Study of Phase Transitions in Supramolecular Systems Incorporated with Active Elements

我们制备了以表面活性剂为基础的各种超分子，并研究了其热性质，以阐明将各种活性元素固定到超分子中的条件。此外，为了构建结构类似于生物超分子的超分子体系，我们研究了弹性纤维蛋白来源的α-弹性蛋白超分子的热性质。测定了水-α-弹性蛋白二元混合物的共存曲线和旋节曲线。我们的结论是，在宏观尺度上，临界浓度波动在α-弹性蛋白的超分子有序化中起着重要作用。基于这些结果，我们将Belousov-Zabotinskii(BZ)反应作为活性元素引入到超分子中。在化学振荡的夹带中观察到了各种吸引人的现象。这些体系对外界扰动很敏感，但稳定性稍差。为了提高结合BZ反应的能力，我们使用了100-500微米的阳离子交换小球和硅胶小球。通过微观光学探测定位在微珠上的化学波，这些微珠可以看作是化学振荡器。我们的注意力尤其集中在两个相互不接触的珠子之间的耦合。结果表明：(1)同步频率高于快振子的固有频率，(2)存在频率比随固有频率不同而不同的耦合状态，(3)稳定耦合状态的边界处出现混沌行为。此外，还发现激光的外部扰动会在极限环上引起随机性。这种随机行为可能是混沌的，这取决于微扰开始时振子的相位。

We made various supramolecules based on surfactants and investigated its thermal properties in order to clarify the conditions to immobilize various active elements into supramolecules. Furthermore, for the purpose to construct the supramolecular system with the structure similar to biological supramolecules, we investigated the thermal properties of supramolecules of alpha-elastin originated from the elastic fibrous protein elastin. We determined the coexistence curve and the spinodal curve of the binary mixture, water-alpha-elastin. We concluded that critical concentration fluctuations play a important role in supramolecular ordering of alpha-elastin over a macroscopic scale. On the basis of these results, we incorporated Belousov-Zabotinskii (BZ) reaction as an active element into supramolecules. Various attractive phenomena in entrainment of a chemical oscillation were observed. These systems are sensitive to extemal perturbations, but lack stability a little.In order to improve the ability to incorporate BZ reaction, we used the cation exchange bead and silica gel bead of 100-500 mum in size. Theses beads could be regarded as chemical oscillators by micro-optically detecting the chemical waves localized on beads. Our attention is particularly focused on the coupling between two beads in no contact with each other. The results are summarized follows : (1) the synchronized frequency is higher than the natural frequency of fast oscillator, (2) there are coupled states with various frequency ratios depending on the ratio of natural frequency and (3) chaotic behaviors appear at the boundary between stable coupled states. Furthermore, a randomness was found to be induced on a limit cycle by external perturbations with a laser beam. Such random behaviors are probably chaotic, which depended on the phase of oscillator at the beginning of the perturbation.