Polymeric nanoparticles with peroxidase-like enzyme mimetic activity were developed by incorporating catalytically active tellurium (Te) functionalities into cross-linked block copolymers. Bis(2-aminophenyl) ditelluride was used as a cross-linker to react with a diblock copolymer bearing pendent activated ester groups to generate of core-cross-linked nanoparticles (DiTe-NP) containing diaryl ditelluride bonds. DiTe-NP nanoparticles exhibit dual redox-responsiveness inherited from the sensitivity of ditelluride to both oxidants and reductants. When DiTe-NP nanoparticles were treated with HO, the oxidation of the ditellurides triggered the cleavage of Te-Te bonds to form Te(IV)-associated species. The oxidation-responsiveness endows DiTe-NP nanoparticles with haloperoxidase (HPO)-mimic activity. With NaBr and hydrogen peroxide, they catalyzed the oxidative bromination of phenol red, bromolactonization of 4-pentenoic acid, and bromination of 1,3,5-trimethoxybenzene due to the generation of hypobromous acid (HOBr) for halogenations. These ditelluride-containing nanoparticles also exhibited glutathione peroxidase (GPx)-like activity and accelerated the reduction of hydroperoxide by a thiol substrate. The cleavage of ditelluride bonds by a thiol substrate leads to the formation of key intermediates in the catalytic cycle of DiTe-NP nanoparticles. DiTe-NP nanoparticles showed enhanced activity for the reduction of hydrophobic cumene peroxide by 4-nitrothiophenol. These dual redox-responsive ditelluride-containing nanoparticles are promising candidates as peroxidase mimetics to apply as catalysts for green halogenation reactions and decompositions of toxic peroxides.

中文翻译：

---

作为过氧化物酶模拟物的氧化还原双响应二芳基二碲化物纳米粒子

通过将催化活性碲 (Te) 功能融入交联嵌段共聚物中，开发出具有类似过氧化物酶酶模拟活性的聚合物纳米颗粒。双(2-氨基苯基)二碲化物被用作交联剂，与带有活性酯侧基的二嵌段共聚物反应，生成含有二芳基二碲化物键的核交联纳米粒子(DiTe-NP)。 DiTe-NP 纳米粒子表现出双重氧化还原响应性，继承自二碲化物对氧化剂和还原剂的敏感性。当 DiTe-NP 纳米粒子用 H2O 处理时，二碲化物的氧化引发 Te-Te 键断裂，形成 Te(IV) 相关物质。氧化响应性赋予 DiTe-NP 纳米粒子模拟卤过氧化物酶 (HPO) 的活性。他们用NaBr和过氧化氢催化酚红的氧化溴化、4-戊烯酸的溴内酯化以及由于卤化生成次溴酸(HOBr)而导致1,3,5-三甲氧基苯的溴化。这些含有二碲化物的纳米粒子还表现出谷胱甘肽过氧化物酶（GPx）样活性，并加速硫醇底物对氢过氧化物的还原。硫醇底物对二碲化物键的裂解导致 DiTe-NP 纳米颗粒催化循环中关键中间体的形成。 DiTe-NP 纳米颗粒表现出增强的 4-硝基苯硫酚还原疏水异丙苯过氧化物的活性。这些双重氧化还原响应的含二碲化物纳米颗粒是作为过氧化物酶模拟物的有前途的候选者，可用作绿色卤化反应和有毒过氧化物分解的催化剂。