Key Takeaways & Executive Findings
- •• • PDA@TEMPO nanozyme achieves sustained catalytic interception of lipid peroxyl radicals (ROO·) via a self-regenerating PCET cycle, overcoming stoichiometric exhaustion of conventional antioxidants. • • The π-conjugated PDA framework enables electric-field-enhanced antioxidant response, dynamically accelerating radical interception under bioelectric fluctuations in a seizure model. • • The nanozyme alleviates oxidative stress in neural microenvironments, as demonstrated in a seizure model, indicating potential for treating neurological disorders. • • The design couples a PDA redox reservoir with TEMPO catalytic centers, establishing a general strategy for catalytic and sustained regulation of oxidative stress.
Abstract
Lipid peroxyl radicals (ROO·) are terminal propagating species in lipid peroxidation, driving oxidative damage in neurological disorders. Their prolonged lifetime and rapid diffusion within lipid membranes render them difficult to neutralize. Here, we report a bioelectric-responsive TEMPO-doped polydopamine (PDA@TEMPO) nanozyme that sustains catalytic interception of ROO· radicals under persistent oxidative stress. By coupling a PDA redox reservoir with TEMPO catalytic centers, the nanozyme establishes a self-regenerating radical-neutralization cycle via proton-coupled electron transfer (PCET). The π-conjugated framework facilitates charge migration and enables an electric-field-enhanced antioxidant response. In a seizure model, the nanozyme dynamically responds to bioelectric fluctuations, accelerating radical interception and alleviating oxidative stress in neural microenvironments. These findings establish bioelectric-coupled nanozymes as a general strategy for catalytic and sustained regulation of oxidative stress in neural microenvironments, providing a potential therapeutic approach for neurological disorders.
1. Introduction
Neurological disorders remain a major global health challenge, with oxidative stress as a key pathological driver of progressive neuronal damage. Among reactive oxygen species (ROS), lipid peroxyl radicals (ROO·) are particularly destructive due to their long lifetime and rapid diffusion within lipid membranes, enabling chain-propagating lipid peroxidation that amplifies oxidative damage. Conventional antioxidant strategies, often targeting superoxide or hydrogen peroxide via enzyme-mimetic pathways or stoichiometric scavenging, are insufficient to intercept ROO·, which require sustained, chain-breaking catalytic suppression. Furthermore, many antioxidant nanomaterials suffer from surface passivation or stoichiometric exhaustion under persistent oxidative stress, lacking intrinsic regenerative pathways.
Proton-coupled electron transfer (PCET), a fundamental mechanism in biological redox regulation, coordinates hydrogen and electron transfer to stabilize radical intermediates and enable regenerative catalytic turnover. Polydopamine (PDA), a mussel-inspired biomimetic polymer, combines facile synthesis and excellent biocompatibility with intrinsic redox activity arising from catechol-quinone interconversion. This work develops a bioelectric-responsive PDA@TEMPO nanozyme that couples a PDA redox reservoir with TEMPO catalytic centers, establishing a self-regenerating radical-neutralization cycle via PCET. The π-conjugated framework facilitates charge migration and enables an electric-field-enhanced antioxidant response, addressing the bottleneck of sustained ROO· interception under oxidative stress.
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GUO Mengnan, WANG Luo, LIU Xianping, CHEN Feixiang, ZHAI Yuyang, WU Yelin, JIANG Xingwu, YUAN Ying, SHI Ruicheng, LIU Yanyan, BU Wenbo (2026). Bioelectric Responsive Nanozymes for Catalytic Control of Lipid Peroxyl Radicals. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-026-4213-x
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Frequently Asked Questions
What is the catalytic mechanism of PDA@TEMPO nanozyme for ROO· interception?
The nanozyme couples a PDA redox reservoir with TEMPO catalytic centers, enabling a self-regenerating radical-neutralization cycle via proton-coupled electron transfer (PCET). The PDA framework undergoes catechol-quinone interconversion, providing electrons and protons to regenerate TEMPO, which intercepts ROO· radicals.
How does the electric-field-enhanced antioxidant response work?
The π-conjugated PDA framework facilitates charge migration, allowing the nanozyme to respond to bioelectric fluctuations. In a seizure model, dynamic electric fields accelerate radical interception by enhancing electron transfer within the nanozyme, thereby increasing the rate of ROO· neutralization.
What are the advantages of PDA@TEMPO over conventional antioxidants?
Conventional antioxidants often act stoichiometrically and become exhausted under persistent oxidative stress. PDA@TEMPO provides sustained catalytic activity through self-regeneration, overcoming stoichiometric limitations. Its bioelectric responsiveness enables dynamic regulation of antioxidant activity in neural microenvironments.
What is the significance of targeting lipid peroxyl radicals (ROO·) in neurological disorders?
ROO· are terminal propagating species in lipid peroxidation, causing chain reactions that amplify oxidative damage. Their long lifetime and rapid diffusion make them difficult to neutralize. By specifically intercepting ROO·, the nanozyme can terminate lipid peroxidation chains, alleviating oxidative stress and potentially mitigating neuronal damage.
What are the potential clinical applications of this nanozyme?
The nanozyme shows promise for treating neurological disorders characterized by oxidative stress, such as epilepsy (seizure model). Its bioelectric responsiveness could allow on-demand antioxidant activity in response to pathological electrical activity, offering a targeted therapeutic approach.
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