The role of the symmetry and the flexibility of the anion on the characteristics of the nanostructures and the viscosities of ionic liquids☆

The transport properties of ionic liquids (ILs) are crucial properties in view of their applications in electrochem-ical devices. One of the most important advantages of ILs is that their chemical–physical properties and conse-quently their bulk performances can be well tuned by optimizing the chemical structures of their ions. This will require elucidating the structural features of the ions that fundamentally determine the characteristics of the nanostructures and the viscosities of ILs. Here we showed for the first time that the“rigidity”, the order, and the compactness of the three-dimensional ionic networks generated by the anions and the cation head groups determine the formation and the sizes of the nanostructures in the apolar domains of ILs. We also found that the properties of ionic networks are governed by the conformational flexibility and the symmetry of the anion and/or the cation head group. The thermal stability of the nanostructures of ILs was shown to be con-trolled by the sensitivity of the conformational equilibrium of the anion to the change of temperature. We showed that the viscosity of ILs is strongly related to the symmetry and the flexibility of the constitute ions rather than to the size of the nanostructures of ILs. Therefore, the characteristics of the nanostructures and the viscosities of ILs, especially the thermal stability of the nanostructures, can be fine-tuned by tailoring the symmetry and the conformational flexibility of the anion.     

Synthesis and Characterization of the Inclusion Complex of β-cyclodextrin and Azomethine

A β-cyclodextrin (β-Cyd) inclusion complex containing azomethine as a guest was prepared by kneading method with aliquot addition of ethanol. The product was characterized by Fourier Transform Infrared (FTIR) spectrometer, ¹H Nuclear Magnetic Resonance (¹H NMR) and Thermogravimetric Analyzer (TGA), which proves the formation of the inclusion complex where the benzyl part of azomethine has been encapsulated by the hydrophobic cavity of β-Cyd. The interaction of β-Cyd and azomethine was also analyzed by means of spectrometry by UV-Vis spectrophotometer to determine the formation constant. The formation constant was calculated by using a modified Benesi-Hildebrand equation at 25 °C. The apparent formation constant obtained was 1.29 × 10⁴ L/mol. Besides that, the stoichiometry ratio was also determined to be 1:1 for the inclusion complex of β-Cyd with azomethine.     

Investigation of the effect of minor ions on the stability of β-C2S and the mechanism of stabilization

In this paper the effect of minor ions on the stability of β-C₂S has been studied. It is discovered that the effect of minor ions on the stability of β-C₂S is closely related to the polarization ability of the ions. According to this the authors propose a new judgement, the ion polarization ability judgement, by which we can determine if minor ions have the stabilizing affect on β-C₂S. The judgement is that those ions, either having smaller polarization ability than that of calcium ion or greater than that of silicon ion, all have the ability to effect the stability of β-C₂S. This judgement is more practical than those made by other authors. In this paper a new mechanism about the stabilization has been described on the basis of applying the principles of thermodynamics and dynamics of the transformation of solid phases in accordance with the above judgement.     

Note of the estimation of the Θ temperature and Ψ parameter from the critical temperature data

Summary Critical values of the polymer volume fraction _2,c and the interaction parameter _c have been computed for the case that the equation for the chemical potential of solvent contains terms _{c 2} ³ and _{c 2} ⁴ in addition to ₂ ² . For 0 _c 1/3, the limits for infinite chain length are _2,c = 0 and _c = 0.5. Quite different results are obtained for _c > 1/3, _2,c being finite and _c lower than 1/2. Conclusions for the estimation of the temperature and the entropy-of-dilution parameter are discussed.     

Kinetics and mechanism of the preparation of Raney® copper

Raney® copper is an active hydrogenation catalyst formed by the selective dissolution of aluminium from a Cu–Al alloy. The structure of Raney® copper is presented in a series of images taken using a focussed ion beam miller (FIB). The images show a structure consisting of a uniform three-dimensional network of fine copper ligaments. A rotating disc electrode, used to control the diffusion layer, enabled a study of the kinetics of the leaching reaction at 269–303K in 2–8m NaOH. Under these conditions, the reaction rate was constant and independent of hydroxide concentration. The activation energy for leaching was determined as 69±7kJmol^–1. The mixed corrosion potential of the dissolving alloy has been related to the exposed copper surface area, which in turn is dependent on the leaching rate and the mechanism of rearrangement. The overall mechanism of formation/rearrangement of the Raney® copper structure was found to be mainly dissolution/redeposition of copper atoms, with surface or volume diffusion, or possibly both, playing a minor role.     

Ionic liquid effects on the reaction of β-enaminones and tert-butylhydrazine and applications for the synthesis of pyrazoles

In order to evaluate the effect of a series of 10 different ionic liquids ([BMIM][BF₄], [BMIM][Br], [OMIM][BF₄], [BMIM][PF₆], [DBMIM][Br], [DBMIM][BF₄], [BMIM][OH], [BMIM][SCN], [HMIM][HSO₄] and [HMIM][CF₃CO₂]) the cyclocondensation reaction between 4-dimethylamino-1-phenyl-3-alken-2-ones (RC(O)CHCHNMe₂, where R = Ph, 4-Me-Ph, 4-F-Ph, 4-Cl-Ph, 4-Br-Ph, 4-NO₂-Ph, thien-2-yl, fur-2-yl, pyrrol-2-yl, pyrid-2-yl, hexyl, dimethoxymethyl) and tert-butylhydrazine was performed. The effects of each ionic liquid are discussed and the best yields for the cyclocondensation reaction studied were obtained using [BMIM][BF₄].     

Effect of the fractional composition of the solid components of coal–water fuel on the characteristics of ignition and combustion

The experimental results of studies of the ignition and subsequent combustion processes of the single drops of organic coal–water fuels (OCWFs) arranged on the junction of a quick-response thermocouple (thermal inertia, <1 s) in an atmosphere of heated (600–1000 K) air are presented. The particles of 2B brown coal and D coal, water, and oils of different types (turbine, motor, and transformer oils) were used as the main OCWF components. The effect of the degree of grinding (fineness) of the solid fuel components of OCWFs on the following integral characteristics of the ignition and combustion of prepared fuel compositions was established: the delay times of ignition and complete combustion. A decrease in the delay times of ignition and complete combustion with decreasing the degree of grinding was detected (in a range of 40–200 μm used as an example). The reasons and special features of the influence of this factor on the integral characteristics of the test processes were recognized.     

Influence of the temperature dependence of the thermophysical properties of coal–water fuel on the conditions and characteristics of ignition

The results of an experimental study and mathematical simulation of the ignition of coal–water fuel (CWF) particles, the main thermophysical characteristics of which (thermal conductivity (λ), heat capacity (C), and density (ρ)) depend on temperature, are reported. Based on the results of the numerical study, the influence of changes in the thermophysical properties upon the heating of the main bed of fuel on the conditions and characteristics of its ignition was analyzed. The ignition delay times (t _i) of CWF particles were determined under the typical furnace conditions of boiler aggregates. As a result of the mathematical simulation of the process of CWF ignition, it was established that the temperature dependence of thermophysical characteristics can exert a considerable effect on the characteristics and conditions of ignition. In this case, it was found that the ignition of coal–water drops is possible under the conditions of their incomplete dehydration. A good agreement of the theoretical ignition delay times of the CWF particles and the experimental values of t _i was established.     

Synthesis and Characterization of the Inclusion Complex of Dicationic Ionic Liquid and β-Cyclodextrin

The supramolecular structure of the inclusion complex of β-cyclodextrin (β-CD) with 1,1',2,2'-tetramethyl-3,3'-(p-phenylenedimethylene) diimidazolium dibromide (TetraPhimBr), a dicationic ionic liquid, has been investigated. The inclusion complex with 1:1 molar ratio was prepared by a kneading method. Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD) analysis, (1)H NMR and thermogravimetric analysis (TGA) confirmed the formation of the inclusion complex. The results showed that the host-guest system is a fine crystalline powder. The decomposition temperature of the inclusion complex is lower than that of its parent molecules, TetraPhimBr and β-CD individually.     

Pollution of Chrome Bearing Materials and the Solutions

This paper summarizes the pollution, situation and solutions of chrome bearing materials used in high temperature industry. Hexavalent chromium compounds are readily soluble in water and associated with carcinogen. Therefore, serious environmental problems appeal for the study and application of chrome free materials. Chrome free products include: magnesia based materials, dolomite based materials, magnesia spinel materials, magnesia hercynite or magnesia galaxite materials and zirconia containing materials,and other substitutes. Although any product has its advantages and disadvantages, the trend to development of chrome free products is inevitable.     

Fatty Acid Composition of the Maternal Diet During the First or the Second Half of Gestation Influences the Fatty Acid Composition of Sows’ Milk and Plasma,and Plasma of Their Piglets

Dietary supplements of olive oil (OO) or fish oil (FO) during the first (G1: day 1–60) or second half of gestation (G2: day 60 to term, day 115) were offered to pregnant sows. The proportion of fatty acids in milk and plasma were determined by gas chromatography. When supplements were given during G1, the proportions of oleic acid (OA) and arachidonic acid (AA) in the plasma were higher in the OO group than in the FO group, whereas docosahexaenoic acid (DHA) was higher in the latter group at day 56 of gestation. These differences in plasma DHA were still apparent at day 7 of lactation. Similarly, DHA was also higher in the colostrum and milk on days 3 and 21 of lactation and in the plasma of piglets from FO dams compared to the OO group, whereas AA was lower. When the FO supplement was given during G2, AA was lower and DHA higher in the plasma at day 105 of gestation and at day 7 of lactation compared with the OO group. Likewise, DHA was greater in FO than in OO animals during lactation in colostrum and in milk on days 3 and 21 of lactation, and in 3-day old suckling piglets plasma, whereas AA was lower in these animals. Thus, maternal adipose tissue plays an important role in the storage of dietary long-chain polyunsaturated fatty acids (LCPUFA) during G1. They are mobilized around parturition for milk synthesis, and an excess of dietary n-3 LCPUFA decreases the availability of AA in suckling newborns.     

Could the Epigenetics of Eosinophils in Asthma and Allergy Solve Parts of the Puzzle?

Epigenetics is a field of study investigating changes in gene expression that do not alter the DNA sequence. These changes are often influenced by environmental or social factors and are reversible. Epigenetic mechanisms include DNA methylation, histone modification, and noncoding RNA. Understanding the role of these epigenetic mechanisms in human diseases provides useful information with regard to disease severity and development. Several studies have searched for the epigenetic mechanisms that regulate allergies and asthma; however, only few studies have used samples of eosinophil, a proinflammatory cell type known to be largely recruited during allergic or asthmatic inflammation. Such studies would enable us to better understand the factors that influence the massive recruitment of eosinophils during allergic and asthmatic symptoms. In this review, we sought to summarize different studies that aimed to discover differential patterns of histone modifications, DNA methylation, and noncoding RNAs in eosinophil samples of individuals with certain diseases, with a particular focus on those with asthma or allergic diseases.     

Effect of the Location of the Detonation Initiation Point and the Position of the Air–Fuel Cloud on Explosion‐Field Parameters

The effect of the location of the initiation point on explosionfield parameters is studied numerically using as an example the detonation of a stoichiometric mixture of propane with air. The shape of the cloud of the mixture (toroid) and the ratio of its dimensions in calculations are typical of the volumes of air–fuel mixtures formed in accidents. The effect of the initiation point location within the cloud cross section was studied with variation in the position of the lower edge of the cloud above the underlying surface.     

Influence of the glass–calcium carbonate mixture's characteristics on the foaming process and the properties of the foam glass

We prepared foam glasses from cathode-ray-tube panel glass and CaCO₃ as a foaming agent. We investigated the influences of powder preparation, CaCO₃ concentration and foaming temperature and time on the density, porosity and homogeneity of the foam glasses. The results show that the decomposition kinetics of CaCO₃ has a strong influence on the foaming process. The decomposition temperature can be modified by varying the milling time of the glass–CaCO₃ mixture and thus for a specific CaCO₃ concentration an optimum milling time exists, at which a minimum in density and a homogeneous closed porosity are obtained. Under the optimum preparation conditions the samples exhibit a density of 260 kg/m³. The thermal conductivity of the foam glass was measured to be 50–53 mW/(m K). The observed dependence of the foaming process on the decomposition kinetics of the foaming agent can be applied as a universal rule for foaming processes based on thermal decomposition.     

Determination of the laminar burning velocity and the Markstein length of powder–air flames

This work deals with the determination of the laminar burning velocity and introduces the Markstein length of powder–air mixtures. A powder burner was used to stabilize laminar cornstarch–air dust flames and the laminar burning velocity was determined by means of laser Doppler anemometry. The dust concentration was varied from 0.26 to 0.38 kg m⁻³. The measured laminar burning velocities were found to be sensitive to the shape of the flame. With the same dust concentration, parabolic flames were found to have a laminar burning velocity, which was almost twice that of a planar flame (ca. 30 cm s⁻¹ for the latter as compared with ca. 54 cm s⁻¹ for the former). From this discrepancy and the flame curvature, the Markstein length could be determined. It was found to have a value of 11.0 mm. This Markstein length was subsequently used to correct the measured laminar burning velocities at various dust concentrations in order to obtain the unstretched laminar burning velocity. The unstretched laminar burning velocity lies between 15 and 30 cm s⁻¹ and is thought to be a property of the dust and of the concentration.     

Effect of calcination conditions on the species formed and the reduction behavior of the cobalt–magnesia catalysts

The structural characteristics and the reduction behavior of the Co/MgO catalysts were investigated using temperature‐programmed reduction (TPR) and X‐ray diffraction (XRD). The variables investigated included the preparation method and the heat treatment conditions (calcination temperature and time). Depending on these factors, one, two or three of the following Co‐containing species, Co₃O₄, MgCo₂O₄ and (Co, Mg)O (solid solution of CoO and MgO) were identified. The extent of solid solution formation increased as the calcination temperature and calcination time increased. A much lower calcination temperature was needed to form a solid solution in the impregnated catalysts than in the physically mixed ones. The formation of a solid solution rendered the catalyst less reducible. Finally, the decomposition of CH₄, as a probe reaction, was performed and it was found that the amount of carbon deposited decreased with increasing extent of solid solution formation. This revised version was published online in July 2006 with corrections to the Cover Date.