A dual-excitation-driven full-component-responsive lanthanide-basedmetal-organic framework for switchable profiling of multi-diseasemarkers  

双激发驱动的全组分响应镧系金属-有机骨架用于多元疾病标志物的双模式检测

作　　者：Guoli Chen Bin Dai Ji-Na Hao Yongsheng Li 陈国礼;代斌;郝继娜;李永生(Lab of Low-Dimensional Materials Chemistry,Key Laboratory for Ultrafine Materials of Ministry of Education,Frontier Science Center of the Materials Biology and Dynamic Chemistry,Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China;School of Chemistry and Chemical Engineering,State Key Laboratory Incubation Base for Green Processing of Chemical Engineering,Shihezi University,Shihezi 832003,China)

机构地区：[1]Lab of Low-Dimensional Materials Chemistry,Key Laboratory for Ultrafine Materials of Ministry of Education,Frontier Science Center of the Materials Biology and Dynamic Chemistry,Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China [2]School of Chemistry and Chemical Engineering,State Key Laboratory Incubation Base for Green Processing of Chemical Engineering,Shihezi University,Shihezi 832003,China

出　　处：《Science China Materials》2025年第2期666-676,共11页中国科学(材料科学)(英文版)

基　　金：supported by the National Key Research and Development Program of China (2022YFC2403203, 2024YFF0508601);the National Natural Science Foundation of China (52172279);the Basic Research Program of Shanghai (21JC1406003);the Shanghai Rising-Star Program (21QA1402200);the Leading Talents in Shanghai in 2018, the Key Field Research Program (2023AB054);the Higher Education Discipline Innovation Project (B14018)。

摘　　要：Accurate detection of multiple small end-metabolic biomarkers is more sensitive than large biomoleculesto provide real-time feedbacks of physiological/pathologicalstate, but is more challenging due to lack of specific identifyinggroups. Current optical platforms suffer from unsatisfactoryresolutions to differentiate each target because they producesimilar output to different targets using a single excitation,and inevitably involve non-functional components that increase chances of interacting with non-target molecules.Herein, by taking full advantage of each building unit’sfunctionality to integrate multivariate recognition elements inone interface, a dual-excitation-driven full-component-responsive metal-organic framework (MOF)-based luminescentprobe, namely CeTMA-TMA-Eu, is successfully custom-tailored for detecting both pseudouridine (Ψ) and N-acetylaspartate (NAA), the diagnostic hallmarks of cancer andneurodegenerative disorder. Remarkably, Ψ interacts withMOF’s organic building unit (trimesic acid, TMA) and filtersout its absorptions of 262 nm-light to reduce its energytransferred to Eu^(3+), while NAA induces the valence transitionof Ce^(4+)/Ce^(3+) nodes to improve the cooperative energy transferefficacy from TMA and Ce^(3+) to Eu^(3+). As a result, this platformexhibits completely reverse photoresponses towards Ψ(“switch-off” at 262 nm excitation) and NAA (“switch-on”upon 296 nm excitation), and demonstrates excellent selectivity and sensitivity in complex biofluids, with low detection limits of 0.16 and 0.15 μM, and wide linear ranges of0–180 and 0–100 μM, respectively. Such full-componentresponsive probe with dual-excitation-mediated reverse responses for multi-small targets intrinsically minimizes its interaction with non-target molecules and amplifies resolutionto discriminate each target, providing a new strategy for improving assay accuracy of multi-small biomarkers in diagnostics.检测多种小分子代谢标志物比生物大分子更能灵敏、实时地反馈生理或病理状态,但因其缺乏特定识别基团,使其精准检测更具挑战性.现有荧光探针大多仅在单一激发波长下对不同分析物产生类似的输出且含非功能组分,难以同时准确检测多个小分子标志物.针对此,我们充分利用MOFs有机和无机构建单元,导向设计了一种双激发驱动、全组分响应的MOF荧光探针(CeTMA-TMA-Eu),分别在262和296 nm激发下实现了对疾病标志物假尿苷(Ψ,与TMA配体作用过滤262 nm激发光)和N-乙酰天冬氨酸(NAA,诱导Ce^(4+)节点价态变化)的特异荧光猝灭和增强响应,其检出限低至0.16和0.15μM,检测范围分别为0-180和0-100μM.该探针减少了与非目标分子的相互作用,显著提高了探针区分各目标物的选择性和分辨率.

关 键 词：luminescent probes lanthanide-based metal-organic frameworks dual-excitation regulation multi-disease markers detection 

分 类 号：G63[文化科学—教育学]