{“_”：“尿酸酶-过氧化氢酶级联纳米凝胶中过氧化氢酶功能状态工程的可编程交叉活性。”，“i”：[“via”]}
{"_":"Programmable cross-activity of catalase functional state engineering in a uricase-catalase cascade nanogel.","i":["via"]}
摘要(中文译文)
过氧化物酶体中的过氧化氢酶（CAT）在解毒主导型和代谢偶联催化模式之间发生功能性转换，这一过程由底物可用性、氧化还原微环境和血红素铁氧化还原态转变所驱动。这种动态活性转变使过氧化氢酶不仅作为抗氧化酶发挥作用，还作为整合活性氧信号、脂质代谢和氧化还原稳态的调控枢纽。受此天然机制启发，我们提出了一种纳米限域自聚合策略，用于合理设计氧化酶-过氧化氢酶级联系统，其中单分子水平H₂O₂的生成被精确控制，从而调控过氧化氢酶的底物诱导功能性转换，并成功诱导其CAT与过氧化物酶（POD）交叉活性之间的转变。激活的POD活性驱动˙OH生成，触发自限性聚合，形成尿酸酶（UOx）-CAT级联的级联酶纳米凝胶平台（Gel@UOx/CAT）。自由基分析和理论计算证实，过氧化氢酶的功能性转换受反应场结构而非底物丰度支配，其中H₂O₂在局部水凝胶网络中生成并被引导至活性位点，竞争性催化分解途径在动力学上被抑制或在空间上被隔离。值得注意的是，所制备的限域纳米凝胶依赖其主导的CAT活性降解过量的病理性H₂O₂，从而发挥解毒主导的抗氧化效应（途径A），并在痛风微环境中同时完成尿酸代谢偶联催化（途径B）。这一范式实现了酶交叉活性和功能互变的精确调控，为构建自适应生物催化系统、人工代谢网络和可编程生物电子界面提供了新机遇。
Abstract
Catalase (CAT) in peroxisomes undergoes functional switching between detoxification-dominant and metabolism-coupled catalytic modes, driven by substrate availability, redox microenvironment, and heme iron redox state transitions. This dynamic activity transformation enables catalase to function not only as an antioxidant enzyme but also as a regulatory hub integrating ROS signaling, lipid metabolism, and redox homeostasis. Inspired by this natural mechanism, we propose a nanoconfined self-polymerization strategy for the rational design of an oxidase-catalase cascade system, in which the single-molecule-level generation of HO is precisely controlled, thereby modulating catalase's substrate-induced functional switching and successfully inducing the transition between its cross-activities of CAT and peroxidase (POD). The activated POD activity drove ˙OH generation, triggering self-limited polymerization to form an cascading enzyme nanogel platform (Gel@UOx/CAT) uricase (UOx)-CAT cascades. Radical analysis and theoretical calculations confirmed that the functional switching of catalase is governed by reaction field architecture rather than substrate abundance, in which HO is generated and channeled in a localized hydrogel network to the active site, and competing catalytic decomposition pathways are kinetically suppressed or spatially segregated. Notably, the prepared confined nanogel relied on its dominant CAT activity to degrade excess pathological HO, thereby exerting a detoxification-dominated antioxidation effect (Pathway A), and to fulfill the uric acid metabolism-coupled catalysis (Pathway B) simultaneously within the microenvironment of gout. This paradigm enables precise regulation of enzymatic cross-activities and functional interconversion, offering new opportunities for constructing adaptive biocatalytic systems, artificial metabolic networks, and programmable bioelectronic interfaces.
如何引用
AMA
Manting Jin, Guangce Yuan, Qiao Zhao, Haojie Yang, Yuting Guo, Yujing Tang, et al. {"_":"Programmable cross-activity of catalase functional state engineering in a uricase-catalase cascade nanogel.","i":["via"]}. Materials horizons. 2026; doi:10.1039/d6mh01182a.
APA
Manting Jin, Guangce Yuan, Qiao Zhao, Haojie Yang, Yuting Guo, Yujing Tang, et al (2026). {"_":"Programmable cross-activity of catalase functional state engineering in a uricase-catalase cascade nanogel.","i":["via"]}. Materials horizons. https://doi.org/10.1039/d6mh01182a
GB/T 7714
Manting Jin, Guangce Yuan, Qiao Zhao, Haojie Yang, Yuting Guo, Yujing Tang, et al. {"_":"Programmable cross-activity of catalase functional state engineering in a uricase-catalase cascade nanogel.","i":["via"]}[J]. Materials horizons, 2026 doi:10.1039/d6mh01182a.
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