传统的癌症治疗方法已不能满足当前癌症精准治疗和个性化治疗的需求，必须开发新的治疗模式并研究新的联合抗肿瘤机制。因此，设计并合成了以己二酸二酰肼（ADH）为pH响应中心连接甲氧基聚乙二醇（mPEG）和肉桂醛（CA）的两亲性前药聚合物链，该聚合物链可以在水溶液中自组装成PAC胶束。基于α-环糊精（α-CD）和PAC胶束之间的主客体相互作用形成超分子水凝胶。采用溶剂热法制备了聚醚酰亚胺（PEI）修饰的铜锰硫化物纳米酶催化剂（PCMS NPs），该催化剂可以均匀分散在水凝胶中形成复合超分子水凝胶（PCMS@PAC/α-CD Gel）。在酸性肿瘤环境下，pH响应性腙键断裂，导致CA缓慢释放和过氧化氢（H2O2）水平放大。 PCMS NPs具有类过氧化物酶（POD）活性和类过氧化氢酶（CAT）活性，可将H2O2转化为羟基自由基（˙OH）和氧气（O2）以缓解肿瘤内缺氧并诱导细胞凋亡，同时发挥谷胱甘肽氧化酶作用。 GPX）样活性消耗谷胱甘肽（GSH），进一步增强化学动力学疗法（CDT）的效果。在近红外光（NIR）照射下，PCMS NPs表现出优异的光热转换性能，可以将肿瘤细胞的温度迅速升高至42℃以上进行光热治疗（PTT），并将O2转化为超氧阴离子（˙O2- ）通过发挥氧化酶（OXD）样活性进行光动力疗法（PDT）。体外和体内实验表明，PCMS@PAC/α-CD Gel对癌细胞具有高度细胞毒性，可有效抑制肿瘤生长，具有在生物医学和智能材料领域的应用潜力。

Traditional cancer therapies no longer meet the current demand for cancer precision therapy and personalized treatment and it's essential to develop new therapeutic modalities as well as to investigate new combination anti-tumor mechanisms. Therefore, amphiphilic prodrug polymer chains linking methoxy poly(ethylene glycol) (mPEG) and cinnamaldehyde (CA) with adipic acid dihydrazide (ADH) as the pH-responsive center were designed and synthesized, which could self-assemble into PAC micelles in aqueous solution. A supramolecular hydrogel was formed based on the host-guest interaction between α-cyclodextrin (α-CD) and PAC micelles. Polyetherimide (PEI) modified copper manganese sulfide nanoenzyme catalysts (PCMS NPs) were prepared by a solvothermal method, which could be uniformly dispersed in the hydrogel to form a composite supramolecular hydrogel (PCMS@PAC/α-CD Gel). Under an acidic tumor environment, pH-responsive hydrazone bonds were broken, resulting in the slow release of CA and the amplification of hydrogen peroxide (H2O2) levels. PCMS NPs exerted peroxidase (POD)-like activity and catalase (CAT)-like activity, which could convert H2O2 into hydroxyl radicals (˙OH) and oxygen (O2) to alleviate intra-tumor hypoxia and induce apoptosis, while exerting glutathione oxidase (GPX)-like activity to consume glutathione (GSH) to further enhance the effect of chemodynamic therapy (CDT). Under near-infrared light (NIR) irradiation, PCMS NPs exhibited an excellent photothermal conversion performance, which could rapidly increase the temperature of tumor cells to above 42 °C for photothermal therapy (PTT) and convert O2 to a superoxide anion (˙O2-) by exerting oxidase (OXD)-like activity for photodynamic therapy (PDT). It was demonstrated by in vitro and in vivo experiments that the PCMS@PAC/α-CD Gel was highly cytotoxic to cancer cells and could effectively inhibit tumor growth, indicating the potential for applications in the fields of biomedicine and smart materials.