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.     

γ-sets and other singular sets of real numbers

A family of $\text{J}$ of open subsets of the real line is called an ω-cover of a set X iff every finite subset of X is contained in an element of $\text{J}$. A set of reals X is a γ-set iff for every ω-cover $\text{J}$ of X there exists $\text{〈D}{}_{\mathrm{n}}\text{: n < ω〉?}\text{J}{}^{\mathrm{\omega }}$ such that

In this paper we show that assuming Martin's axiom there is a γ-set X of cardinality the continuum.     

Poly(ethylene glycol) as Impregnator for Silica Gel in Salting-Out Thin-Layer Chromatography of Some Co(III) Complexes

Silica gel impregnated with poly(ethylene glycol) of different molecular mass (400, 1000, 1540, 4000, and 5500) was investigated for salting-out thin-layer chromatography of 15 mixed aminocarboxylato Co(III) complexes using eight ammonium sulphate solutions as mobile phases. Regularities established earlier for non-impregnated adsorbents are also valid in this work. Poly(ethylene glycol) of high molecular mass increases the hydrophobicity of the adsorbent. Positive linear dependence of R_M values and of salting-out efficiency on average poly(ethylene glycol) molecular mass was usually observed. In contrast with non-impregnated silica gel, separation was achieved between complexes with the smallest hydrocarbon groups.     

Low detection limit spectrophotometry

An efficient, more sensitive and accurate spectrophotometric process is possible and can be used to obtain qualitative or quantitative results for analytes at limiting concentrations lower than usual. Transmission measurements (incident light power, P₀, or transmitted, P) are performed with a fluorescence spectrometer. One cell only is used to measure standards or unknown solutions, placed between the standard holder cuvette and the emission monochromator of the instrument. The source of the radiant power (P₀) is not the xenon lamp but the fluorescence or scattered radiation from the holder cuvette filled with an appropriate solution. The analyte concentration is found from a calibration graph, based upon Beer’s law or the approximate formula P₀−P=2.303P₀εbc, which is valid for dilute solutions. Determination of iron in a reference material, using 1,10-phenanthroline as the chromogenic reagent, was chosen as an example to demonstrate the suitability of the proposed method and clarify several important statistical questions. Also discussed is why and to what extent molecular fluorescence methods are more sensitive than molecular absorption methods.     

Acetylenic/cyanoacetylenic complexes: simulation of the Titan’s atmosphere chemistry

The structures and energies of the 1:1 acetylene/cyanoacetylene, acetylene/dicyanoacetylene and cyanoacetylene/dicyanoacetylene complexes in solid argon matrices have been investigated using FT-IR spectroscopy and ab initio calculations, at the B3LYP/6-31G** level of theory. For the three complexes, predicted frequency shifts for the L shaped structures, characterized by a hydrogen bond between the nitrogen of the cyano group and the acetylenic proton, were found to be in good agreement with those experimental. Only in the case of acetylene/cyanoacetylene complex, we obtained a second minimum with a T shaped structure characterized by an interaction between the proton of cyanoacetylene and the Π system of acetylene. It appears clearly that HC₃N acts as an electrophile or as a nucleophile in these complexes.     

SYNTHESIS AND PROPERTIES OF SULFONATED POLY（ARYLENE ETHER） CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.