{"title":"磁mof辅助自由基聚合信号在均相系统中的超灵敏PEC-EC双模检测Caspase-3活性","authors":"Huan Wang, , , Yiyuan Yang, , , Cuicui Du*, , , Xinfa Cai, , , Xiaohua Zhang, , and , Jinhua Chen*, ","doi":"10.1021/acs.analchem.5c03981","DOIUrl":null,"url":null,"abstract":"<p >Enhancing detection sensitivity and reliability is critical in analytical chemistry, particularly for disease diagnosis and biological analysis. Innovative radical polymerization signal amplification strategies, integrated with dual-mode sensing approaches, offer promising avenues for highly sensitive and reliable photoelectrochemical (PEC)-based biosensing. Herein, a novel ultrasensitive PEC-electrochemical (EC) dual-mode biosensing platform was developed for detecting a model analyte of caspase-3, leveraging magnetic metal–organic framework (MOF)-assisted radical polymerization signal amplification in a homogeneous system. Specifically, a magnetic MOF material of MB-UiO-66-NH<sub>2</sub> (mMOFs) was employed to load abundant chain-transfer agent (4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, CPAD) to form mMOFs-CPAD, which was immobilized on a 96-well microplate via caspase-3-specific peptides (DEVD peptides). Upon caspase-3 recognition, the DEVD peptides experienced enzymatic cleavage, releasing mMOFs-CPAD. Following magnetic separation, the released mMOFs-CPAD served as a scaffold for grafting poly(ferrocenylmethyl methacrylate) (PFcMMA), thus forming the mMOFs/PFcMMA composite via reversible addition–fragmentation chain-transfer (RAFT) radical polymerization in a homogeneous system. The mMOFs/PFcMMA composite not only effectively suppressed the photocurrent of MWCNTs/PTCA/CdS-modified electrode for PEC assay but also generated an enhanced electrochemical signal for EC assay. Based on the bifunctional polymeric signal probe, the PEC-EC dual-mode biosensing platform exhibited a wide linear detection range of 10<sup>–17</sup>–10<sup>–8</sup> g mL<sup>–1</sup> (PEC/EC) and ultralow detection limits of 1.8 ag mL<sup>–1</sup> (PEC) and 5.1 ag mL<sup>–1</sup> (EC) for ultrasensitive caspase-3 detection. This work pioneers the utilization of RAFT radical polymerization for improving sensitivity and reliability in PEC-based multimode biosensing technologies.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 38","pages":"21021–21029"},"PeriodicalIF":6.7000,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Magnetic MOF-Assisted Radical Polymerization Signal Amplification in Homogeneous System for Ultrasensitive PEC-EC Dual-Mode Detection of Caspase-3 Activity\",\"authors\":\"Huan Wang, , , Yiyuan Yang, , , Cuicui Du*, , , Xinfa Cai, , , Xiaohua Zhang, , and , Jinhua Chen*, \",\"doi\":\"10.1021/acs.analchem.5c03981\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Enhancing detection sensitivity and reliability is critical in analytical chemistry, particularly for disease diagnosis and biological analysis. Innovative radical polymerization signal amplification strategies, integrated with dual-mode sensing approaches, offer promising avenues for highly sensitive and reliable photoelectrochemical (PEC)-based biosensing. Herein, a novel ultrasensitive PEC-electrochemical (EC) dual-mode biosensing platform was developed for detecting a model analyte of caspase-3, leveraging magnetic metal–organic framework (MOF)-assisted radical polymerization signal amplification in a homogeneous system. Specifically, a magnetic MOF material of MB-UiO-66-NH<sub>2</sub> (mMOFs) was employed to load abundant chain-transfer agent (4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, CPAD) to form mMOFs-CPAD, which was immobilized on a 96-well microplate via caspase-3-specific peptides (DEVD peptides). Upon caspase-3 recognition, the DEVD peptides experienced enzymatic cleavage, releasing mMOFs-CPAD. Following magnetic separation, the released mMOFs-CPAD served as a scaffold for grafting poly(ferrocenylmethyl methacrylate) (PFcMMA), thus forming the mMOFs/PFcMMA composite via reversible addition–fragmentation chain-transfer (RAFT) radical polymerization in a homogeneous system. The mMOFs/PFcMMA composite not only effectively suppressed the photocurrent of MWCNTs/PTCA/CdS-modified electrode for PEC assay but also generated an enhanced electrochemical signal for EC assay. Based on the bifunctional polymeric signal probe, the PEC-EC dual-mode biosensing platform exhibited a wide linear detection range of 10<sup>–17</sup>–10<sup>–8</sup> g mL<sup>–1</sup> (PEC/EC) and ultralow detection limits of 1.8 ag mL<sup>–1</sup> (PEC) and 5.1 ag mL<sup>–1</sup> (EC) for ultrasensitive caspase-3 detection. This work pioneers the utilization of RAFT radical polymerization for improving sensitivity and reliability in PEC-based multimode biosensing technologies.</p>\",\"PeriodicalId\":27,\"journal\":{\"name\":\"Analytical Chemistry\",\"volume\":\"97 38\",\"pages\":\"21021–21029\"},\"PeriodicalIF\":6.7000,\"publicationDate\":\"2025-09-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Analytical Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.analchem.5c03981\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ANALYTICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Analytical Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.analchem.5c03981","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
引用次数: 0
摘要
提高检测灵敏度和可靠性在分析化学中至关重要，特别是在疾病诊断和生物分析中。创新的自由基聚合信号放大策略与双模传感方法相结合，为高灵敏度、高可靠性的光电化学（PEC）生物传感提供了有前途的途径。本文利用磁性金属有机框架（MOF）在均相体系中辅助自由基聚合信号放大，开发了一种新型超灵敏的pec -电化学（EC）双模生物传感平台，用于检测caspase-3的模型分析物。具体而言，采用MB-UiO-66-NH2磁性MOF材料（mMOFs）负载丰富的链转移剂（4-氰基-4-（苯基碳硫基）戊酸，CPAD）形成mMOFs-CPAD，并通过caspase-3特异性肽（DEVD肽）固定在96孔微孔板上。在caspase-3识别后，DEVD肽经历酶切，释放mMOFs-CPAD。经磁分离后，释放的mMOFs- cpad作为接枝聚二茂铁基甲基丙烯酸甲酯（PFcMMA）的支架，在均相体系中通过可逆加成-破碎链转移（RAFT）自由基聚合形成mMOFs/PFcMMA复合材料。mMOFs/PFcMMA复合材料不仅有效抑制了用于PEC测定的MWCNTs/PTCA/ cds修饰电极的光电流，还产生了用于EC测定的增强电化学信号。基于双功能聚合物信号探针，PEC-EC双模生物传感平台具有10-17-10-8 g mL-1 （PEC/EC）的宽线性检测范围和1.8 ag mL-1 （PEC）和5.1 ag mL-1 （EC）的超低检出限。这项工作开创了RAFT自由基聚合的应用，以提高基于pec的多模式生物传感技术的灵敏度和可靠性。
Magnetic MOF-Assisted Radical Polymerization Signal Amplification in Homogeneous System for Ultrasensitive PEC-EC Dual-Mode Detection of Caspase-3 Activity
Enhancing detection sensitivity and reliability is critical in analytical chemistry, particularly for disease diagnosis and biological analysis. Innovative radical polymerization signal amplification strategies, integrated with dual-mode sensing approaches, offer promising avenues for highly sensitive and reliable photoelectrochemical (PEC)-based biosensing. Herein, a novel ultrasensitive PEC-electrochemical (EC) dual-mode biosensing platform was developed for detecting a model analyte of caspase-3, leveraging magnetic metal–organic framework (MOF)-assisted radical polymerization signal amplification in a homogeneous system. Specifically, a magnetic MOF material of MB-UiO-66-NH2 (mMOFs) was employed to load abundant chain-transfer agent (4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, CPAD) to form mMOFs-CPAD, which was immobilized on a 96-well microplate via caspase-3-specific peptides (DEVD peptides). Upon caspase-3 recognition, the DEVD peptides experienced enzymatic cleavage, releasing mMOFs-CPAD. Following magnetic separation, the released mMOFs-CPAD served as a scaffold for grafting poly(ferrocenylmethyl methacrylate) (PFcMMA), thus forming the mMOFs/PFcMMA composite via reversible addition–fragmentation chain-transfer (RAFT) radical polymerization in a homogeneous system. The mMOFs/PFcMMA composite not only effectively suppressed the photocurrent of MWCNTs/PTCA/CdS-modified electrode for PEC assay but also generated an enhanced electrochemical signal for EC assay. Based on the bifunctional polymeric signal probe, the PEC-EC dual-mode biosensing platform exhibited a wide linear detection range of 10–17–10–8 g mL–1 (PEC/EC) and ultralow detection limits of 1.8 ag mL–1 (PEC) and 5.1 ag mL–1 (EC) for ultrasensitive caspase-3 detection. This work pioneers the utilization of RAFT radical polymerization for improving sensitivity and reliability in PEC-based multimode biosensing technologies.
期刊介绍：
Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.
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