Tian Sipeng, Tang Baobing, Sun Mingzi, Xu Zhangpeng, Zhai Tongtong, Xing Huanhuan, Huang Bolong, Liu Yunling, Li Jing, Wang Erkang
College of Chemistry, Jilin University, Changchun, Jilin 130012, China.
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, China.
Anal Chem. 2025 Jul 1;97(25):13442-13452. doi: 10.1021/acs.analchem.5c01821. Epub 2025 Jun 18.
Classic luminol-HO chemiluminescence (CL) systems are plagued by inherent self-decomposition, which compromises detection reliability. Although luminol-dissolved oxygen systems circumvent this issue, their ultralow reactivity necessitates innovative catalytic microreactor design. Herein, we pioneer a hydrogen-bonded organic framework (HOF) constructed from metal-organic square units and 1,2-propanediamine ligands as terminal hydrogen-bonding sites, achieving an unprecedented 4284-fold CL enhancement in luminol-O systems. HOF with porous zeolite-like supramolecular assemblies (ZSA) serves as the coreaction accelerator with strong O adsorption at tetrahedral Co-N/O sites that activates O to generate reactive oxygen species (ROS). And the kinetic confinement effect provided by the ZSA host with suitable channel and hydrogen-bonding contributions efficiently captured the luminol emitter in the nanocages, shortening electron-transfer pathways and reducing nonradiative energy loss. And the synergistic confinement catalysis enhanced CL performance is linearly related to the O adsorption capacity of the ZSA series (ZSA-1, ZSA-3, and ZSA-4). Theoretical calculations further confirmed that the adsorption of O and luminol in ZSA-1 optimizes the electron-transfer pathways to promote CL emission performances compared with those of zeolitic imidazolate framework-67 (ZIF-67). This work not only expands the application of HOF in the field of CL but also provides new insights for engineering materials to boost the CL photon emission efficiency of weak luminol-O systems.
经典的鲁米诺 - 过氧化氢化学发光（CL）系统受到固有自分解的困扰，这损害了检测可靠性。尽管鲁米诺 - 溶解氧系统规避了这个问题，但其超低的反应活性需要创新的催化微反应器设计。在此，我们开创了一种由金属有机方形单元和作为末端氢键位点的1,2 - 丙二胺配体构建的氢键有机框架（HOF），在鲁米诺 - 氧系统中实现了前所未有的4284倍的化学发光增强。具有类似沸石的超分子组装体（ZSA）的HOF作为共反应促进剂，在四面体Co - N/O位点具有强烈的氧吸附，可激活氧以产生活性氧（ROS）。并且由具有合适通道和氢键贡献的ZSA主体提供的动力学限制效应有效地捕获了纳米笼中的鲁米诺发射体，缩短了电子转移途径并减少了非辐射能量损失。并且协同限制催化增强的化学发光性能与ZSA系列（ZSA - 1、ZSA - 3和ZSA - 4）的氧吸附能力呈线性相关。理论计算进一步证实，与沸石咪唑酯框架 - 67（ZIF - 67）相比，ZSA - 1中氧和鲁米诺的吸附优化了电子转移途径，从而促进了化学发光发射性能。这项工作不仅扩展了HOF在化学发光领域的应用，还为工程材料提高弱鲁米诺 - 氧系统的化学发光光子发射效率提供了新的见解。
