基于超支化星型聚合物构筑多重响应性、自修复纳米复合水凝胶及性能研究

Nanocomposite (NC) hydrogels are composed of specific polymer chains combined with functional nanomaterials evenly through a certain physical or chemical interaction. Nanocomposite hydrogels not only has the three-dimensional network structure and water swelling ability as traditional polymer hydrogels, but also shows unique stimuli-responsive property from nanomaterials, widely applied in many areas, including molecular separation, energy storage, biomedicine, molecular sensing and detection. At present, due to the limited function of nanomaterials employed and lack of effective interaction between polymer chains and nanomaterials, the mechanical properties and stimuli-responsive performances of gels are greatly restricted, needing further research to be resolved..In this proposal, based on the previous studies on the controlled synthesis of stimuli-responsive, topology polymers and their application research on controlled drug delivery and release, we put forward the preparation of self-healing, multi-responsive, hyperbranched star-shaped nanocomposite hydrogels based on functional hyperbranched polymer combined with gold nanostructures through gold-thiolate coordination interaction, as large crosslinking agent and in the polymerization. In view of their multi-stimuli responsiveness and functions from nanomaterials, the potential application on biomedicine is investigated systematically. Through the implementation of this project, we will expand the multi-stimuli responsive nanocomposite hydrogel system, and develop the new characteristics of nanocomposite hydrogel, providing more experimental evidence for the research and application of the new nanocomposite hydrogel.

纳米复合水凝胶是功能性纳米材料通过一定的物理或化学作用力与聚合物链均匀复合的水凝胶材料。它既具有传统高分子水凝胶的三维网络结构和水溶胀能力，同时赋予纳米材料的功能响应性，从而被广泛应用于诸如分子分离、能量存储、生物医药、分子传感与检测等领域。目前由于纳米材料的功能单一性及缺乏与聚合物链间有效的相互作用等方面，凝胶的机械性能和刺激响应性受到极大的限制，急需深入研究加以解决。基于申请人在刺激响应性拓扑结构高分子控制合成及药物可控释放领域的研究基础，本申请拟以含硒自引发单体与功能性单体可控聚合获得功能性超支化聚合物，将其通过金-硒动态配位键与金纳米颗粒复合以作为大分子交联剂，引入响应性单体以制备具有自修复、多重响应性超支化星型纳米复合水凝胶并探讨其生物应用。通过本项目的实施，扩展多重响应性纳米复合水凝胶体系，开发纳米复合水凝胶新特性，为新型纳米复合水凝胶的研究和应用提供更丰富的实验依据。

纳米复合水凝胶是功能性纳米材料通过一定的物理或化学作用力与聚合物链均匀复合的水凝胶材料。它既具有传统高分子水凝胶的三维网络结构和水溶胀能力，同时赋予纳米材料的功能响应性，从而被广泛应用于诸如分子分离、能量存储、生物医药、分子传感与检测等领域。目前由于纳米材料的功能单一性及缺乏与聚合物链间有效的相互作用等方面，凝胶的机械性能和刺激响应性受到极大的限制，急需深入研究加以解决。本项目主要基于动态配位作用构建了刺激响应性纳米复合水凝胶并对其性能进行了研究。项目研究结果如下：.1）设计合成含硒小分子，以金-硒配位作用构建了高强度纳米复合水凝胶，该水凝胶具有优异的机械性能，可实现光、pH和超声波下良好的自修复性，具有优异的光热转换性，在生物医药领域具有良好的应用前景。.2）基于金-硫配位作用，将BACA修饰在TiO2@Au纳米复合物表面并作为大交联剂，制备了具有高强度的纳米复合水凝胶。该纳米复合水凝胶在紫外、可见以及近红外光下显现出高效、快速的自修复行为。.3）基于金-硫配位作用，以表面修饰BACA的Au NPs为多功能交联剂，合成了高强度、自修复导电性纳米复合水凝胶。.4）以小分子BACA作为交联剂，基于双硫键的在紫外诱导下动态性，制备具有规则网络结构的水凝胶。基于金属离子和硫原子的配位作用，在凝胶中引入金属离子有助于进一步提高凝胶的机械性能，丰富凝胶的应用范围。.本项目的实施扩展了多重响应性纳米复合水凝胶体系，为新型纳米复合水凝胶的研究和应用提供更为丰富的实验依据。