A characteristic effect of pressure on inclusion complexation of phenothiazine dyes with p-sulfonatocalix[6]arene in a room-temperature ionic liquid

The inclusion complexation of p-sulfonatocalix[6]arene (Calix-S6) with three kinds of phenothiazine dyes was studied spectrophotometrically in a mixture of a room-temperature ionic liquid [bmim]BF₄ (1-butyl-3-methylimidazolium tetrafluoroborate) and ethanol. We have determined the association constants of Calix-S6 with phenothiazine dyes under external static pressure up to 767 bar in the [bmim]BF₄-ethanol and alcohol-water mixtures. With increasing external pressure, the inclusion equilibrium in the alcohol-water mixtures was shifted to the dissociation side. Conversely, the inclusion equilibrium of methylene blue (MB) and azure A (AA) in the ionic liquid mixture was shifted to the association side. From the analysis of the pressure effects, the reaction volumes ΔV for inclusion complexation were estimated as −7 to 9 cm³ mol⁻¹ in the [bmim]BF₄-ethanol mixture and 20–32 cm³ mol⁻¹ in the alcohol-water mixtures. Based on the results, we have suggested that there is a competing complexation between the included dye and [bmim]BF₄ molecules in the ionic liquid.     

Thermally reversible light scattering films based on the melting/crystallization of organic crystals dispersed in an epoxy matrix

Films that can be reversibly switched from opaque to transparent states by varying temperature (TRLS films), have potential applications in thermal sensors, optical devices, recording media, etc. A dispersion of organic crystals in a thermoset may be used for these purposes provided that at temperatures higher than the melting point there is a matching of refractive indices of both phases. A model system consisting on a dispersion of diphenyl (DP) crystals in an epoxy matrix based on diglycidyl ether of bisphenol A and m-xylylenediamine, was analyzed as a possible TRLS film encapsulated between transparent covers to avoid sublimation of DP. To obtain a uniform dispersion of DP-rich domains in the epoxy matrix by polymerization-induced phase separation, it was necessary to add 5 wt% of polystyrene (PS) to the initial formulation. Phase separation induced by polymerization at 80 °C led to a dispersion of PS/DP domains in the epoxy matrix due to the low compatibility of PS with the epoxy and its high compatibility with DP. Crystallization and melting processes were confined to the interior of dispersed domains leading to an excellent reproducibility of the optical properties of TRLS films in the course of successive heating-cooling cycles.     

Rapid Mo(CO)6 catalysed one-pot deoxygenation of heterocyclic halo-benzyl alcohols with Lawesson’s reagent

A fast and efficient microwave promoted one-pot method for deoxygenation of heterocyclic halo-benzyl alcohols has been developed. The method does not cause dehalogenation of the substrates and provides the deoxygenated products in high yield after only 30 min.     

1,6-二氢-S-四嗪催化重排及其反应的研究--Ⅱ. 与氯甲酸三氯甲酯反应

在4－二甲胺基吡啶的存在下，1，6－二氢－S－四嗪重排成3，6－二氢－S－四嗪，与双光气反应后再与不同的胺反应，合成了11种1，4－二取代产物，产物经元素分析、IR和^1H NMR确证。用UV和^1H NMR分析结果对反应机理进行了初步探讨。     

烷基和烷基苯磺酸钠系列的反相高效液相色谱法

用移动相中含有磷酸二氢钠的反相高效液相色谱法分析了烷基磺酸钠和烷基苯磺酸钠。对前者用电导检测器直接进行检测(无抑制柱),后者用紫外检测器检测。对几种商品十二烷基苯磺酸钠的组分和微乳液中十二烷基磺酸钠的含量进行了测定。得到了满意的结果。     

Dealkylation ofpara-nitrophenyldimethyl thiophosphate in micellar and liquid-crystalline media of then-decylammonium chloride-n-decylamine-water system

The kinetics of decomposition of p-nitrophenyldimethyl thiophosphate (1) were investigated spectrophotometrically in the n-decylammonium chloride-n-decylamine-water system (DAC-DA-H₂O), in which micellar or lamellar liquid-crystalline phases are formed as a function of the concentration of components. It was shown that1 is dealkylated in both phases. An increase in the surface charge density of associates decreases the rate of dealkylation. The activation energy in the lamellar phase is significantly higher than in the micellar phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1992.     

Synthesis and characterization of surface-cyanofunctionalized poly (N-isopropylacrylamide) latexes

 A series of P[N-isopropylacrylamide (NIPAM)] latexes with different contents of cyano groups were successfully prepared by either seeded or shot-growth polymerizations of an aqueous solution containing acrylonitrile (AN) onto a seed P[NIPAM] latex, respectively, and further characterized by FT-IR, ¹H-NMR, elemental analysis, as well as by quasielastic light scattering (QELS) and scanning electron microscopy (SEM). All prepared surface-cyanofunctionalized P[NIPAM] latexes exhibited the same range of lower critical solution temperature (LCST) as a pure P[NIPAM] latex. The shot polymerization process proved more efficient at yielding cyano derivatized latexes than the seeded polymerization technique. The amount of incorporated cyano groups onto the particles was determined with a good correlation both by ¹H-NMR and elemental analysis. The higher the amount of initially introduced AN monomer in the reaction mixture, the more cyano groups were incorporated onto the particles. The surface of the particles with high content of cyano groups appeared quite rough by SEM in comparison with that of the pure P[NIPAM] particles. Received: 25 February 1998 Accepted: 23 June 1998     

2，6－双（1′－苯基－3′－甲基－5′－氧代－4′－甲酰吡唑）吡啶稀土配合物的合成与表征

在乙醇－水溶液中合成了１４种２，６－双（１′－苯基－３′－甲基－５＇－氧代－４＇－甲酰吡唑）吡啶稀土配合物。元素分析确定其化学组成为ＲＥ＿２Ｌ＿３·ｎＨ＿２Ｏ，并用紫外可见光谱、红外光谱、核磁共振谱、热分析、荧光光谱、摩尔电导等进行了表征。     

两亲嵌段共聚物聚乙二醇-聚谷氨酸苄酯纳米粒药物载体的合成研究

用磺酸酯法制备单端氨基聚乙二醇引发剂,引发谷氨酸苄酯羧酸酐开环聚合,生成可生物降解的两亲嵌段共聚物聚乙二醇﹣聚谷氨酸苄酯(PEG-PBLG),用IR,NMR和GPC表征了共聚物。用超微透析法制备PEG-PBLG聚合物纳米粒,荧光芘探针法测定纳米粒的临界聚集浓度(cac)。紫外分光光度计考察纳米粒对疏水性药物的增溶作用,PEG-PBLG可作为亚微粒药物输送系统的载体。     

Development of the FTIR properties of nano-structure silica gel doped with different rare earth elements,prepared by sol-gel route

Structural characteristics of pure silica gel (silica-xerogel, SiO₂) and silica gel doped with some rare earth elements (REEs) such as, praseodymium Pr³⁺, and Europium Eu³⁺, Erbium Er³⁺ and Holmium Ho³⁺ ions, with different concentrations ranging from 1 up to 6%, in the form of monolith materials were prepared by sol-gel technique, Using tetra-ethoxysilane as precursor materials, which are of particular interest for sol-gel integrated optics applications. Some structural features of sol-gel derived monolith are analyzed, namely the structure of nano-particle momolith samples, based on X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR). We show that the XRD spectra of α-crystobalite are obtained for the pure samples at 1100°C and even by doping with the four REEs ions.