Establishment of Self-assembled Rotaxane Ultrathin Film Chemistry

自组装轮烷单层膜的制备建立了一种利用电位扫描法制备由氨基硫代烷硫醇和a-环糊精组成的自组装轮烷单层膜（轮烷- sam）的简单工艺。使用假环紫杉烷制备轮紫杉烷- sam时，过量的CD分子在电极表面的物理吸附会干扰轮紫杉烷- sam的制备。相比之下，由于CD分子在负电位下从电极表面解吸，使用电位扫描法制备轮烷- sam的方法非常简单。以偶氮二苯并-24-冠-8醚为机械键交联点分子的聚氨酯PU0、PU11和PU33除PU0外，还合成了3种具有[3]轮烷结构的聚氨酯。PU0和PU11在DMF和DMSO中均可溶解，而PU33在两种溶剂中均膨胀，表明PU33通过机械键交联形成3d网络结构。从ATR-FT-IR测量的结果来看，由于1形成[3]轮烷结构的位阻，1的引入导致聚氨酯键段之间以及聚氨酯键的羰基与pu中的铵单元之间的氢键断裂。pu的热性能表明，随着pu含量比为1的增加，pu的玻璃化转变比热增加，表明PU33比PU0含有更多的非晶态区。PU33在Tg后无过渡峰，而PU11有结晶和熔融峰。通过动态粘弹性测试，确定了PU11的玻璃化转变和熔体的热性能。

Preparation of a self-assembled rotaxane monolayerSimple fabrication technique of a self-assembled rotaxane monolayer (rotaxane-SAM) consisting of a viologen-functionalized Alkanethiol and a-cyclodextrin (CD) using potential sweep has been established. Use of a pseudorotaxane to prepare the rotaxane-SAM often suffers with physical adsorption of excess CD molecules onto electrode surface that interferes with fabrication of the rotaxane-SAM. In contrast, use of the potential sweep for the pseudorotaxane method results in simple fabrication of the rotaxane-SAM because of desorption of the CD molecules form the electrode surface at negative potential.Synthesis and characterization of polyurethanes cross-linked with a rotaxaneThree polyurethanes (PU0, PU11 and PU33) containing azobis (dibenzo-24-crown-8 ether) 1 as a molecule for a mechanical bonding cross-link point with a [3]rotaxane structure except PU0 were synthesized. PU0 and PU11 were soluble in DMF and DMSO whereas PU33 swelled in both the solvents, suggesting that PU33 forms a 3D-network structure via the mechanical bonding cross-links. From the result of ATR-FT-IR measurements, introduction of 1 causes break of hydrogen bonds between urethane bond moieties as well as between carbonyl of urethane bond and ammonium unit in the PUs due to steric hindrance of 1 forming the [3]rotaxane structure. Thermal properties of the PUs revealed that specific heats of glass-transitions increased with increase in the content ratio of 1, suggesting that PU33 contains more amorphous region than PU0. PU33 showed no transition peaks after Tg, whereas PU11 gave the peaks for crystallization and melt. Thermal properties of glass-transition and melt for PU11 were also confirmed by dynamic viscoelastic property measurement.