吡啶羧酸类配位聚合物的研究进展

作为潜在的新型功能材料,吡啶羧酸类配位聚合物近年来得到科学家的普遍关注.本文主要对吡啶羧酸类配位聚合物在手性拆分和催化、分子磁体、非线性光学方面的研究进行了综述,列举了近年来这类配位聚合物的研究成果和开发进展,并对其发展前景作出了展望.     

Construction of Chiral 2‐Substituted Octahydroindoles from Cyclic Ketones and Nitroolefins Bearing only One α‐Substituent

A dual catalytic system has been developed following the screening of a series of chiral primary amine catalysts and chiral phosphoric acid catalysts for the Michael addition of cyclic ketones to nitroolefins bearing only one α‐substituent. The resulting γ‐nitro ketones, which contain a substituent on the carbon connected to the nitro group, were formed in excellent yields (>80%) with high levels of stereoselectivity (up to 94:6 dr and 98% ee) when the reaction was performed in benzene at 0 °C with 10 mol% of the optimal amine/phosphoric acid combination (1:1) as a catalyst. Subsequent reduction of the nitro group followed by intramolecular reductive amination could afford optically active cis‐octahydroindole analogues bearing a non‐functional substituent at their 2‐position.

     

(6S)2,6-二氨基-4,5,6,7-四氢苯并噻唑的制备

以2-氨基-6-乙酰氨基-4,5,6,7-四氢苯并噻唑氢溴酸盐为原料,经过水解反应除去乙酰基,然后用L(+)酒石酸成盐、解析拆分后合成了制备普拉克索的重要中间体-(-)-(6S)2,6-二氨基-4,5,6,7-四氢苯并噻唑,总收率>75%,并对合成产物进行1H NMR、IR表征分析。     

S-(1H-苯并咪唑-2-基)甲基烷基黄原酸酯的合成及其摩擦学性能初步研究

合成了2个新型S-(1H-苯并咪唑-2-基)甲基烷基黄原酸酯无灰无磷环境友好型润滑油添加剂烷基黄原酸基亚甲基苯并咪唑衍生物;利用1H NMR、13C NMR、IR、UV、MS和元素分析对其结构进行了表征;利用热重实验和油溶性实验考察了其热稳定性及其在有机溶剂中的溶解性;利用四球摩擦磨损实验机考察了合成的添加剂在液体石蜡中的摩擦学性能。结果表明,制备的添加剂可有效地提高液体石蜡的承载力。     

吸电子基团对[60]富勒烯吡咯烷空间结构的理论研究

借助密度泛函量子力学程序对硝基、甲氧基和羟基3种吸电子基团对[60]富勒烯吡咯烷空间结构的影响进行了研究。结果表明,结构优化后的[60]富勒烯吡咯烷衍生物的LUMO与HOMO能量差ΔE并不随基团吸电子能力的增强而增加,吸电子基团对[60]富勒烯衍生物吡咯烷键长和键角的影响大小为NO2>OH>OCH3。     

邻杂环(噁二唑)甲酰苯胺类化合物的设计合成及杀虫活性初步研究

以超高效杀虫剂氯虫苯甲酰胺为先导,在酰胺部分引入了邻杂环(噁二唑),设计并合成了16个含邻杂环(噁二唑)甲酰苯胺类新化合物。生测结果表明,化合物普遍具有高杀虫活性,在10 mg/L剂量下对小菜蛾的致死率均大于80%。本研究结果为该类化合物的创制提供了参考。     

3-（2-羟基-4,5-二甲氧基苯基）丙酸钠的合成

丹参素有良好的药效,它的生物活性可能跟苯基乳酸结构有关,本论文以3,4-二甲氧基苯丙酸为原料,经溴代、水解反应合成了丹参素类似物3-（2-羟基-4,5-二甲氧基苯基）丙酸钠。     

姜黄素结构修饰的研究进展

对姜黄素衍生物类药物的结构修饰进行归类,探讨了姜黄素衍生物的生物活性与化学结构的关系,分析了姜黄素衍生物中化学基团对生物活性的影响,为以后合成具有高效专一的生物活性姜黄素衍生物提供依据。     

CdS Quantum Dots Encapsulated in Chiral Nematic Mesoporous Silica: New Iridescent and Luminescent Materials

Simultaneous integration of light emission and iridescence into a semiconducting photonic material is attractive for the design of new optical devices. Here, a straightforward, one‐pot approach for liquid crystal self‐assembly of semiconductor quantum dots into cellulose nanocrystal‐templated silica is developed. Through a careful balance of the intermolecular interactions between a lyotropic tetraalkoxysilane/cellulose nanocrystal dispersion and water‐soluble polyacrylic acid/mercaptopropionic acid‐stabilized CdS quantum dots, CdS/silica/nanocellulose composites that retain both chiral nematic order of the cellulose nanocrystals and emission of the quantum dots are successfully co‐assembled. Subsequent removal of the cellulose template and organic stabilizers in the composites by controlled calcination generates new freestanding iridescent, luminescent chiral nematic mesoporous silica‐encapsulated CdS films. The pores of these materials are accessible to analytes and, consequently, the CdS quantum dots undergo strong luminescence quenching when exposed to TNT solutions or vapor.     

Fluorene derivatives for highly efficient non-doped single-layer blue organic light-emitting diodes

Diphenylamino- and triazole-endcapped fluorene derivatives which show a wide energy band gap, a high fluorescence quantum yield and high stability have been synthesized and characterized. Single-layer electroluminescent devices of these fluorene derivatives exhibited efficient deep blue to greenish blue emission at low driving voltage. The single-layer OLED of PhN-OF(1)-TAZ shows a maximum current efficiency of 1.54 cd/A at 20 mA cm⁻² with external quantum efficiency (EQE) of 2.0% and CIE coordinates of (0.153, 0.088) in deep blue region, while the single-layer device of oligothienylfluorene PhN-OFOT-TAZ shows a maximum brightness of 7524 cd/m² and a maximum current efficiency of 2.9 cd/A with CIE coordinates of (0.20, 0.40) in greenish blue.