Mobility of water molecules in Li+, Na+ and Cs+ ionic forms of Nafion membrane studied by NMR

Correlation times and diffusion coefficients of water molecules were measured for the first time by ¹H spin relaxation and pulsed field gradient NMR in Li⁺, Na⁺ and Cs⁺ ionic forms of Nafion 117 membrane. Hydration numbers of Li⁺, Na⁺ and Cs⁺ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules.     

Theoretical studies on the influence of metallic cations on ring opening of propylene oxide catalyzed by metal-salen complexes

We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH⁻ group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH⁻ group and the Fukui function condensed on the OH⁻ group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts.     

Holographic sensors for the determination of ionic strength

Holographic sensors for monitoring ionic strength have been fabricated from charged sulphonate and quaternary ammonium monomers, incorporated into thin, polymeric hydrogel films which were transformed into volume holograms. The diffraction wavelength or reflected colour of the holograms was used to characterise their swelling or de-swelling behaviour as a function of ionic strength in various media. The effects of co-monomer structure, buffer composition, ion composition, pH and temperature were evaluated, whilst the reversibility and reproducibility of the sensor was also assessed. An acrylamide-based hologram containing equal molar amounts of negatively and positively charged monomers was shown to be able to quantify ionic strength independent of the identity of the ionic species present in the test solution. The sensor was fully reversible, free of hysteresis and exhibited little response to pH between 3 and 9 and temperature within the range 20-45 °C. The system was successfully used to quantify the ionic strength of milk solutions, which contain a complex mixture of ions and biological components.     

空心阴极灯激发的微波等离子体炬原子/离子荧光光谱研究--钙的原子/离子荧光光谱

用强短脉冲供电技术的空心阴极灯作激发源、微波等离子体炬作原子／离子化器，建立了原子／离子荧光光谱实验装置。详细研究了微波等离子体功率、观察高度、空心阴极灯电流等因素对原子／离子荧光信号强度的影响，测量了系统对Ca的原子／离子荧光光谱的检出限。     

New protonic solid electrolyte with tetragonal tungsten bronze structure obtained through ionic exchange

Proton exchange reactions have been performed on tetragonal tungsten bronze-like NaNbWO₆ by using nitric acid as an exchanging agent. The characterization of the exchange reaction products has been made by means of chemical analysis, X-ray diffraction, thermal analysis, and IR spectroscopy. The exchange reaction takes place topotactically and the following formula is proposed for the obtained phase of variable composition: Na_1−xH_xNbWO₆·yH₂O (0<x?0.46 and 0?y?0.12). Impedance spectroscopy on the present proton exchanged samples indicated that these samples behaved as solid electrolytes under high humidity. As an example, the compound with the composition Na_0.68H_0.32NbWO₆·0.1 H₂O exhibits ionic conductivity of 8×10⁻³ and 1×10⁻² S cm⁻¹ at 70°C and 90°C, respectively.     

Catalysis by ionic liquid: a simple, green and efficient procedure for the Michael addition of thiols and thiophosphate to conjugated alkenes in ionic liquid, [pmIm]Br

A room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes Michael addition of thiols and diethyl dithiophosphate to a variety of conjugated alkenes such as α,β-unsaturated carbonyl compounds, carboxylic esters, nitriles and chalcones without requiring any other organic solvent and catalyst. The ionic liquid can be recycled for subsequent reactions without any appreciable loss of efficiency.     

InCl3·4H2O Promoted Green Preparation of Xanthenedione Derivatives in Ionic Liquids

Xanthenediones derivatives have attracted considerable interests in recent times because they constitute a structural unit in a number of natural products1 and have been used as versatile synthons due to the inherent reactivity of the inbuilt pyran ring2. The conventional syntheses of xanthenediones were acid or base catalyzed condensation of appropriate active methylene carbonyl compounds with aldehydes3. However, many of these procedures involved longer reaction times,low yields and side reactions of aldehydes. In recent years, room temperature ionic liquids (RTILs) have been used as novel green reaction media4. Considering that InCl3 is an efficient Lewis acid catalyst used in promoting many organic reactions, especially in several condensation processes, we herein wish to report a very simple and green method for the preparation of poly-hydrogenated xanthenediones through InCl3·4H2O promoted cascade reaction of aldehydes and 5,5-dimethyl-l,3-cyclohexanedione in ionic liquid,1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]). The preparative process presented here is operationally simple, environmentally benign and has the advantage of enhanced atom utilization. Furthermore, the solvent and the catalyst used can be recovered easily and reused efficiently.     

NASICON型化合物结构的NMR研究

在水热晶化合成一系列NASICON型化合物的基础上,应用固体高分辨³¹P和²⁹Si MAS NMR,研究了几种NASICON化合物的结构,观察其骨架原子P和Si在结构中的状态及分布,并解释了由于在结构中发生取代作用而引起,Si或P的化学位移的变化.     

The concentration effect on the ‘hydrophobic’ and ‘hydrophilic’ behaviour around DMSO in dilute aqueous DMSO solutions. A computer simulation study

We have carried out a molecular dynamics study of dimethyl sulfoxide (DMSO) in water at 298 K at two different densities by simulating two different concentrations: 0.055 and 0.19 mole fraction. We have found an enhancement in the structure of water, an effect that becomes more pronounced as the concentration of DMSO increases. At both concentrations there is a well-defined hydration structure around the oxygen atom of DMSO, which is able to establish strong hydrogen bonds with surrounding water molecules. An increase in the concentration of DMSO depletes the solution of bulk water molecules, reducing the number of hydrogen bonds that water can have in the immediate vicinity of DMSO but increasing the strength of the hydrogen bonds made between the oxygen atom of DMSO and water. There is clear evidence of ‘hydrophobic’ hydration around the methyl groups of DMSO, which is enhanced as the concentration of DMSO increases.     

Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007