Sharif Digital Repository

Solvatochromic parameters (E T N , normalized polarity parameter; π, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (IL; 2-hydroxyethylammonium formate) at 25 °C. In all solutions except aqueous solution, E T N values of the media increase abruptly with the ILs mole fraction and then increase gradually to the value of pure IL. A synergistic behavior is observed for the α parameter in all solutions. The behavior of π and β are nearly ideal for all solutions except for solutions of methanol with the IL. The... 

Betaine-based natural deep eutectic solvents (NADESs), a new class of green solvents, were immobilized into a porous polyvinylidene fluoride (PVDF) support and evaluated for the separation of CO2 from CO2/N2 and CO2/CH4 mixtures. Two types of NADESs were synthesized by mixing betaine (hydrogen bond acceptor-HBA) with malic acid and tartaric acid (hydrogen bond donors-HBD) respectively. FTIR and Raman spectroscopy were studied to confirm the synthesis and purity of the NADESs. The thermal strength of the NADESs was investigated using thermogravimetric analysis. The gas permeation results of the fabricated NADES-based-supported liquid membranes (NADES-SLMs) showed that the permeability of CO2... 

The microscopic features of binary solvent systems formed by molecular solvents (methanol, ethanol, 2-methylpropan-2-ol, water, pyridine, acetonitrile, 1-propanol, 2-propanol, dimethylformamide) and the ionic liquid ([bmim]BF4) as cosolvent were used to select mixed solvents with particular characteristics. Molecular-microscopic solvent parameters corresponding to these binary mixtures were utilised to study the kinetics of the nucleophilic substitution reaction between 2-chloro-3,5-dinitropyridine and aniline to investigate and compare the effects of the solvents on a model chemical reaction. For these mixtures, the solvation behaviour is dominated by both the dipolarity/ polarisability and... 

Synchronous heterogeneous catalytic hydrogenation of cyclohexene and acetone, catalyzed by Pt/Al2O3, was carried out in solutions of 2-hydroxy ethylammonium formate (a room temperature ionic liquid, RTIL) with ethanol and propan-1-ol at 25 °C. Rate constants and selectivity of the reaction (relative to cyclohexene hydrogenation) increase with mole fraction of the ionic liquid (IL). The reactants tendency to the catalyst surface increases by addition of the ionic liquid and thus the reaction rate increases, especially for cyclohexene hydrogenation. Consequently the selectivity to cyclohexene hydrogenation was increased. Single-parameter correlations of log kvs.π* (dipolarity/polarizibility)... 

By combination of 1-ethyl-3-methyl immidazolium ethyl sulfate as a typical room temperature ionic liquid (IL) and graphene oxide (GO) nanosheets, a nanocomposite was introduced for improving the direct electrochemistry and electrocatalytic activity of glucose oxidase (GOx). The enzyme on the IL–GO-modified glassy carbon electrode exhibited a quasireversible cyclic voltammogram corresponding to the flavine adenine dinucleotide/FADH2 redox prosthetic group of GOx. At the scan rate of 100 mV s−1, the enzyme showed a peak-to-peak potential separation of 82 mV and the formal potential of −463 mV (vs Ag/AgCl in 0.1 M phosphate buffer solution, pH 7.0). The kinetic parameters of the charge transfer... 

A novel basic poly(ionic liquid) (PIL) was synthesized by miniemulsion polymerization of ionic liquid monomer 1-ethyl-3-vinylimidazolium bromide [EVim][Br] which was cross-linked by ionic liquid cross-linker 1,4-butanediyl-3,3'-bis-l-vinylimidazolium dibromide (BVD). Exchange of bromide anions in PIL nanogel with hydroxide, produced a supported basic ionic liquid catalyst. The catalytic performances of PIL nanogel with a size of about 200. nm was evaluated in the synthesis of 4. H-benzo[. b]pyrans by multi-component reaction in water. The present protocol represents a simple, ecologically safe and cost-effective route to synthesize 4. H-benzo[. b]pyrans with high products yield  

A novel silica-functionalized dual Brønsted acidic ionic liquid (ionic liquid with two Brønsted acidic species) has been reported as a highly efficient catalyst for thioacetalization of carbonyl compounds. The reaction was efficiently performed in water as an environmentally benign solvent with good to high yields. Thermal gravimetric analysis showed that the catalyst is stable at least up to 350 C. Furthermore, the catalyst can be recycled and reused for six runs of reaction without appreciable loss of activity. The structure of the catalyst is modelized to gain more realistic structural insight about the functionalized ionic liquid  

An environmentally benign, aqueous synthesis of 1,2-azidoalcohols via regioselective ring opening of their epoxides using magnetic imidazolium based dicationic room temperature ionic liquid, [pbmim](FeCl4)2, as an efficient magnetic phase transfer catalyst in water has been described. The present approach offers the advantages of clean reaction, simple methodology, short reaction time, high yield, easy purification and reusable catalyst  

A discussion covers the general descriptions and basic properties of ionic liquids (IL); main application areas, e.g., solvent replacement, purification of gases, homogenous and heterogeneous catalysis, biological reactions media, and removal of metal ions; and results of the research and works relating to gas solubility measurement and thermodynamic modeling of gas solubility with focus on acid gas solubility in IL. This is an abstract of a paper presented at the CHISA 2012 - 20th International Congress of Chemical and Process Engineering and PRES 2012 - 15th Conference on Process Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction (Prague, Czech Republic... 

The current work deals with the catalytic application of bis(1-butyl-3-methylimidazolium) tungstate ([BMIm]2WO4) for green synthesize of glutaric acid (GA) through oxidative cleavage of cyclopentene. In this method, 30% hydrogen peroxide (H2O2) was used as oxidant with water as the sole by-product of the reaction. Compared to the current synthetic procedures, this protocol is significantly improved in the environmental point of view. Moreover, the effect of the various parameters was investigated on the reaction efficiency. It was found that high yield of GA could obtain without using special methodologies or precautions. The catalytic system is reusable for several times  

Abstract: The current study deals with the applications of a surfactant-like Brønsted acidic ionic liquid (IL) 1-dodecyl-3-methylimidazolium hydrogen sulfate ([DMIm]HSO4) for Mannich reaction at room temperature. The reaction was efficiently preceded in water as solvent without using any harmful and expensive organic additives. Our findings showed that the reaction is selective for cyclohexanone and no Mannich product was observed when cyclopentanone was used as starting material. Density functional theory (DFT) calculations were performed to provide an evidence about the nature of reactivity of the cyclohexanone/cyclopentanone. The activity of the catalyst was also tested for biodiesel... 

The new model for the Morita–Baylis–Hillman reaction based on the proton transfer were inquired by MP2 and DFT methods with 6-311G++(d, p) basis set combined with IEF-PCM solvent model. We focused on the reaction between acrylonitrile and benzaldehyde, catalyzed by CaO cluster and CaO modified with [Pyr][HSO4] ionic liquid. Our results indicate that in the presence of ionic liquid, the ionic liquid acts as a shuttle for the proton transfer between species in a lower energy pathway. The proton transfer step from enolate to catalyst is predicted to be the rate-limiting step for the whole process. In order to investigate the catalyst basicity, the pKa values of acrylonitrile and methyl acrylate... 

Proton affinity (PAs) and molecular basicities (GBs) of the CaO cluster and CaO modified with protic and aprotic ionic liquids in the gas phase have been calculated at the DFT/B3LYP level with a 6-311++G (d, p) basis set. The investigations of PAs and GBs in the solution phase have been studied by means of SCRF solvent effect computations using PCM solvation model for water solvent. The influence of the ILs cations and anions on the PA and GB in the gas phase and solution at the same level of theory has been investigated. We also studied the effect of [bmTr][NO3] ionic liquid on the basicity of CaO. The calculations display that this energetic ionic liquid has a high ability to improve the... 

Hexyltriphenylphosphonium bromide (HTPB) is used as an efficient ionic liquid catalyst in the chemoselective addition of malononitrile to carbonyl group moiety of chalcones through the three-component reaction of aryl aldehydes, acetophenone derivatves, and malononitrile to produce (E)-2-(1,3-diarylallylidene)malononitriles at ambient temperature. The method is simple, solvent-free, environmentally friendly, and gives excellent yields in a short reaction times. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim  

In this work, a calixarene based ionic liquid was successfully prepared and characterized by different techniques. This ionic liquid was used as an efficient catalyst for the synthesis of a series of polysubstituted pyridines from aldehydes, malononitrile, 1,3-diketones and arylamines in water as a green solvent. Also, for the first time, symmetric and unsymmetric polysubstituted bis-pyridines were obtained in high yields from diamines using this catalyst. Mild reaction conditions, high to excellent yields, easy work-up, excellent activity and reusability of the catalyst are the key features of this method which make it an interesting and novel alternative for the synthesis of the above... 

Fe3O4 magnetic structure was synthesized with co-precipitation method. Surface of magnetic core was modified with hydrophobic BMIM[PF6] ionic liquid. The samples became antibacterial by loading gold, copper and silver nanoparticles and denoted as Fe3O4/IL/X (X=Ag, Au, Cu). X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermal gravimetric analysis (TGA), Atomic absorption spectroscopy (AAS), Fourier transform infrared (FTIR) and vibration sample magnetometer (VSM) technics were applied for catalysts characterization, metal concentration analysis and morphology monitoring. Modified nanostructures were used for inactivation of Escherichia coli as... 

Designing drug delivery systems for therapeutic compounds whose receptors are located in the cytosol of cells is challenging as a bilayer cell membrane is negatively charged. The newly designed drug delivery systems should assist the mentioned drugs in passing the membrane barriers and achieving their targets. This study concentrated on developing novel ionic liquids (ILs) that interact effectively with cell membranes. These ILs are based on glucose-containing choline and are expected to be non-toxic. The binding energies of the known pharmaceutically active ionic liquids were calculated at the B3LYP/6-311++G(d,p) level in the gas phase and compared with those of our newly designed... 

A task-specific Brønsted acidic ionic liquid (BAIL), 1-benzyl-3-methylimidazolium hydrogensulfate ([BnMIm]HSO4), was prepared and confined onto the high surface area silica gel. The catalyst has shown extraordinary activity in comparison of homogeneous ionic liquid (IL) system for Fischer esterification of fatty acid with ethanol. The ester derivatives were synthesized in high yields and catalyst was easily separated from the reaction mixture by simple filtration. The structure of the catalyst is theoretically modelized to investigate the unusual catalytic activity. Hence, a hydroxylated cage-like nano-cluster, H6Si8O12(OH)2, was selected to mimic the surface of silica gel. The interactions... 

Interesting properties of ionic liquids lead to their application as sub-component of membrane structures. Supported ionic liquid membranes (SILMs) are porous membranes whose pores are saturated with ionic liquids. Two ionic liquids, pr[mim]2[Tf2N]2 [1,3-di(3-methyl-imidazolium) propane bis(trifluoromethylsulfonyl) imide] and, h[mim]2 [Tf2N]2 [(1,6-di(3-methylimidazolium)hexane bis(trifluoromethylsulfonyl)imide)], were synthesized in our laboratory and stabilized on an alumina porous support. Permeability and permselectivity of carbon dioxide and methane using membranes containing these ionic liquids were then measured. The experiments were performed in the pressure range of 10-50kPa and... 

1-Butyl-3-methylimidazolium tungstate ([BMIm] 2WO 4) ionic liquid supported onto silica sulphamic acid demonstrated desirable performance for oxidation of cyclohexene to adipic acid. Simple experimental procedure, easy product isolation, catalyst recovery and reusability are some attractive features of this protocol