Dou Baoting, Shen Hui, Li Zhimin, Cheng Huanyu, Wang Po
School of Chemistry and Materials Science, Jiangsu Normal University Xuzhou 221116 China
Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, State College PA 16802 USA.
Chem Sci. 2025 Jan 8;16(8):3470-3478. doi: 10.1039/d4sc05512h. eCollection 2025 Feb 19.
Reactive oxygen species (ROS) play a critical role in regulating various physiological processes. To gain a comprehensive understanding of their distinct functions in different physiological events, it is imperative to detect binary ROS simultaneously. However, the development of the sensing method capable of binary ROS detection remains a significant challenge. In this study, we address this challenge by integrating chemically modified DNAzyme probes with a functionalized metal-organic framework (MOF) to create an efficient electrochemical sensing platform for the binary detection of ROS. ROS targets would activate the DNAzyme cleavage activity by removing the phenylboronate (BO) and phosphorothioate (PS) modifications, leading to the controlled release of doxorubicin (DOX) and methylene blue (MB) enclosed within MOF nanocomposites. This process generates two distinct voltammetric current peaks, with their potentials and intensities reflecting the identity and concentration of the ROS targets. The sensor demonstrates simultaneous detection of multiple ROS (HO and HClO) produced by cancer cells with high sensitivity across a broad linear range of 1 to 200 nM and a low detection limit in the sub-nanomolar range. The design strategies behind the developed ROS sensing system could also be exploited to create other biosensors with highly sensitive and binary detection to promote clinical research and revolutionize disease diagnostics.
活性氧（ROS）在调节各种生理过程中起着关键作用。为了全面了解它们在不同生理事件中的独特功能，同时检测二元ROS势在必行。然而，开发能够进行二元ROS检测的传感方法仍然是一项重大挑战。在本研究中，我们通过将化学修饰的DNAzyme探针与功能化金属有机框架（MOF）相结合，来应对这一挑战，从而创建了一个用于二元检测ROS的高效电化学传感平台。ROS靶标会通过去除苯硼酸（BO）和硫代磷酸酯（PS）修饰来激活DNAzyme的切割活性，导致包裹在MOF纳米复合材料中的阿霉素（DOX）和亚甲蓝（MB）的可控释放。这个过程产生两个不同的伏安电流峰，其电位和强度反映了ROS靶标的身份和浓度。该传感器能够在1至200 nM的宽线性范围内高灵敏度地同时检测癌细胞产生的多种ROS（HO和HClO），并且检测限低至亚纳摩尔范围。所开发的ROS传感系统背后的设计策略也可用于创建其他具有高灵敏度和二元检测功能的生物传感器，以促进临床研究并彻底改变疾病诊断。
