Flexoelectric Polarization‐Enhanced Gd‐Based Nanoflowers for Efficient Phosphatase‐Mimicking Dephosphorylation

IF 8.9
Linjing Su, Jingyan Xu, Rong Huang, Jinlan Liao, Lingyan Zhao, Ling Li, Zhi Zhang, Yuhao Xiong
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引用次数: 1

Abstract

Phosphatase‐mimicking nanozymes provide highly stable enzyme‐like activity but remain limited by their static catalytic nature. Herein, this study achieves flexoelectricity‐driven dynamic modulation of nanozyme activity by employing gadolinium‐based nanoflowers (GNF) with hierarchical ultrathin architectures. These structures possess curvature‐induced strain gradients and hydroxyl‐rich surfaces, which generate pronounced flexoelectric polarization under mild ultrasonic excitation. Finite element simulations reveal that mechanical loading induces localized strain gradients and surface potential anisotropy, forming a structural basis for dynamic interfacial charge redistribution. Density functional theory calculations demonstrate that flexoelectric polarization lowers the activation barrier and shifted the rate‐determining step, transforming the reaction pathway. This polarization enhances the Lewis acidity of Gd 3+ sites and stabilized transition states, thereby accelerating phosphate ester hydrolysis. The GNF nanozyme exhibits excellent phosphatase‐like catalytic activity and enables the ultrasensitive colorimetric detection of biologically relevant targets, such as bovine serum albumin and fluoride ions, with low detection limits and robust matrix tolerance. This study pioneers the integration of strain‐gradient‐induced polarization into nanozyme catalysis, establishing a generalizable framework for constructing adaptive and mechanically responsive artificial enzymes.
柔性电极化增强的基于Gd的纳米花用于高效磷酸酶模拟去磷酸化
磷酸酶模拟纳米酶提供了高度稳定的酶样活性,但仍然受到其静态催化性质的限制。在此,本研究通过采用分层超薄结构的钆基纳米花(GNF)实现了柔性电驱动的纳米酶活性动态调节。这些结构具有曲率诱导的应变梯度和富含羟基的表面,在温和的超声激励下产生明显的挠曲电极化。有限元模拟结果表明,机械加载引起局部应变梯度和表面电位各向异性,为界面电荷的动态再分配奠定了结构基础。密度泛函理论计算表明,挠曲电极化降低了激活势垒,改变了速率决定步骤,改变了反应途径。这种极化增强了Gd 3+位点的Lewis酸性,稳定了过渡态,从而加速了磷酸酯的水解。GNF纳米酶具有优异的磷酸酶样催化活性,能够对生物相关靶标(如牛血清白蛋白和氟离子)进行超灵敏比色检测,具有低检测限和强大的基质耐受性。该研究率先将应变梯度诱导极化整合到纳米酶催化中,为构建自适应和机械响应的人工酶建立了一个可推广的框架。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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CiteScore
17.30
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