Coerced photodimerization reaction in the solid state through amine salt formation

Photodimerization of fumaric or several γ-form trans-cinnamic acids proceeded successfully in the solid state through amine salt formation with ammonia or some aromatic heterocyclic amines (especially, imidazole). It appears that this success is due to a small size or a planar structure of the amine. A layered or a channel-type clathrate crystal structure was revealed, respectively.     

环氧树脂体系固化反应及其复合材料介电性能

环氧树脂是一类综合性能优异的热固性高分子材料，作为胶粘剂、复合材料用树脂基体、涂料等形式广泛应用于电子电气、机械制造、化工防腐、航空航天等众多领域中，成为各工业领域中不可缺少的基础材料。本文综述了本研究室在咪唑／环氧树脂体系，稀土有机化合物、叔胺羧酸复盐／酸酐／环氧树脂体系，氰酸酯／环氧树脂体系，硼胺络合物／环氧树脂体系的固化反应机理、固化反应动力学及其固化物结构与性能关系，纤维含量、排列方向、偶联剂种类等对玻璃纤维增强环氧树脂基复合材料及其界面介电性能的影响等6个方面的研究进展。     

Existence of dynamic tautomerism and divalent N(I) character in N‐(pyridin‐2‐yl)thiazol‐2‐amine

N‐(Pyridin‐2‐yl)thiazol‐2‐amine is a versatile chemical functional unit present in many therapeutically important species. Quantum chemical analysis shows that there are six competitive isomeric structures possible for this class of compounds within a relative energy difference of ～4 kcal/mol. Some of the isomeric structures possess divalent N(I) character. There appears to be a competition between the thiazole and pyridine groups to accommodate the tautomeric hydrogen, and consequently show electron donating property in the structure with R‐N←L representation. Details of electron distribution, tautomeric preferences, protonation energy, and divalent N(I) character, and so on, of this class of compounds are presented in this article. Subsequently, upon protonation, (L→N←L)^⊕ character is clearly evident in these moieties as molecular orbital analysis clearly shows two lone pairs of electrons on the central nitrogen, in this system. © 2013 Wiley Periodicals, Inc.     

Efficiency of antidepressant drugs as monoamine reuptake inhibitors: analysis of the hydrophobicity influence using biopartitioning micellar chromatographic data

The reuptake blockade of biogenic amines by antidepressants is related not only to their therapeutics effects, but also to their side effects and potential drug-drug interactions. As an alternative to classical quantitative structure-activity relationships studies, in this work we propose different quantitative retention-activity relationships (QRAR) models that are able to describe the monoamine reuptake inhibition by antidepressants. The retention of compounds is measured using a biopartitioning micellar chromatography (BMC) system that can simulate the same hydrophobic, electronic and steric molecular interactions as those that condition drug activity. Since all the compounds considered in this work are structurally related because all of them share the same molecular features as the corresponding basic pharmacophore, the results obtained show that there is a retention range in which antidepressants present the highest monoamine reuptake inhibitor potency.     

Alkylative Aziridine Ring-Opening Reactions

In this study, the highly strained three-membered aziridine ring was successfully activated as the aziridinium ion by alkylation of the ring nitrogen with a methyl, ethyl or allyl group, which was followed by ring opening with external nucleophiles such as acetate and azide. Such alkylative aziridine ring opening provides an easy route for the synthesis of various N-alkylated amine-containing molecules with concomitant introduction of an external nucleophile at either its α- or β-position.     

Tunable Viscoelastic Properties of Sodium Polyacrylate Solution via CO2-Responsive Switchable Water

Upon stimulus by CO₂, CO₂-switchable viscoelastic fluids experience a deliberate transition between non-viscous and highly viscous solution states. Despite attracting considerable recent attention, most such fluids have not been applied at a large- scale due to their high costs and/or complex synthesis processes. Here, we report the development of CO₂-switchable viscoelastic fluids using commercially available sodium polyacrylate (NaPAA) and N,N-dimethyl ethanol amine (DMEA)-based switchable water. Upon bubbling CO₂, into the solutions under study, DMEA molecules are protonated to generate quaternary ammonium salts, resulting in pronounced decreases in solutions viscosity and elasticity due to the influence of increased ionic strength on NaPAA molecular conformations. Upon removal of CO₂ via introduction of N₂, quaternary salts are deprotonated to tertiary amines, allowing recovery of fluid viscosity and elasticity to near the initial state. This work provides a simple approach to fabricating CO₂-switchable viscoelastic fluids, widening the potential use of CO₂ in stimuli-responsive applications.     

Excess enthalpies of alcohol + amine mixtures. Experimental results and theoretical description using the ERAS-model

New experimental data of the molar excess enthalpy H^E of mixtures containing eight liquids - propylamine + methanol, ethanol, propan-1-ol, butan-1-ol, butylamine + methanol, ethanol, propan-1-ol, butan-1-ol - are presented using a quasi-isothermal flow calorimeter. The results are used for testing the ERAS-model which provides a theoretical concept accounting for the self-association and cross-association of alcohol and amine molecules, as well as for non-associative intermolecular interactions. Excess molar volumes V^E are also successfully described by the model. It turns out that the strong cross-association occurring between alcohol and amine molecules is the predominant reason for the remarkably low exothermic values of H^E observed for the mixtures studied.     

Synthesis and properties of novel aromatic poly(ester amide)s derived from 1,5-bis(4-aminobenzoyloxy)naphthalene and aromatic dicarboxylic acids

A new naphthalene ring-containing bis(ester amine), 1,5-bis(4-aminobenzoyloxy)naphthalene (2), was synthesized from the condensation of 1,5-dihydroxynaphthalene with 4-nitrobenzoyl chloride followed by catalytic hydrogenation. A series of naphthalene-containing poly(ester amide)s having inherent viscosities of 0.34-0.82 dl/g were prepared by the direct phosphorylation polyamidation from bis(ester amine) 2 with various aromatic dicarboxylic acids. The poly(ester amide)s derived from terephthalic acid, 4,4′-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-oxydibenzoic acid were semicrystalline and showed less solubility. The other polymers were amorphous and readily soluble in polar organic solvents and gave flexible and tough films via solution casting. Except for four examples, the poly(ester amide)s displayed discernible glass transitions between 190 and 227 °C by differential scanning calorimetry. These poly(ester amide)s did not show significant decomposition below 400 °C in nitrogen or air.     

含三(2-吡啶甲基)胺识别体的荧光化学敏感器核磁共振谱分析

采用二维核磁共振谱技术对新型丹磺酰胺和1,8-萘酰亚胺荧光化学敏感器的结构进行了测定。应用'H—'HCOSY、HSQC、HMBC等二维相关核磁谱对化合物的C和H进行了正确的归属。     

基于聚醚胺(PEA)动态交联网络的多重响应性表面褶皱图案

刺激响应性表面图案赋予了材料动态可调的表面性能,是智能材料领域研究的热点,然而如何通过简单有效的方法构建这类动态表面图案也是该领域的难点.本文将动态硼酸酯键和光可逆二聚基团引入到聚醚胺(PEA)交联网络中,通过双层褶皱体系构建一系列具有光和湿度刺激响应性表面褶皱图案.在365 nm紫外光照和加热的条件下,蒽基团(AN)的光二聚与硼酸键的形成使得上表层聚醚胺模量变大,产生微米级表面褶皱图案;在254 nm紫外光照射或水蒸气作用下,聚醚胺网络解交联,表面褶皱图案消失;利用光化学时空分辨的特性,通过光掩膜板光照还可以制备多层次动态表面褶皱图案.这种多重刺激响应性表面褶皱图案为构建智能聚合物表面提供了新思路,在传感和防伪等领域具有潜在的应用前景.