolium cation with 1 of 7 anions. Using the acetate anion, we predict a large enhancement in solubility of acetaminophen relative to water. We show how this is caused by a synergistic effect of favorable interactions between the ionic liquid and the phenyl, hydroxyl and amide groups of acetaminophen, demonstrating how the ionic liquid cation and anion may be chosen to preferentially solvate different functional groups of complex pharmaceutical compounds. Additionally, while the use of charge scaling in ionic liquid force fields has previously been found to have a minute effect on ionic liquid structural properties, we find it appreciably affects the computed solvation free energy of acetaminophen, which in turn affects the predicted solubility.

Room temperature ionic liquids have been proposed as replacement solvents in a wide range of industrial separation processes. Here, we focus on the use of ionic liquids as solvents for the pharmaceutical compound lidocaine. We show that the solubility of lidocaine in seven common 1-n-butyl-3-methylimidazolium based ionic liquids is greatly enhanced relative to water. The predicted solubility is greatest in [BMIM](+)[CH3CO2](-), which we find results from favorable hydrogen bonding between the lidocaine amine hydrogen and the [CH3CO2](-) oxygen, favorable electrostatic interactions between the lidocaine amide oxygen with the [BMIM](+) aromatic ring hydrogens, while lidocaine does not interfere with the association of [BMIM](+) with [CH3CO2](-). Additionally, by removing functional groups from the lidocaine scaffold while maintaining the important amide group, we found that as the van der Waals volume increases, solubility in [BMIM](+)[CH3CO2](-) relative to water increases.

In this paper, we report an ionic liquid-in-water (IL/w) microemulsion (ME) formulation which is able to solubilize etodolac (ETO), a poorly water soluble drug for topical delivery using BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) as IL, Tween 80 as surfactant and ethanol as co-surfactant. The prepared ME was characterized for physicochemical parameters, subjected to ex-vivo permeation studies as well as in-vivo pharmacodynamic evaluation. The ex-vivo drug permeation studies through rat skin was performed using Franz-diffusion cell and the IL/w based ME showed maximum mean cumulative percent permeation of 99.030±0.921% in comparison to oil-in-water (o/w) ME (61.548±1.875%) and oily solution (48.830±2.488%) of ETO. In-vivo anti-arthritic and anti-inflammatory activities of the prepared formulations were evaluated using different rodent models and the results revealed that ETO loaded IL/w based ME was found to be more effective in controlling inflammation than oily solution, o/w ME and marketed formulation of ETO. Histopathological studies also demonstrated that IL/w based ME caused no anatomical and pathological changes in the skin., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

In this paper, the joint effect of 0.5 mmol·L(-1) Cd(2+) and various concentrations (50-400 mg·L(-1)) of the ionic liquid 1-butyl-3-methyl-imidazolium acetate ([C4min][OAc]) on the growth and photosynthetic performance of wheat seedlings in hydroponic culture was investigated. Seedlings grown in presence of Cd(2+) and [C4min][OAc] showed significant (p < 0.05) improvement in growth (shoot and root lengths and dry weights) and photosynthetic performance (photosynthetic rate, stomatal conductance, transpiration rate, and chlorophyll a but not chlorophyll b) compared to seedlings grown in the presence of Cd(2+) but without [C4min][OAc]. However, this only happened under the lower range of [C4min][OAc] concentrations (50-200 mg·L(-1)). In addition, significant reduction in the level of Cd(2+) was also observed in the leaf tissue of wheat seedlings grown in the presence of 0.5 mmol·L(-1) Cd(2+) and 100 mg·L(-1) [C4min][OAc]. Overall, Cd(2+) exerted a stronger inhibition than [C4min][OAc] on the growth and photosynthetic performance of wheat seedlings. However, when both Cd(2+) and [C4min][OAc] were present in the culture, the toxicity of Cd(2+) could be mitigated by lower concentrations of [C4mim][OAc]. This phenomenon could be due to [C4mim][OAc] forming metal complexes with Cd(2+), thus reducing the toxicity of Cd(2+).

Although considered as "green" solvents, the toxic effects of ionic liquids (ILs) on organisms have been widely investigated in recent years. However, studies on the toxic effects of ILs on plants all focus on toxicity in nutrient solution. In the present paper, the toxic effects of 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) on Vicia faba seedlings in soil at 0, 500, 1500, and 2500 mg kg(-1) on day 10 were studied. The present results showed that the growth of V. faba seedlings may be seriously inhibited when the IL concentrations were higher than 500 mg kg(-1). The EC50 values for shoot length, root length, and dry weight were 3886, 2483, and 3359 mg kg(-1), respectively. In addition, [C4mim]Cl caused lipid peroxidation and DNA damage at 500 mg kg(-1) and oxidative stress at 1500 mg kg(-1), which indicated that [C4mim]Cl may have genotoxicity and cytotoxicity on V. faba seedlings. Moreover, oxidative damage may be the main toxic mechanism of ILs., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this paper, a simple and efficient ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (UA IL-DLLME) coupled with high-performance liquid chromatography for the analysis of ulipristal acetate (UPA) was developed. UPA could be easily migrated into 1-octyl-3-methylimidazolium hexafluorophosphate [C8mimPF6] IL phase without dispersive solvent. The research of extraction mechanism showed that hydrophobic interaction force played a key role in the IL-DLLME. Several important parameters affecting the extraction recovery were optimized. Under the optimized conditions, 25-fold enrichment factor was obtained and the limit of detection (LOD) was 6.8 ng mL(-1) (tablet) or 9.3 ng mL(-1) (serum) at a signal-to-noise ratio of 3. The calibration curve was linear over the range of 0.03-6.0 µg mL(-1). The proposed method was successfully applied to the UPA tablets and the real mice serum samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The present study investigated the impact of regeneration process on the crystalline structure and enzymatic hydrolysis behaviors of microcrystalline cellulose (MCC) regenerated from ionic liquid 1-butyl-3-methylimidazolium chloride. The crystalline structures of these regenerated samples were analyzed by X-ray diffraction. Results suggested that almost amorphous cellulose was obtained by regenerating MCC in acetone (DRC-a), while partial cellulose II structure could be found in these regenerated samples from water and ethanol. Additionally, the enzymatic hydrolysis behaviors of MCC and its regenerated samples were comparatively studied. Results showed that above 90% of cellulose could be converted into glucose within 4h for DRC-a and regenerated cellulose without drying (WRC-w) as compared to that of MCC (9.7%). Therefore, the regeneration process could significantly influence the crystallinity and digestibility of cellulose., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

From the environmental protection point of view, the growing interest of ionic liquids in various industrial branches has raised concerns for the toxicity assessment of these compounds. The paper discusses the effect of salts containing the shared 1-ethyl-3-methylimidazolium [EMIM] cation as coupled with five different anions: bromide [Br], nitrate [NO3], p-toluenesulfonate (tosylate) [Ts], dimethylphosphate [dMP] and methanesulfonate [MS] on the growth and development of higher land plants - spring barley and common radish. The experiment was done according to the ISO Standard 11269-2:1995 and the OECD/OCDE Guide 208/2006. As the indications of phytotoxicity, the percentage of sprouts and the level of dry and fresh plant mass were used; in addition, the visual assessment of any signs of damage to the examined plant species, such as growth inhibition and chlorotic changes, was also made. Results of our study has proved the negative impact of ILs on the tested plants and the toxic effect of imidazolium salts was dependent primarily on the applied ionic liquids concentration. The common radish revealed the higher tolerance to the imidazolium as compared to spring barley. The anion type of ionic liquid was crucial for the toxicity against common radish., (Copyright © 2014 Elsevier B.V. All rights reserved.)