【作者】 吴杰；

【导师】 林晨； 胡晓玉；

【作者基本信息】 南京大学 ， 化学， 2015， 硕士

【摘要】 柱芳烃是继冠醚、环糊精、杯芳烃、葫芦脲之后的第五代大环分子,具有高度对称的刚性骨架结构。自2008年首次被报道以来受到广泛的关注,已逐渐成为超分子化学领域的一个研究热点。功能化的柱芳烃分子可以用来构筑多种类型的准轮烷体系,其对外界的环境刺激具有灵敏的响应性,在纳米材料、化学传感器、跨膜通道和超分子聚合物等方面有着潜在的应用价值。本文中,我们研究了基于四苯基乙烯功能化的柱[5]芳烃构筑的网状聚准轮烷体系的性质,设计了基于水溶性柱[5]芳烃的靶向纳米载药体系,并进行了其合成工作的探索。本论文主要包括以下两个部分:第一部分的工作主要是通过铜催化的"点击"化学反应合成了四苯基乙烯功能化的柱[5]芳烃(TPEP5)以及含有三氮唑基团的中性客体分子(G1),利用柱[5]芳烃与G1之间的主客体相互作用制备了网状聚准轮烷。由于四苯基乙烯基团上苯环的内旋转通过非辐射的途径消耗了激发态能量,TPEP5溶液的荧光强度较弱。当加入G1后,G1穿入柱[5]芳烃空腔内部,形成了网状聚准轮烷,限制了苯环的内旋转,减少了非辐射能的消耗,TPEP5溶液荧光发射强度增加,这表明了 TPEP5为典型的聚集诱导发光分子。此外,向网状聚准轮烷溶液中加入竞争客体分子己二腈后,该聚准轮烷发生解组装,体系回到弱荧光强度状态。第二部分,我们设计了一种基于单功能化水溶性柱[5]芳烃的靶向纳米载药体系,该单功能化柱[5]芳烃3-17的末端通过烷基链修饰上抗癌药物阿霉素,形成超两亲分子,其在水溶液中能够自组装形成囊泡结构,并可对另一种药物进行同时包载。同时,我们设计合成一端带有靶向多肽RGD的磺酸盐客体分子,期望通过客体与柱[5]芳烃的主客体作用将靶向多肽修饰到囊泡表面,形成对癌细胞具有靶向性的囊泡体系。目前,我们已经完成大部分的合成工作,在目标主客体分子得到后,将会进行主客体相互作用的研究,探索囊泡形成的条件,并进行囊泡的载药与控制释放实验。更多还原

【Abstract】 Pillararene is the 5th new macrocyclic host after crown ethers,cyclodextrins,calixarenes and cucurbiturils.Since reported in 2008,pillararenes have attracted great attention owing to its highly rigid and symmetrical pillar architecture.So far,various types of pseudorotaxanes are constructed by functionalized pillararenes,which are sensitive to environmental stimuli,and they will play an important role in nano-materials,chemical sensors,transmembrane channel and supramolecular polymers.In this dissertation,we investigated the property of the supramolecular polypseudorotaxane networks constructed by pillar[5]arene-functioned tetraphenylethylene(TPEP5)as a fluorescent sensor.Furthermore,we designed a target drug delivery system based on functionalized water-soluble pillar[5]arene.This main content consists of the following two parts:In the first part,we synthesized a pillar[5]areae-functionalized tetraphenylethylene(TPEP5)derivative and a neutral guest molecule containing triazole groups(Gl)through Cu-catalyzed;"click" reaction,and supramolecular polypseudorotaxane networks could be obtained driven by the host-guest interactions between pillar[5]arene and Gl.The fluorescence emission of TPEP5 in solution is weak due to the active intramolecular rotations of the multiple phenyl rings in tetraphenylethylene that consumes its excitation energy through nonradiative channels.However,after adding G1 to the solution of TPEP5,the formation of the polypseudorotaxane networks via the threading of G1 into the cavity of the pillar[5]arene units restricted the rotation of phenyl rings in tetraphenylethylene,which blocks the nonradiative energy dissipation pathways,then the emission of TPEP5 is gradually enhanced as a result.These results indicate that TPEP5 is a typical aggregation-induced emission molecule.Moreover,the collapse of the polypseudorotaxane networks occurred upon addition of the completive guest adiponitrile,which facilitates the internal rotation within tetraphenylethy’lene moieties,and thus the fluorescence becomes weak again.In the second part,we designed a target drug delivery system based on functionalized water-soluble pillar[5]arene,which is modified by introducing an anticancer drug doxorubicin via an alkyl chain.This functionalized pillar[5]arenes are expected to form vesicles in water.At the same time,we are synthesizing a sulfonate guest molecule bearing target group RGD peptide,assume it can be decorated on the surface of vesicles through the host-guest interaction between sulfonate guest and water-soluble pillar[5]arene.Follow-up research work is currently underway.更多还原