School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China.
College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China.
J Hazard Mater. 2022 Aug 15;436:129321. doi: 10.1016/j.jhazmat.2022.129321. Epub 2022 Jun 8.
Although light-responsive nanozyme have been widely used in colorimetric sensing, some limitations such as poor catalytic activity, low detection efficiency, and unclear structure-activity relationships remain unresolved. Herein, we prepared an excellent light-responsive peroxidase (POD) mimic, perylenediimide (PDI-OH) modified SiO @TiO yolk-shell spheres (SiO @TiO/PDI-OH), based on DFT-assisted design. The experiment and DFT calculation revealed that the enhanced POD-like activity was mainly attributed to a suitable built-in electric field among adjacent PDI-OH molecules on the surface of the SiO @TiO and the unique yolk-shell structure with more reaction sites of SiO @TiO. Consequently, the highly selective and ultrasensitive detection of HO is achieved with a detection limit (LOD) of 7.6 × 10M. Further, the selective detection of sarcosine with LOD of 1.2 × 10 M was also achieved by introducing sarcosine oxidase (SOx). This colorimetric assay is successfully applied to selectively detect HO and sarcosine levels in real samples. Controlled response time, anti-interference, and the robustness of the developed colorimetric sensor are the key advantages. And the present work firstly clarifies the effect of PDIs substituents on the POD-like activity of light-responsive nanozymes and provided new guidelines to develop high-performance nanozymes for hazardous substances detection.
尽管光响应纳米酶已广泛应用于比色传感,但一些限制,如催化活性差、检测效率低和结构-活性关系不明确等问题仍未得到解决。在此,我们基于密度泛函理论(DFT)辅助设计,制备了一种优异的光响应过氧化物酶(POD)模拟物,即芘二酰亚胺(PDI-OH)修饰的 SiO@TiO 核壳球(SiO@TiO/PDI-OH)。实验和 DFT 计算表明,增强的 POD 样活性主要归因于表面相邻 PDI-OH 分子之间的适当内置电场和具有更多 SiO@TiO 反应位点的独特核壳结构。因此,通过引入肌氨酸氧化酶(SOx),实现了对 HO 的高选择性和超灵敏检测,检测限(LOD)为 7.6×10-7 M。此外,还通过引入肌氨酸氧化酶(SOx),实现了对肌氨酸的选择性检测,检测限(LOD)为 1.2×10-6 M。该比色测定法成功应用于选择性检测实际样品中的 HO 和肌氨酸水平。可控的响应时间、抗干扰性和开发的比色传感器的稳健性是关键优势。本工作首次阐明了 PDIs 取代基对光响应纳米酶 POD 样活性的影响,为开发用于危险物质检测的高性能纳米酶提供了新的指导。