Polymerization-Induced Self-Assembly for the Synthesis of Multi-Responsive Micelles Hydrogel and its Versatile Applications

Poly(N-isopropyl acrylamide) (PNIPAM) is well-known for its lower critical solution temperature (LCST) and widely studied as
thermo-responsive micelles for various applications. However, the synthesis of micelles with precise structures often involves
complex process. Herein, we developed a novel multi-responsive micelles hydrogel GBN, which was prepared by combining the
polymerization-induced self-assembly (PISA) of poly(N-isopropyl acrylamide)-poly (glycerol methacrylate) (PGMAx-PNIPAM)
and B─Ocrosslinking the micelles. The yielded micelles with stable worm-like structures, easily form a hydrogel through
significant entanglement. The thermo-responsiveness of these micelles facilitates a reversible gel-sol transition, accompanied
by changes in transparency, making them suitable for thermal management in smart window applications. Additionally, the
glucose responsiveness associated with the dynamic B─Obonds address the incompatibility of PNIPAM’s LCST temperature for
drug release applications. Importantly, we discovered that the GNB hydrogel can also function as sealing material; its thermo-
responsiveness enables the formation of liquid gaskets that uniformly fill rough surfaces. In its gel state, it exhibits stable
load-bearing capacity, sealing strength, and consistent friction coefficients, making it applicable in both static and dynamic
sealing scenarios to tackle sealing challenges in extreme environments. Thus, this work offers a novel approach for fabricating
stimulus-responsive materials, broadening the application scope of PNIPAM in various fields.

聚(N-异丙基丙烯酰胺)[Poly(N-isopropyl acrylamide, PNIPAM)] 因具备最低临界溶液温度(lower critical solution temperature, LCST)而广为人知，并作为热响应胶束被广泛研究以应用于诸多领域。然而，构建结构精确的胶束往往涉及复杂的合成流程。本研究开发了一种新型多响应胶束水凝胶GBN，其通过结合聚(N-异丙基丙烯酰胺)-聚(甲基丙烯酸甘油酯)[poly(N-isopropyl acrylamide)-poly(glycerol methacrylate), PGMAₓ-PNIPAM]的聚合诱导自组装(polymerization-induced self-assembly, PISA)与B─O键交联胶束制备得到。所获得的胶束具有稳定的蠕虫状结构，可通过显著的分子缠结轻易形成水凝胶。这类胶束的热响应特性使其可实现可逆的凝胶-溶胶转变，同时伴随透明度变化，因此适用于智能窗(smart window)的热管理场景。此外，依托动态B─O键所赋予的葡萄糖响应性，解决了PNIPAM的LCST温度不适用于药物释放(drug release)场景的兼容性问题。值得注意的是，本研究发现GBN水凝胶还可作为密封材料使用：其热响应特性可使其形成可均匀填充粗糙表面的液态密封垫。在凝胶状态下，该材料具备稳定的承载能力、密封强度与一致的摩擦系数，可应用于静态与动态密封场景，以应对极端环境下的密封挑战。综上，本研究为刺激响应型材料的制备提供了全新思路，拓宽了PNIPAM在诸多领域的应用范围。