Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃ could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

Novel,biodegradable, functional poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate bearing a pendent carboxylic group

Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (M_n) and molecular weight distribution (M_w/M_n) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (M_n = 6000–14,700 g mol^?1) with reasonable molecular weight distributions (M_w/M_n = 1.11–2.23). The values of the glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the T_g increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004     

神经网络法计算镉（Ⅱ）,羟基及碳酸根三元体系的形态分布

采用前馈线笥网络ＢＰ算法，计算了Ｃｄ６２＋－ＯＨ＾－ＣＯ＾２－３三元体系的累积稳定常数。用Ｈｏｐｆｉｅｌｄ反馈网络研究了体系中络合物的形态分布。溶液中溶解的ＣＯ２对ｌｇβ１的计算结果有重要影响，对ｌｇβ２，ｌｇβ３，ｌｇβ４的结果影响不大。     

Synthesis of Dimethyl Carbonate from CO2 , Methanol, and Epoxides Using Re（CO） 5 Cl/K2 CO3 as Catalyst System

IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb     

Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Amending cultures of selenium-resistant bacteria with dimethyl selenone

A possible biological intermediate in the reduction and methylation of selenium oxyanions, dimethyl selenone, was synthesized, and the first experiments involving the amendment of selenium resistant bacterial cultures with this compound are reported. The amount of volatile, reduced selenium-containing species released from these cultures into the headspace is significantly more than that produced in analogous experiments involving sodium selenate amended cultures. Dimethyl selenone is reduced in the presence of dimethyl sulfide and dimethyl disulfide in a complex growth medium, trypticase soy broth with 0.1% nitrate. This reduction occurs whether or not the reduced sulfur compounds are biologically produced.     

Effects of barium on the nonlinear electrical characteristics and dielectric properties of SnO2-based varistors

The effects of barium on electrical and dielectric properties of the SnO_2·Co_2O_3·Ta_2O_5 varistor system sintered at 1250℃ for 60min were investigated. It is found that barium significantly improves the nonlinear properties. The breakdown electrical field increases from 378.0 to 2834.5V/mm, relative dielectric constant (at 1kHz) falls from 1206 to 161 and the resistivity (at 1kHz) rises from 60.3 to 1146.5kΩ·cm with an increase of BaCO_3 concentration from 0mol% to 1.00mol%. The sample with 1.00mol% barium has the best nonlinear electrical property and the highest nonlinear coefficient (α=29.2). A modified defect barrier model is introduced to illustrate the grain-boundary barrier formation of barium-doped SnO_{2}-based varistors.     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the ¹³C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006