Aggregation and Adsorption Behavior of Cationic Surfactants (Cetyltrimethylammonium Bromide and Dodecyltrimethylammonium Bromide) in Aqueous Solutions of Antibiotic Drug (Amikacin Sulphate) at Different Temperatures

Conductivity and spectroscopy techniques have been accomplished to comprehend the mechanism of supramolecular assembly of cetyltrimethylammonium bromide (CTAB) and dodecyltrimethylammonium bromide (DTAB) in aqueous solution of amikacin sulphate (0.001, 0.005, and 0.010 mol kg⁻¹). For CTAB, the normal boost of the CMC value with rise in temperature manifests the significant role of aquaphilic dehydration. However, the aquaphobic dehydrations become prominent with temperature and depict typical U-shaped behavior of CMC for DTAB. The thermodynamic parameters of micellization have been derived from CMC values. The outcomes have been conferred in terms of solvation of hydrophobic part of surfactants by hydrophobic part of amikacin sulphate and micellization becomes more favorable for surfactant with more hydrophobic character in the presence of drug. The alteration in micro-environment of the ternary (drug/surfactant/water) system has been explained in terms of fluorescence emission intensity of surfactant solutions which has been found to decrease by the addition of drug. The obtained absorbance spectrum by varying concentrations of surfactant/drug affords noteworthy information regarding the diverse interactions in studied systems. Moreover, the exhaustive understanding of surfactant micellar behavior have been discussed in consideration of use of surfactants as drug delivery agents and hence to amplify drug bioavailability consequently remodeling its treatment efficacy.     

Aggregation Behavior of Task-Specific Acidic Ionic Liquid N-Methyl-2-Pyrrolidinium Dihydrogen Phosphate [NMP][H2PO4] in Aqueous and Aqueous Salt Solutions

The effect of alkali salt (NaCl, NaBr, and KCl) addition on aggregate formation of N-methyl-2-pyrrolidinium dihydrogen phosphate [NMP][H₂PO₄] ionic liquid in aqueous solution was determined using surface tension at 298.15K and conductance from 288.15 to 308.15K. The surface parameters such as critical aggregation concentration (CAC), adsorption efficiency, surface pressure, surface tension at CAC, minimum surface cover by a single molecule, and maximum area excess concentration were calculated from surface tension measurements with and without salts. The results show that [NMP][H₂PO₄] forms aggregates at lower concentrations and is more surface active than classical cationic surfactants.     

Salt Effect on Mixed Micelle and Interfacial Properties of Conventional Cationic Surfactants and the Ionic Liquid Surfactant 1-Tetradecyl-3-methylimidazolium Bromide ([C14mim]Br)

The surface properties and mixed micellization behavior of binary combinations of an ionic liquid surfactant, namely, 1-tetradecyl-3-methylimidazolium bromide ([C₁₄mim]Br) with common cationic surfactants viz. tetradecyltrimethylammonium bromide and tetradecylpyridinium bromide in the presence of sodium bromide (NaBr) were investigated by surface tension and conductivity measurements. The critical micelle concentration (CMC) and interfacial parameters, such as the maximum surface excess (Γ_max), minimum area per molecule (A_min) and surface pressure at the CMC (π_CMC) were determined from the surface tension data. The CMC and Γ_max values were found to decrease with increasing salt concentrations. The $ \Updelta G_{\text{ad}}^{ \circ } $ and $ \Updelta G_{\text{m}}^{ \circ } $ values are negative indicating the spontaneity of micelle formation.     

Salting-out in Aqueous Solutions of Ionic Liquids and K3PO4: Aqueous Biphasic Systems and Salt Precipitation

The salting-out effect produced by the addition of potassium phosphate, K₃PO₄ to aqueous solutions of water-miscible ionic liquids, viz. 1-ethyl-3-methylimidazolium ethyl sulfate, 1-butyl-3-methylimidazolium methyl sulfate, or 1-alkyl-3-methylimidazolium chloride (alkyl = butyl, octyl or decyl) is investigated. The effects are analyzed using both the corresponding temperature–composition pseudo-binary and composition ternary phase diagrams. Different regions of liquid-liquid and solid-liquid phase demixing are mapped. The phase behavior is interpreted taking into account the complex and competing nature of the interactions between the ionic liquid, the inorganic salt and water. In the case of solutions containing 1-octyl- or 1-decyl-3-methylimidazolium chloride, the smaller magnitude of the salting-out effects is explained in terms of the possibility of self-aggregation of the ionic liquid.     

Micellar Properties of Surface Active Ionic Liquid Lauryl Isoquinolinium Bromide and Anionic Polyelectrolyte Poly(Acrylic Acid Sodium Salt) in Aqueous Solution

The complex formation between anionic polyelectrolyte poly(acrylic acid sodium salt) [NaPAA] and surface active ionic liquid (SAIL) lauryl isoquinolinium bromide [C₁₂iQuin][Br] in aqueous media has been investigated by surface tension, isothermal titration calorimetry (ITC), and conductance. The self‐assembled structures have been characterized using dynamic light scattering (DLS) and turbidity measurements. A range of surface parameters have been calculated from tensiometric measurements including critical micelle concentration (CMC), surface excess concentration (Γ_cmc), surface pressure at the interface (Π_cmc), minimum area occupied at air–solvent interface (A_min), adsorption efficiency (pC₂₀), and surface tension at the CMC (γ_cmc). The thermodynamic parameters, i.e., standard enthalpy of micellization , standard free energy of micellization (), and standard entropy of micellization () have also been evaluated. Four different stages of transitions, corresponding to the progressive formation of NaPAA–[C₁₂iQuin][Br] complex (C₁)_, critical aggregation concentration (CAC), critical saturation concentration (C₃) and CMC have been observed owing to strong electrostatic and hydrophobic interactions. The results obtained from DLS and turbidity measurements show that size of the aggregates first decreases and then increases in the presence of polyelectrolyte. The binding isotherms obtained using isothermal titration calorimetry (ITC) show the concentration dependence as well as the highly cooperative nature of interactions corresponding to formation of polyelectrolyte–SAIL complexes.     

离子液体[Amim]Cl中3-溴-4-羟基苯甲醛的水解反应研究

研究了3-溴-4-羟基苯甲醛在离子液体氯化烯丙基-3-甲基咪唑([Amim]Cl)中的水解反应,考察了反应温度、反应时间以及氢氧化钠、[Amim]Cl和催化剂的用量等对水解反应的影响,确定了水解反应的优化条件为:反应温度100℃,反应时间2h,催化剂用量为6.4g/mol反应物,[Amim]Cl用量为1.2L/mol反应物,氢氧化钠用量为2mol/mol反应物,水解反应产率83.6%,产品纯度达99.4%。离子液体[Amim]Cl回收简单,可以重复使用10次。     

Synthesis and Aggregation Behavior of Trisiloxane Ionic Liquids in Aqueous Solution

Trisiloxane ionic liquids with polyether groups (Si₃pyCl-EO₃) were synthesized via thiol-ene reaction between 1-methyl-1-[bis(vinyldimethylsiloxy)methyl]silylpropylpyrrolidinium chloride (Vi-Si₃pyCl) and tri(ethylene glycol) methyl ether thiol. The aggregation behavior of the trisiloxane ionic liquids, Si₃pyCl-EO₃ and Vi-Si₃pyCl, in aqueous solution was investigated using surface tension, electrical conductivity, dynamic light scattering, and transmission electron microscopy. The structures of trisiloxane ionic liquids can obviously influence their aggregation behavior. Vi-Si₃pyCl has excellent surface activity (22.3 mN m⁻¹). However, Si₃pyCl-EO₃ can only reduce the surface tension of water to 33.5 mN m⁻¹. In comparison with Vi-Si₃PyCl, Si₃PyCl-EO₃ has a bulkier hydrophobic group and a higher Α_min value (127.8 Ų) caused by the introduction of the tri(ethylene glycol) methyl ether groups by thiol-ene reaction. The micellization of Vi-Si₃PyCl is entropy driven, while the aggregation process of Si₃PyCl-EO₃ in aqueous solution is enthalpy driven.     

Conductometric Probe Analysis of the Effect of Benzyldimethylhexadecylammonium Chloride on the Micellization Behavior of Dodecyltrimethylammonium Bromide in Aqueous/Urea Solution: Investigation of Concentration and Temperature Effect

Surfactant mixtures are used in many different industrial formulations. In this study, the mixed micelle formation behavior of 2 different cationic surfactants, namely dodecyltrimethylammonium bromide (DTAB) and benzyldimethylhexadecylammonium chloride (BDHAC), in the absence and presence of urea at various temperatures (298.15–318.15 K) was studied using the conductometric method. The attractive interaction between DTAB and BDHAC was estimated from the values of critical micelle concentration (CMC) and the CMC for ideal mixing (CMC^id). Urea increases the CMC value as a result of the enrichment in the surface charge of the micelles/mixed micelles. The values of micellar mole fraction (X₁^Rub [Rubingh], X₁^M [Motomura], X₁^Rod [Rodenas]) and ideal micellar (X₁^id) of surfactant BDHAC were obtained by different models and are shown to exhibit the high contribution or effective involvement of BDHAC in mixed micelles and increase with increasing BDHAC mole fraction (α₁). Activity coefficients (f₁ and f₂) were also evaluated from the relevant formula given in the literature. The negative values of the interaction parameters (β) show the attractive interaction among the studied components. Excess Gibbs free energy (?G_ex) of micellization revealed that the stability of mixed micelles is higher in aqueous solution than in urea solution. The thermodynamic parameters, namely the Gibbs free energy change, enthalpy change, and entropy change (?G^o_m, ΔH^o_m, and ?S^o_m, respectively), were also calculated from the conventional standard equations.     

金属Al和不锈钢在[bmim]BF4离子液体中的电化学

离子液体作为有潜力的绿色电化学介质,在电解、电镀、电催化、电分析化学等领域具有非常好的应用前景。本文采用循环伏安法和塔夫尔曲线法研究了金属Al和不锈钢在[bmim]BF4离子液体中的电化学行为,结果表明金属Al在[bmim]BF4离子液体中非常稳定,不锈钢在该离子液体中显示一定的活性。     

氯铝酸盐离子液体催化苯与十二烯烷基化反应

针对酸性氯铝酸盐室温离子液体[BMIM][AlCl4]催化苯与1-十二烯烷基化合成十二烷基苯反应体系的物理化学特性,设计了一套可以分别进行间歇和连续操作的连续流动搅拌反应装置。间歇操作的反应结果表明．[BMIM][AlCl4]催化剂体系的总体结果优于传统催化剂无水AlCl3和氢氟酸,催化剂的用量和反应温度可以大大降低,2-苯基异构体的选择性较高。在连续操作条件下,一定的流量范围内实现了离子液体催化剂和反应料液的原位分离,催化剂被有效地局限在反应区域,并因在运转过程中始终未暴露从而得到了比间歇操作更加稳定和高效的反应结果。     

功能离子液体[N4MIM]Cl的合成及其配合Cu 催化ATRP反应研究

以N-甲基咪唑为骨架引入1,2-二氯乙烷合成中间体氯化1-氯乙基-3-甲基咪唑([CeMIM]Cl),再与三乙烯四胺反应合成了氯化1-（三乙基四氨基）乙基-3-甲基咪唑离子液体（[N4MIM]Cl）。通过红外光谱IR、核磁共振氢谱1HNMR对[N4MIM]Cl进行分析测试,确证了[N4MIM]Cl的化学结构。通过循环伏安法测得[N4MIM]Cl具有较低的氧化还原电势,E1,2为-0.472V,与有机配体相比[N4MIM]Cl具有较好的配位性能。将[N4MIM]Cl与CuBr配位用于催化氯化1-烯丙基-3-甲基咪唑离子液体（[AMIM]Cl）体系中甲基丙烯酸甲酯（MMA）的原子转移自由基聚合（ATRP）反应,经凝胶渗透色谱法（GPC）测试证明[N4MIM]Cl对ATRP反应具有较好的可控性。原子吸收光谱（AAS）测定聚合产物聚甲基丙烯酸甲酯（PMMA）中Cu2 的残留量仅为360mg穔g-1,表明与传统有机配体相比,[N4MIM]Cl有利于催化剂与聚合产物的分离。     

离子液体[bmim]PF6对聚乳酸的增塑作用

合成了离子液体[bmim]PF6(1-丁基-3-甲基咪唑六氟磷酸盐),并对其进行了表征。用TG、DSC和偏光显微镜等手段研究了[bmim]PF6对聚乳酸的增塑作用,并比较了它与聚乙二醇300(PEG300)的增塑效果。热重分析结果表明,PEG300作增塑剂时,由于其热降解温度较低,聚乳酸热稳定性变差;离子液体[bmim]PF6作增塑剂时,由于其热失重温度高于聚乳酸热降解温度,用其增塑的聚乳酸热稳定性变好。当[bmim]PF6的质量分数从2%增加到10%时,聚乳酸材料的玻璃化转变温度(Tg)随之降低,当加入质量分数为10%的[bmim]PF6时,聚乳酸材料的Tg降至40℃。偏光显微镜观察看出,加入[bmim]PF6后聚乳酸分子链段的活动能力增强,促进了聚乳酸的结晶,且随其用量增加,结晶度增加。该文报道工作的新颖性,已为教育部科技查新工作站(Z12)于2008年2月26日出具的第ZDT2008017号《科技查新报告》所证实。     

[bmim]Cl/[FeCl_3] Ionic Liquid as Catalyst for Alkylation of Benzenewith 1-Octadecene

1 INTRODUCTION Linear alkylbenzenes (LAB), important interme- diates in the detergent industry, have usually been manufactured by alkylation of benzene with C10 14 olefins in the presence of HF or AlCl3 catalyst. It is known that HF or AlCl3, to some extent, is hazardous to the environment. Therefore, the HF or AlCl3 proc- ess is a typical example of a “non-green” process be- cause of cooling and separation problems, high oper- ating costs and safety aspects. Many efforts have bee…     

Aggregation Behavior of Imidazolium-Based Amino Acid Ionic Liquid Surfactants in Aqueous Solution: The Effect of Amino Acid Counterions

Three kinds of imidazolium-based amino acid ionic liquid surfactants (AAILS), 1-tetradecyl-3-methylimidazolium _L-aminopropionic acid salt ([C₁₄mim][Ala]), 1-tetradecyl-3-methylimidazolium _L-2-pyrrolidinecarboxylic acid salt ([C₁₄mim][Pro]), and 1-tetradecyl-3-methylimidazolium _L-aminohydrocinnamic acid salt ([C₁₄mim][Phe]), were synthesized by employing natural amino acids as counterions. Their adsorption and self-aggregation behaviors in aqueous solution were investigated systematically by means of surface tension and electrical conductivity measurements. Surface tension results indicate that surface properties and micellization behavior of AAILS are significantly affected by counterions. The micellization of [C₁₄mim][Pro] and [C₁₄mim][Phe] is entropy-driven at low temperatures but enthalpy-driven at high temperatures, whereas [C₁₄mim][Ala] is enthalpy-driven throughout the whole temperature range, owing to the variation in hydrophobicity and size of amino acid counterions. The surface activity of [C₁₄mim][Phe] is superior to that of conventional imidazolium-based ionic liquid surfactants with the same hydrocarbon chain length, 1-tetradecyl-3-methylimidazolium bromide (C₁₄mimBr), indicating that the aromatic counterion can promote the micellar formation process.     

Separation of N2O and CO2 using Room-Temperature Ionic Liquid [bmim][Ac]

We have developed a ternary equation of state (EOS) model for the N₂O/CO₂/1-butyl-3-methylimidazolium acetate ([bmim][Ac]) system in order to understand the separation of N₂O and CO₂ using room-temperature ionic liquids (RTILs). The present model is based on a generic RK (Redlich-Kwong) EOS, with empirical interaction parameters for each binary system. The interaction parameters have been determined using our measured VLE (vapor-liquid-equilibrium) data for N₂O/[bmim][Ac] and literature data for CO₂/[bmim][Ac] and N₂O/CO₂. The binary EOS model for the N₂O/[bmim][Ac] system correctly predicted the liquid-liquid phase separation found in VLLE experiments. The validity of the ternary EOS model has been checked by conducting VLE experiments for the N₂O/CO₂/[bmim][Ac] system over a temperature range from 296 to 313 K. With this EOS model, solubility (VLE) behavior has been calculated for various (T, P, and feed compositions) conditions. Over a range of N₂O/CO₂ feed ratios, the N₂O/CO₂ gas selectivity [α _{N 2 O/CO 2}  = (y _{N 2 O} /x _{N 2 O} )/(y _{CO 2} /x _{CO 2} )] increases by at least 5 orders of magnitude when adding [bmim][Ac] (α = 1 × 10² to 1 × 10⁷), compared with the absence of the ionic liquid (α = 0.96 to 0.98). The addition of [bmim][Ac] may provide a practical means of separating CO₂ and N₂O.

Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science and Technology to view the free supplemental file.     

New Alkylation Route of Benzene with Ethylene Catalyzed by [bmim]Cl/FeCl_3 Ionic Liquid

Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR     

[Bmim]Cl/AlCl3离子液体催化C16~C18直链烯烃/苯烷基化反应

采用不同AlCl3摩尔分数的[Bmim]Cl/AlCl3离子液体，研究了不同工艺条件下C16~C18直链烯烃与苯烷基化反应. 常温下，采用AlCl3摩尔分数为0.67的[Bmim]Cl/AlCl3离子液体催化剂，在苯烯摩尔比为6，AlCl3与烯烃摩尔比为0.04的条件下，30 min内烯烃转化率可以达到98%，2位烷基苯选择性为46%左右. 通过红外乙腈分子探针表征离子液体的Lewis酸性并结合烷基化反应结果表明，离子液体中AlCl3摩尔分数增加，Lewis酸性增强，催化活性增高. 通过红外苯分子探针对离子液体极化能力进行表征，发现离子液体具有较强的极化能力，可以促进碳正离子的稳定性. 另外，还考察了烯烃碳链长度对苯烷基化反应的影响.     

A Comparative Study of Micellization Behavior of an Ethoxylated Alkylphenol in Aqueous Solutions of Glycine and Leucine

Densities (d) and sound velocities (v) of an ethoxylated alkyl phenol surfactant in aqueous solutions of two amino acids, namely glycine and leucine, have been measured over a temperature range of 25–40 °C at intervals of 5 °C by using density and sound analyzers. Experimental data have been used to calculate the isentropic compressibilities (κ_s), apparent molar volumes (?_v) and apparent molar adiabatic compressions (?_κ) in order to explain amino acid–surfactant interactions. The results have been discussed in terms of the effect of amino acids on the micellization behavior of the surfactant. A comparative study of both the amino acids has been carried out and is found that both amino acids produce a decrease in the CMC value of nonionic surfactant but to different extents.     

Extraction Kinetics of Lanthanum in Chloride Medium by Bifunctional Ionic Liquid [A336][CA-12] Using a Constant Interfacial Cell with Laminar Flow☆

The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12] (tricaprylmethylammonium sec-octylphenoxy acetic acid) ...     

[bmim]Cl／FeCl3离子液体催化苯与乙烯烷基化反应的新型机理

Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of [bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shifts of proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl3 content and shifted downfield when FeCl3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to be disengaged from imidazolium ring with formation of H^ to initiate the reaction. The isotope-substituted method was employed to prove this mechanism, through the GC-MS analysis of alkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeC13 ionic liquid was found to follow the carbocation mechanism, the resource of H was presented and proved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found that the intensity of 2-H reduced 23% after reaction showing that the H arising from alkylation reaction was supplied by 2-H on the imidazole ring.