Mesoscopic pattern formation of supramolecules incorporated with an autonomous function

采用乳化聚合法制备了亚微米级聚N-异丙基丙烯酰胺（PNIPA）凝胶，并将其固定在钌催化剂Ru（bpy）3 ^<2+>上。利用Nd^<3+>：YVO_4激光光阱技术，我们构建了由Ru（bpy）_3^<2+>-co-PNIPAM微凝胶粒子组成的系综。一个粒子。在一定激光功率以上形成直径5μm的薄膜。通过将Ru（bpy）_3 ^<2 +>共价键合到PNIPAM上，我们合成了一种共聚物（Ru（bpy）_3 ^<2+>-co-PNIPAM），该共聚物表现出有节律的可逆的线团-小球（CG）转变。在22℃时，透过BZ溶液的透射率显示出周期为60 s的振荡曲线。我们用动态光散射证实了这一现象与有节律的CG跃迁有关。当用红外激光束照射聚合物溶液时，可以形成软网络结构。在焦斑附近产生直径约5μm的激光束。研究了Ru（bpy）_3^<2+>掺杂微凝胶对噪声等外力作用的动力学响应。在一个振荡系统中，当阈下周期信号和噪声同时作用于振荡器时，随机共振以噪声增强锁相的形式出现。这些实验结果定性再现在数值模拟与强制Oregonator模型。在可激系统中，当噪声幅值增大到一定值以上时，系统出现振荡状态。我们用各种统计量证明了相干共振的存在。我们证明，在最佳的噪声水平，相干振荡的周期是由系统的内在动力学的时间尺度。

Submicron-sized poly(N-isopropyl acrylamide) (PNIPA) gels immobilized the ruthenium catalyst (Ru(bpy)_3^<2+>) of Belousov-Zhabotinsky (BZ) reaction was prepared by emulsification polymerization. We constructed of an ensemble consisting of many Ru(bpy)_3^<2+>-co-PNIPAM micro gel particles by an optical trapping using Nd^<3+>: YVO_4 laser. A particle of ca. 5μm in diameter was formed above a certain laser power. We observed an oxidized wave propagating on the trapped particle.We created a copolymer (Ru(bpy)_3^<2+>-co-PNIPAM) showing rhythmical and reversible coil-globule (CG) transitions by covalently bonding Ru(bpy)_3^<2+> to PNIPAM. A transmittance through its BZ solution showed the oscillation profiles with the period of 60 s at 22℃. We confirmed that this phenomenon is related to the rhythmical CG transition by using a dynamical light scattering. When a polymer solution was irradiated with an IR laser beam, a soft network structure of ca. 5μm in diameter was produced in the vicinity of the focal spot. This structure showed a rhythmical change with the BZ reaction.Dynamical responses of a Ru(bpy)_3^<2+>-doped microgel to external forcing including noise were investigated. In an oscillatory system, when a subthreshold periodic signal and noise were simultaneously imposed on the oscillator, stochastic resonance manifested itself in the form of noise-enhanced phase locking. These experimental findings were qualitatively reproduced in the numerical simulation with a forced Oregonator model . In the excitable system, when a noise amplitude was increased above a certain value, and oscillatory state appeared. We showed the evidence of coherence resonance by using various statistical quantities. We demonstrated that, at an optimal noise level, the period of coherent oscillation is determined by the time scale of the intrinsic dynamics of the system.