Novel azobenzene-phthalocyanine dyads―― design of photo-modulated J-aggregation

Based on the J-aggregation mechanism of α-aryl/alkoxy-substituted zinc phthalocyanines(Pcs) in non-coordinating solvents, two novel azobenzene-phthalocyanine dyads (3-azo-ZnPc and 4-azo-ZnPc) were synthesized with the aim of developing Pc compounds whose ability to form J-aggregation could be photo-modulated. It was found that 3-azo-ZnPc in chloroform could be effectively photo-controlled in a wide range. This phenomenon could be explained by the changes in the geometry and dipole moment of azobenzene during the photo-isomerization process. 4-azo-ZnPc did not have this ability at all, with or without UV light illumination. The positions of the oxygen atoms to which the aryl/alkoxy substitution was attached relatively were found important in determining the aggregation ability. Supported by the National Natural Science Foundation of China (Grant Nos. 20572059, 20502013 and 20773077), National Key Fundamental Research Program (Grant No. 2007CB808000)     

自组装方法制作带有缺陷的三维光子晶体

采用自组装方法制作三维光子晶体及其反相结构,并将自组装方法与光刻技术联合,制备出具有各种缺陷的三维光子晶体。SEM显示出晶体具有较高质量,缺陷层也具有均匀性。     

RAFT 分散聚合诱导自组装制备 PDMAs-PSx 嵌段共聚物纳米颗粒

可逆加成-断裂-链转移(reversible addition-fragmentation-chain transfer, RAFT)聚合诱导自组装(polymerization-induced self-assembly, PISA)是制备具有特定形貌嵌段共聚物纳米颗粒的高效手段. 以苯乙烯(styrene, St)为分散聚合的单体, PDMA可逆加成-断裂-链转移(reversible addition-fragmentation-chain transfer,RAFT)聚合诱导自组装(polymerization-induced self-assembly,PISA)是制备具有特定形貌嵌段共聚物纳米颗粒的高效手段.以苯乙烯(styrene,St)为分散聚合的单体,PDMA_(23)和PDMA_(38)为大分子链转移剂(chain transfer agent,CTA),乙醇为溶剂,在70℃下探究了纳米颗粒的形貌随不同聚合度(degree of ploymerizations,DPs)的转变情况.由实验结果可知:以PDMA_(23)为链转移剂,可调控苯乙烯的聚合度,得到球、虫、囊泡、复合囊泡等形貌;以PDMA_(38)为链转移剂,可在较宽的聚合度范围内得到均匀的球形纳米颗粒.     

瓜环与链状客体自组装结构模式的考察

以核磁共振技术为研究手段,系统考察了瓜环(Cucurbit[n]urils n=6)为主体,链状多元胺化合物N,N'-二(吡啶甲基)-二胺基烷烃为客体的主客体包结实体自组装过程及其特殊结构,这些结构还得到ESMS质谱分析的支持.     

三嵌段共聚物自组装结构的分子调控

 利用耗散粒子动力学方法研究三嵌段共聚物的链构型对其在本体中自组装行为产生的影响. 通过系统调节共聚物的链构型, 得到了形态各异的嵌段共聚物相态结构, 如规则层状结构、 小尺寸相区无规堆积结构以及扭曲阶梯状结构等. 为使体系总的自由能降低, 不同链构型的嵌段共聚物会自发产生各种有序相态结构.     

纳米Fe3O4/氟碳树脂磁场诱导自组装抗反射薄膜的制备及表征

为了获得高度取向的阵列材料,以水热合成的纳米Fe₃O₄磁性颗粒为功能物质,氟碳树脂为薄膜基体,在磁场作用下定向生长成具有磁性针状阵列结构的自组装抗反射薄膜,并考察不同Fe₃O₄含量对磁性阵列结构的影响;利用体视显微镜和扫描电镜（SEM）对薄膜表面结构进行了表征;采用紫外可见近红外分光光度计（UV/Vis/NIR）来表征自组装薄膜的反射率。结果表明:随着Fe₃O₄含量的增加,阵列高度逐渐增高;当粉体质量分数为10%时,阵列的间距为300～600μm,阵列中单个针状结构中间的直径约为100μm;薄膜表面的阵列结构对于反射率的降低有明显效果     

光电功能型超分子聚合物的研究进展

超分子聚合物是重复单元经超分子弱键作用链接而形成的聚集体,是功能软物质中一种新的组织方式。文中基于众多超分子聚合物的分类,重点论述主链式光电功能型超分子聚合物(optoelectronic supramolecular poly-mer,OSP)在太阳能电池、有机电致光、电致变色等得到深入研究领域的应用进展;通过调控能量转移、电荷转移、载流子迁移率等可以实现OSP的白光、光电转换、电致变色等性质和相关器件,并使OSP日渐成为超分子化学与有机电子等学科交叉领域研究的新热点;最后展望了OSP的研究趋势。     

HRP-PAMAM-MCNT修饰电极的研制及其在油脂中过氧化物测定中的应用

以自组装方式,将多壁碳纳米管、聚酰胺-胺和辣根过氧化物酶修饰到玻碳电极表面,构建了H2O2生物传感器.研究了影响传感器工作性能的因素,确定了最佳分析条件,即pH值6.8的PBS缓冲溶液,工作电位为-0.15 V.在最佳工作条件下,电极对H2O2快速响应(响应时间<1 s),在9×10-7～1×10-4mol/L范围内,电极的电流响应值与H2O2浓度呈现良好的线性关系,线性回归方程为i(μA)=20.76 C(mmol/L)+0.223 0,R=0.999 0,检出限为5.0×10-7mol/L,电极的电流响应灵敏度为0.247 A mol-1.cm-2.电极应用于食用油脂中过氧化物测定,结果与碘量法一致.     

纳米粒子液/液界面自组装：结构化液体的设计与构筑

 概述了利用纳米粒子与高分子配体液/液界面协同组装构筑新型结构化液体的研究进展；分析了结构化液体在封装、分离、催化、储能、生物医学等领域展现出的广阔应用前景；指出新型纳米粒子表面活性剂的开发、多重响应型结构化液体的构筑及其应用拓展等将成为未来结构化液体研究的重点方向。     

Improved photostability of Vitamin A palmitate originating from self-assembled supramolecular gels

Retinyl palmitate(RP) is a derivative of Vitamin A and widely applied as the active component in the fields of cosmetic and pharmaceutics.RP can easily lose its physiological activity under UV irradiation due to its photosensitivity.In this work,it was found that the activity of RP remained 75% after 80 min of UVA irradiation when RP was entrapped in supramolecular gels formed by self-assembly of sorbitol-based gelators.By contrast,the activity of RP in conventional hydroxyethyl cellulose gels only remained 10% under the same conditions.These results showed that the supramolecular gels exhibited a significant protective effect on the photostability of RP.UV spectra of RP in supramolecular gels and corresponding solutions showed no distinct differences,indicating no change of the physicochemical properties of RP.The images of field-emission scanning electron microscopy and fluorescent optical microscopy suggested that the protection by supramolecular gels on the photostability of RP may be attributed to the three-dimensional network structure formed by the self-assembly of the gelators,which reduced the molecular collisions and the degradation process of the photoactivated RP.The present results showed that this protection can be influenced by the structures and the concentration of gelators as well as by the solvent composition.