光致取向调控偶氮苯侧链液晶聚合物的阻隔特性研究

研究了液晶分子的排列方式对聚合物膜阻隔特性的影响,采用473 nm线偏振光照无定形偶氮液晶聚合物,使其介晶基元发生从无序到有序的取向排列.用膜透射率变化和锥光干涉图表征了分子的取向,其锥光干涉图为粗黑十字,说明在线偏振光下作用下液晶分子取向形成了单相畴沿面内排列的有序态.用金属表面氧化法进一步研究了取向态聚合物膜的阻隔...     

偶氮苯聚合物的光控图案化

将自组装得到的聚苯乙烯胶体晶体,利用反应离子刻蚀和软刻蚀法复形到偶氮苯聚合物膜表面,获得六方非紧密排列的偶氮苯聚合物半球状阵列微图案膜。采用场发射扫描电子显微镜(FESEM)、原子力显微镜(AFM)和接触角测量仪等对膜的微阵列结构和表面润湿性能进行了表征。研究了光照对膜微图案结构和润湿性能的影响。结果表明:基于偶氮苯基团的光致取向特性,偶氮苯聚合物膜的微图案在偏振光照射下,可由初始的半球状阵列微结构形变成纺锤状和椭球状等结构,这种微结构的改变可以改变膜表面润湿性,实现偶氮苯聚合物膜表面不同微图案和润湿性能的光照调控。     

新型可溶性偶氮聚酰亚胺及其作为液晶光定向层应用的初步研究

以 4 ,4′ 二 (1,2 苯二酸酐 4 羧酸酯 )偶氮苯为二酐单体 ,4 十六烷氧基 4′ ,4″ 二氨基三苯甲烷为二胺单体 ,通过缩聚反应合成了可溶性偶氮聚酰亚胺 .采用红外光谱、氢核磁共振、紫外光谱和热分析等手段 ,对产物的结构、热性能及光学性能等进行了表征 .在紫外光辐照下 ,上述聚合物表现出明显的光色效应 .经线性偏振紫外光 (LPUV)辐射后的上述偶氮聚酰亚胺定向层能诱导液晶盒中液晶分子发生定向沿面排列 ,且取向均匀 .上述实验表明 ,合成的偶氮聚酰亚胺是一类潜在的液晶光定向材料 .     

偶氮苯型侧链液晶聚合物的阻隔特性研究

合成了偶氮苯侧链液晶聚合物聚甲基丙烯酸(3-[4-(4′-氰基偶氮苯)苯氧基]丙酯)(PM3ABCN),采用原位掠入射X射线衍射(GIXRD)方法研究了该聚合物膜在向列相和各向同性态(无定形相)时对气体的阻隔特性.并采用X射线能谱仪(EDS)分析铁片氧化后的氧含量,计算得到渗透通过聚合物膜的氧气的量.结果表明,当PM3ABCN膜处于各向同性态时,通过聚合物膜的氧气平均渗透量为1.92×10-3cm3 day-1m-2;而处于液晶态的膜对氧气的阻隔性提高了4.4倍,氧气平均渗透量为4.38×10-4 cm3day-1 m-2.结合样品表面的显微分析结果,探讨了液晶凝聚相结构对气体小分子的阻隔机理.     

偶氮苯聚合物(PGMAA-20)膜光栅结构的分子取向机制

设计合成及表征了一种含偶氮苯聚合物(PGMAA 20)材料.利用两束S偏振光作为泵浦光在PGMAA 20膜上刻写光栅并观察光栅的衍射信号;然后再用相衬显微镜直接观察偶氮苯薄膜上的光栅结构,并以分子取向机制为基础对光栅形成和消除过程提出了新解释,这种观点被实验观察结果进一步证实.     

偶氮苯为探针的液晶聚合物聚集形态研究

利用紫外-可见光谱,对比研究了尾挂侧链液晶聚合物和腰挂侧链液晶聚合物在结晶相和液晶相转变过程中的液晶基元取向情况.研究表明,石英基材表面倾向于诱导偶氮液晶基元垂直于基材排列;观察到了在液晶态尾挂侧链液晶聚合物和腰挂侧链液晶聚合物的不同取向行为.在室温下重新结晶数天后,腰挂液晶聚合物的紫外可见光谱缓慢回复.     

光致变色液晶聚合物的光致再取向性能研究进展

光致变色分子经掺杂或键合作用嵌在液晶聚合物中可形成光致变色液晶聚合物,在线性偏振光或非偏振光的照射下,此物质中光致变色分子的构型变化会引起整个液晶分子的二维或三维光致再取向的形成,本文综述了光致变色液晶聚合物的光致再取向的近期研究进展.     

偶氮液晶在光学材料中的应用进展

偶氮液晶是一类分子中含有偶氮苯结构的液晶,其偶氮基团在光照射下,能发生可逆的顺反异构反应。由于偶氮苯的顺式结构不能形成稳定的液晶相,因此,偶氮液晶在具有向列液晶温敏性质的同时,也具有特有的光敏性质,其相变与分子取向能够通过光照进行控制。这种特性使得偶氮液晶在光学功能材料方面具有广泛的应用。本文介绍了偶氮液晶的基本特性,结合作者自身的研究工作阐述了其在光学材料应用方面的研究进展。     

非线性光学活性的侧链型聚丙二酸酯液晶的合成和性质

通过熔融缩聚法合成了含非线性光学活性硝基偶氮苯液晶基元的聚丙二酸酯侧链液晶聚合物 ,采用FTIR、NMR对其结构进行了表征 ,DSC确定其液晶转变温度 ,并用变温WAXD及偏光显微镜 (POM )研究其液晶性质 ,该聚合物为近晶型液晶聚合物 ,POM观察到典型焦锥织构 ,近晶相WAXD有对应层间距为2 74nm和 1 35nm的两个衍射峰 .聚合物旋涂膜经电晕极化 ,紫外光谱测试求得其取向序参数 =0 33 .     

重氮偶合方法合成主链型光响应偶氮聚合物

提出了一种利用重氮偶合方法合成主链偶氮聚合物的新方法,合成了一种主链含有假芪型偶氮生色团的聚合物.对合成聚合物的结构、热性能以及光响应性能进行了详细表征.在线偏振激光的作用下,聚合物膜中的偶氮苯生色团发生光致取向,用偏振紫外-可见光光谱测量了此聚合物膜的二向色性,得到聚合物膜的取向有序度为0.03.用波长为488 nm,能量密度为150 mW/cm2的相干Ar+激光对聚合物膜照射1000 s,得到形貌规整的正弦波形表面起伏光栅,光栅的周期为900 nm,起伏深度为89 nm.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.