Description of the turbidity measurements near the phase transition temperature of poly(N-isopropyl acrylamide) copolymers: the effect of pH, concentration, hydrophilic and hydrophobic content on the turbidity

Absorbance values between 300 and 800 nm of aqueous solutions of poly(N-isopropyl acrylamide-co-itaconic acid-9.80), poly(N-isopropyl acrylamide-co-itaconic acid-52.05) and poly(N-isopropyl acrylamide)s containing Tegomer H-Si 2111 end groups and/or blocks were measured using a Shimadzu 160-A UV-visible spectrometer. Turbidities obtained from these absorbance values were used to interpret the macromolecular phase transition from a hydrophilic to a hydrophobic structure of the polymers. The effects of comonomer type and content, concentration of the solutions, pH and temperature on the coil-globule transition were discussed in terms of turbidity form factor, β related to size and shapes of particles and calculated by using the simplified form of Debye equation.The results presented in this work show that the presence of Tegomer H-Si 2111 (Si containing end groups and/or blocks) or high amount of itaconic acid (IA) in the chains prevent a collapse transition from hydrated extended coils to hydrophobic globules, which aggregate and form a separate phase (β<2). Furthermore, it was observed that in the case of concentrated solutions intermolecular hydrophobic interactions between isopropyl groups overcame the repulsive forces resulting from the ionized carboxylic acid groups of IA or surface active nature of Si containing hydrophobic groups (β>2). This stage of the transition corresponds to macroscopic phase separation after an intramolecular process.     

Analyzing electrochemical noise with Chebyshev’s discrete polynomials

The principles underlying a novel method intended for analyzing experimental data obtained when studying fluctuation processes are considered. The method in question is Chebyshev’s spectroscopy. The application of this method allows one to determine statistic characteristics of steady-state electrochemical noise against the background of severe deterministic interference without invoking the procedure of the fitting of the initial data. The potentialities of this novel method, which is intended for treating noise experiment, are demonstrated by examining model examples and analyzing the electrochemical noise generated by a lithium electrode placed in an aprotic organic electrolyte.     

纳米级NiTiO3粉体的合成

以Ｈ２ＴｉＯ３，Ｈ２Ｏ２及ＮｉＣｌ２为主要原料，用化学共沉淀法制备了纳米级ＮｉＴｉＯ３。确定了反应物Ｈ２ＴｉＯ３，Ｈ２Ｏ２，ＮＨ３的最佳摩尔比为１：８：２，用不同的退火温度和退火时间对样品处理得到相应粒径的纳米级粉体。     

New stationary phases of conjugated π-electron systems for HPLC—characterization of structure and dynamics by solid state NMR spectroscopy

Four new stationary phases for HPLC were prepared by modifying silica gel with a trifrnctional aminoalkyl silane. A conjugated π-electron system was linked to the amino group either directly or with a carboxylic anhydride as a spacer in between. Characterization and dynamic measurements of the new stationary phases were performed by solid state NMR spectroscopy. The results of the ²⁹si and ¹³C CP/MAS techniques were compared with the recently developed ¹H MAS-only technique. Despite strong homonuclear dipole-dipole interactions it was possible to obtain well resolved ¹H MAS spectra of those stationaru phases with a high degree of crosslinking. Limited mobility of the aromatic ligand fragments is common for all examined stationaryu phases. The chromatographic properties of the new phases were tested by their ability tio sepatate a mixture of eight PAHS. It could be shown that the π-π interaction mechanism is responsible for the separation of the eight PAHs, because the elution order of the PAHs did not changem despite the use of both a nonpolar mobile phase (n-heptane) and a polar mobile phase (methanol/ water mixture).     

Coadsorption of carbofuran and lead at the water/silica interface. Possible impact on environment

Despite its extremely weak adsorption at the water/silica interface, carbofuran can, however, induce the coadsorption of metallic salts, like, for example, lead nitrate, and thus enhance its adsorption. We quantitatively studied this phenomenon with a depletion method and under concentration conditions close to the environmental ones. Heavy metal salt was found to positively adsorb, whereas carbofuran relative adsorption is generally slightly negative. This study provides evidence that considering these facts is of paramount importance in environmental prospects. To cite this article: G. Elmanfe et al., C. R. Chimie 9 (2006).     

On the Rigidity of Polynorbornenes with Dipolar Pendant Groups

A range of polynorbornenes (PNBs) with fused dipolar pendant groups at C‐5,6 positions was synthesized by ring‐opening metathesis polymerization catalyzed by a ruthenium carbene complex (Grubbs I). Photophysical studies, EFISH measurements, and atomic force microscopy images have been used to investigate the structures and morphology of these polymers. These results suggest that the polymers may adopt rigid rod‐like structures. The presence of the double bonds in PNBs appeared to be indispensable for the rigidity of the polymers. Interaction between unsaturated pendant groups may result in coherent alignment leading to a rod‐like structure.     

液体色谱,凝胶色谱分析低聚芳砜及其双烯大分子单体

本文用液相色谱和凝胶色谱对双酚A、双酚S型低聚芳砜及α,ω-双甲基丙烯酸聚芳砜酯大分子单体进行了组分分析,通过改合成条件、测定数均分子量等辅助手段确定液相色谱各峰的归属,计算其分子量及分子量分布指数,并对两种方法测定的结果进行了比较。用液相色谱观察低聚体每个组分的含量及其反应过程中的消长情况比凝胶色谱清晰。     

新型热反应大分子单体的合成与表征

溶液法合成了一些低分子量的羟端基低聚苯醚砜,并由相转移催化剂将之转为热反应大分子单体——α,ω-双甲基丙烯酸聚苯醚砜酯;用FTIR、~1H-NMR对其结构进行了表征,GPC、VPO对其分子量进行了分析和测定;用DSC、DTA对聚苯醚砜双烯大分子单体的转变温度、热反应过程进行了测定和分析。     

Direct organocatalytic in situ generation of novel push-pull dienamines: application in tandem Claisen-Schmidt/iso-aromatization reactions

A new, green, regioselective, one-step, tandem reaction of an aldehyde possessing a non-enolizable carbonyl function with a highly substituted cyclohex-2-enone, under amine catalysis afforded highly substituted phenols or 2-arylidenecyclohexanones, respectively. The yields and regioselectivities were good. Evidence for a pathway involving formation of novel push-pull dienamines is presented along with examples demonstrating the amenability of the process to combinatorial chemistry.     

Ring-opening Polymerization of e-Caprolactone Using Lanthanide Tris(4-tert-butylphenolate)s as a Single-component Initiator

The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.