Interaction Between Ionic Liquids and Gemini Surfactant: A Detailed Investigation into the Role of Ionic Liquids in Modifying Properties of Aqueous Gemini Surfactant

Tuning physicochemical properties of aqueous surfactant solutions comprised of normal or reverse micelles by external additives is of utmost importance due to the enormous application potential of surfactant‐based systems. Unusual and interesting properties of environmentally benign ionic liquids (IL) make them suitable candidates for this purpose. To understand and establish the role of IL in modifying properties of aqueous gemini surfactants, we studied the effect of the IL, 1‐hexyl‐3‐methylimidazolium bromide ([Hmim][Br]) and 1‐octyl‐3‐methylimidazolium bromide ([Omim][Br]) on the properties of the aqueous cationic gemini surfactant 1,6‐hexanediyl‐α,ω‐bis(dimethyltetradecyl)ammonium bromide (14‐6‐14,2Br^?). The behavioral changes were investigated by measuring the critical micelle concentration (CMC) using electrical conductance, surface tension, dye solubilization and fluorescence probe measurements at 298.15 K. It was observed that the CMC of 14‐6‐14,2Br^? gemini surfactant decreases with addition of IL, thus favoring the micellization process. An increase in micellar size was observed at lower IL concentration using dynamic light scattering, with a decrease in aggregation number (N_agg) determined from fluorescence probe quenching measurements. It is noteworthy that the extent of modulation of the micellar properties is different for both the IL due to their structural differences. IL behave like electrolytes at lower concentrations and cosurfactants at higher concentrations and form mixed micelles with the cationic gemini surfactant showing an increase in N_agg.     

离子液在常用有机反应中的应用进展

离子液体作为溶剂或载体,它提供了不同于传统分子溶剂的环境,可以改变反应的机理,在反应中使催化剂活性、选择性、转化率更高。文章综述了离子液在常用有机反应中的应用的最新进展,按照不同的反应类型对离子液在有机反应中的促进作用以及离子液的可循环使用状况进行了总结。其中包括:加成反应,烷基化反应,酰基化反应,缩合反应,酯化反应。     

Stetter Reaction in Room Temperature Ionic Liquids and Application to the Synthesis of Haloperidol

Imidazolium‐type room temperature ionic liquids (RTILs) have been used for the Stetter reaction, affording the desired 1,4‐dicarbonyl compounds in good yields. Thiazolium salts and Et₃N are efficient catalysts for this reaction performed in ionic liquid. The possibility to recycle and reuse the solvent has been demonstrated, although it was not possible to recycle the thiazolium catalyst. This method was used in the total synthesis of haloperidol.     

Nocturnal Acidification: A Coordinating Cue in the Euprymna scolopes–Vibrio fischeri Symbiosis

The Vibrio fischeri–Euprymna scolopes symbiosis has become a powerful model for the study of specificity, initiation, and maintenance between beneficial bacteria and their eukaryotic partner. In this invertebrate model system, the bacterial symbionts are acquired every generation from the surrounding seawater by newly hatched squid. These symbionts colonize a specialized internal structure called the light organ, which they inhabit for the remainder of the host’s lifetime. The V. fischeri population grows and ebbs following a diel cycle, with high cell densities at night producing bioluminescence that helps the host avoid predation during its nocturnal activities. Rhythmic timing of the growth of the symbionts and their production of bioluminescence only at night is critical for maintaining the symbiosis. V. fischeri symbionts detect their population densities through a behavior termed quorum-sensing, where they secrete and detect concentrations of autoinducer molecules at high cell density when nocturnal production of bioluminescence begins. In this review, we discuss events that lead up to the nocturnal acidification of the light organ and the cues used for pre-adaptive behaviors that both host and symbiont have evolved. This host–bacterium cross talk is used to coordinate networks of regulatory signals (such as quorum-sensing and bioluminescence) that eventually provide a unique yet stable environment for V. fischeri to thrive and be maintained throughout its life history as a successful partner in this dynamic symbiosis.     

Vapor Pressure of Water in Mixtures with Hydrophilic Ionic Liquids – A Contribution to the Design of Processes for Drying of Gases by Absorption in Ionic Liquids

The low water vapor pressures of mixtures of water with the ionic liquids (ILs), [EMIM][EtSO₄] and [BEIM][EtSO₄], indicate that a process of gas dehydration by absorption in ILs might be an alternative to the classical absorption process with triethylene glycol (TEG). The activity coefficient for an infinite dilution of water in the IL (x_IL → 1), which should be low for efficient dehydration, is only about 0.2 for [EMIM][EtSO₄] compared to 0.6 for triethylene glycol. In contrast to TEG, losses by evaporation are excluded with ILs as solvents, because they have a negligible vapor pressure. The number of separation stages needed for the absorption in the IL and for the subsequent regeneration of the water‐loaded IL is small, about six and eight, respectively. IL regeneration can be achieved by distillation of water out of the IL (e.g., at 120 °C) and stripping with ambient air, which is not possible in the case of TEG (chemical attack by O₂).     

Josiphos Ligands with an Imidazolium Tag and their Application for the Enantioselective Hydrogenation in Ionic Liquids

Josiphos ligands bearing an imidazolium moiety show high efficiency and reusability for the rhodium‐catalyzed enantioselective hydrogenation of methyl acetamidoacrylate (MAA) and dimethyl itaconate (DMI) in biphasic co‐solvent/ionic liquid combinations.     

Biodegradation and Ecotoxicity of Branched Alcohol Ethoxylates: Application of the Target Lipid Model and Implications for Environmental Classification

With the advent of global regulations for safer detergent and an emphasis on a shift toward more environmentally friendly formulations, the environmental profile of surfactant chemistries have moved to the forefront of product formulation and design. The two cornerstones of surfactant environmental profiles are the ability to biodegrade in the natural environment and the ecological hazard profile. The objectives of this article are to describe biodegradation and aquatic toxicity data for a series of branched oxo-alcohol ethoxylate (AEO) surfactants; to apply the target lipid model (TLM) for deriving model-based threshold hazard concentrations (HC5) of AEO; and, finally, to accurately determine aquatic classifications for AEO surfactants for use in regulatory classification frameworks. Biodegradation results indicate a high level of biodegradability of branched AEO, with C8–C13-rich oxo-alcohols with 1–20 mol of ethoxylate meeting the readily biodegradable criteria. Results from acute and chronic toxicity tests indicated comparable or lesser aquatic toxicity versus linear AEO structures previously reported in the literature. The TLM model, applied a priori, resulted in good agreement with acute toxicity data (RMSE = 0.49) and is comparable to the root mean square errors (RMSE) previously determined for other narcotic chemicals (RMSE = 0.46–0.57). Model errors for invertebrates and fish were smaller than those for algae, with the TLM systematically overpredicting acute and chronic classification of two of seven branched AEO. Furthermore, TLM-predicted HC5 values were determined to be sufficiently conservative, with 100% of observed chronic data (N = 79) falling above the HC5 threshold values, providing a useful tool for the risk assessment of AEO.     

Cu(acac)2 Immobilized in Ionic Liquids: A Recoverable and Reusable Catalytic System for Aza‐Michael Reactions

Copper(II) acetylacetonate immobilized in ionic liquids efficiently catalyzes the aza‐Michael reaction of amines with α,β‐unsaturated carbonyl compounds to produce the corresponding β‐amino carbonyl compounds with great alacrity in excellent yields. The reactions are far more facile than those reported earlier. The recovered ionic liquid phase containing the copper catalyst can be reused for several cycles with consistent activity.     

New Approach to Solve a Model for the Effective Solid Stress Distribution in Conical Spouted Beds

Charbel et al. (1999) have investigated the flow stability in conical spouted beds by modeling the effective solid stress distribution in the annular region as a function of the failure state under which the spout‐annulus interface is formed. However, due to the complexity in solving the momentum balance equations for the solid phase, the model application has been restricted to one case. This work is aimed at developing a new methodology to solve this set of algebraic differential equations, using optimization techniques to determine the model parameter. This methodology has improved the model solution extending its application for any other case.     

Synthesis of Bipyridine‐Stabilized Rhodium Nanoparticles in Non‐Aqueous Ionic Liquids: A New Efficient Approach for Arene Hydrogenation with Nanocatalysts

A new approach to stabilize metal nanoparticles with polynitrogen ligands in ionic liquids (ILs) is described. Zerovalent metal nanospecies in the size range of 2.0 nm were easily prepared in various ionic liquids by chemical reduction of a rhodium salt with an excess amount of sodium borohydride (NaBH₄) and efficiently stabilized by 2,2′‐bipyridine. The influence of the bipyridine ratio in various ILs according to the nature of the cation‐anion association was investigated. These nanocatalysts were evaluated in the hydrogenation of aromatic compounds in ILs under various catalytic conditions (P=1–40 bar, T=20–80 °C).     

A New Application of the Severity Factor Kinetic Model: Thermal Plasma Treatment of Black Liquor

The kinetic analysis of the treatment of black liquor by a thermal process can be performed in the conventional overall kinetic approach. However, while the detailed reaction mechanism remains unknown, the experimental analysis of black liquor treatment by submerged plasma demonstrates that the operating conditions (catalyst, plasma gas, temperature…) modify the kinetics and render this approach inefficient. The phenomenological approach based on the severity factor developed for the kinetic analysis of lignocellulose decomposition, is then proposed as an alternative to the conventional approach. The 3‐parameters model is validated for decomposition of formic acid and for sulfur oxidation.     

A Model for the Relative Velocity of a Particle in an Impingement Dryer: Application to Heat Transfer

Abstract

A simplified mathematical model for the relative gas-particle motion in a confined jet impingement dryer is developed. Model predictions based on an unsteady momentum balance are in good agreement with the observed cycling motion of a spherical particle. The model is applied to coriander seeds submerged in a flow field of superheated steam. It is found that relative motion occurs in unsteady turbulent regime, and that steady settling velocity of particles is never achieved. Model results are applied to correlate experimental heat transfer data of an impingement dryer. Experimental Nu numbers compare fairly well with correlations for fluidized systems.     

A Model for the Relative Velocity of a Particle in an Impingement Dryer: Application to Heat Transfer

A simplified mathematical model for the relative gas-particle motion in a confined jet impingement dryer is developed. Model predictions based on an unsteady momentum balance are in good agreement with the observed cycling motion of a spherical particle. The model is applied to coriander seeds submerged in a flow field of superheated steam. It is found that relative motion occurs in unsteady turbulent regime, and that steady settling velocity of particles is never achieved. Model results are applied to correlate experimental heat transfer data of an impingement dryer. Experimental Nu numbers compare fairly well with correlations for fluidized systems.     

A Semi-Empirical Model for Predicting the Onset of Drop Formation in Stratified Horizontal Oil-Water Flow

In this study, a semi-empirical modeling approach for predicting the onset of drop formation in stratified horizontal oil-water flow is presented. The model is suggested based on a correlation for the critical wave amplitude for drop detachment proposed by Al-Wahaibi et al. (2007 Al-Wahaibi , T. , and Angeli , P. ( 2007 ). Transition between stratified and non-stratified horizontal oil-water flows. Part I: Stability analysis , Chem. Eng. Sci. , 62 ( 11 ), 2915 – 2928 .[Crossref], [Web of Science ®] , [Google Scholar]) and an experimentally derived formula of the maximum wave amplitude at different phase flow rates in stratified flows that uses previous data with different viscosity oils. The proposed model was found to satisfactorily predict published experimental data when relatively low viscosity oils were used (less than or equal to 12 mPa.s cp) but was found to over-predict the velocities necessary for drop formation for higher viscosity oils (greater than 28 mPa.s).     

膜蒸馏跨膜传质过程的新模型--TPKPT

以纯水为介质,用直接接触式膜蒸馏测定了材料或性能参数不同的三种孔疏水膜在不同温度下的渗透通量。根据测量结果计算出了各种膜在不同温度下的渗透系数,发现渗透系数均随着温度的升高而升高;这一结果说明Poiseuille流动在跨膜传质中起着非常重要的作用。据此提出了Knudsen扩散－Poiseuille流动两参数跨膜传质模型,即TPKPT模型。用此模型拟合实验数据,得到了三种实验用膜的模型参数。用这些模型参数计算膜在不同温度下的渗透系数,其值与实验测量值吻合较好,说明TPKPT模型能较好地描述膜蒸馏的跨膜传质过程。     

Dissimilar Ligands Bind in a Similar Fashion: A Guide to Ligand Binding-Mode Prediction with Application to CELPP Studies

The molecular similarity principle has achieved great successes in the field of drug design/discovery. Existing studies have focused on similar ligands, while the behaviors of dissimilar ligands remain unknown. In this study, we developed an intercomparison strategy in order to compare the binding modes of ligands with different molecular structures. A systematic analysis of a newly constructed protein–ligand complex structure dataset showed that ligands with similar structures tended to share a similar binding mode, which is consistent with the Molecular Similarity Principle. More importantly, the results revealed that dissimilar ligands can also bind in a similar fashion. This finding may open another avenue for drug discovery. Furthermore, a template-guiding method was introduced for predicting protein–ligand complex structures. With the use of dissimilar ligands as templates, our method significantly outperformed the traditional molecular docking methods. The newly developed template-guiding method was further applied to recent CELPP studies.     

Using the Penalized Likelihood Method for Model Selection with Nuisance Parameters Present only under the Alternative: An Application to Switching Regression Models

Abstract. We study the problem of model selection with nuisance parameters present only under the alternative. The common approach for testing in this case is to determine the true model through the use of some functionals over the nuisance parameters space. Since in such cases the distribution of these statistics is not known, critical values had to be approximated usually through computationally intensive simulations. Furthermore, the computed critical values are data and model dependent and hence cannot be tabulated. We address this problem by using the penalized likelihood method to choose the correct model. We start by viewing the likelihood ratio as a function of the unidentified parameters. By using the empirical process theory and the uniform law of the iterated logarithm (LIL) together with sufficient conditions on the penalty term, we derive the consistency properties of this method. Our approach generates a simple and consistent procedure for model selection. This methodology is presented in the context of switching regression models. We also provide some Monte Carlo simulations to analyze the finite sample performance of our procedure.     

A steady-state shifting technique for the potentiometric method: Application to supersaturated solutions

A novel steady-state shifting technique, which overcomes the limitation of slow molecular diffusion, has been used to extend the applicability of the potentiometric method to highly concentrated and especially supersaturated solutions. The new technique has been verified experimentally and applied to measure the mean ionic activity coefficient ratios of NaCl in ternary glycine+NaCl+water solutions with glycine concentrations ranging from 0.1 m to as high as 4.0 m (i.e. approximately up to a level of relative supersaturation of 20%). New data in the supersaturated glycine region showed interesting indications of significant molecular interactions. Finally, the ternary system data were correlated mathematically to derive the activity coefficient ratios of glycine.     

PIG清洗技术在油改气管线上的应用

通过实例着重介绍了PIG清洗技术在某油田的一条Φ219mm×10mm×12km的输原油改输天然气管线上的应用。描述了该管线的清洗准备工作、工艺选择、过程监控及清洗效果评价。