Thermotropic order-order phase transitions (OOTs) in block copolymers are not commonly observed in the strong segregation region. Phase separation of giant surfactants composed of hydrophilic molecular nanoparticles (MNPs) as heads and hydrophobic flexible polymer chains as tails occurs generally in the strong segregation region. By introducing a rigid molecular segment at the junction point of the giant surfactants, the interface between the MNPs and polymer tails could be delicately manipulated, resulting in the occurrence of thermotropic OOTs that are sensitively dependent on the properties of those junction segments. For samples with hydrophilic junction segments, no thermal-induced OOT has been observed. However, for samples with hydrophobic junction segments, complicated thermotropic OOTs between as many as four different ordered phases in a single giant surfactant system, from lamellae (LAM) to hexagonally perforated layer structure (HPL), double gyroids (DG), and finally to hexagonally packed cylinders (HEX), have been observed with increasing temperature. These results demonstrated that interfacial engineering could be used to regulate the self-assemble behavior of macromolecules at the nanometer scales.

嵌段共聚物中的热致性有序相变（OOT）在强偏析区域通常不可见。由亲水性分子纳米颗粒（MNP）作为头部和疏水性柔性聚合物链作为末端的巨型表面活性剂的相分离通常发生在强分离区域。通过在巨型表面活性剂的交界处引入一个刚性分子链段，可以精确地控制MNP和聚合物尾部之间的界面，从而导致热致OOT的出现，这些OOT敏感地取决于那些交联链段的性质。对于具有亲水性连接片段的样品，未观察到热诱导的OOT。但是，对于具有疏水性连接片段的样品，在单个巨型表面活性剂系统中，多达多达四个不同有序相之间的复杂热致OOT，从薄片（LAM）到六角形穿孔层结构（HPL），双螺旋形（DG），最后到六角形填充圆柱（HEX），随着温度升高观察到。这些结果表明界面工程可用于调节纳米尺度下大分子的自组装行为。