Liu Cheng, Zhou Xiao-Cheng, Li Guoao, Su Jian, Tang Lingyu, Liu Qinglong, Han Xiao, Lv Sen, Mu Zhangyan, Sun Yamei, Yuan Shuai, Gao Fei, Zuo Jing-Lin, Li Shuhua, Ding Mengning
Key Laboratory of Mesoscopic Chemistry, State Key Laboratory of Coordination Chemistry, State Key Laboratory of Analytical Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China.
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, China.
Sci Adv. 2025 Apr 4;11(14):eadq3554. doi: 10.1126/sciadv.adq3554. Epub 2025 Apr 2.
The precise quantification of gaseous radicals in exhaled breath, such as fractional exhaled nitric oxide, serves as an invaluable noninvasive clinical diagnosis particularly in discerning various respiratory disorders. To date, the development of high-performance nitric oxide sensors compatible to modern electronic devices remains fundamentally challenging. We report that metal-organic frameworks (MOFs) with ligand spin immobilization demonstrate superior chemispintronic sensitivity and selectivity toward nitric oxide. Tetrathiafulvalene radical cations (TTF·) within the MOF lattice considerably enhance the nitric oxide recognition via spin exchange interactions, leading to a five-order of magnitude reduction in the limit of detection (LOD), as compared to volatile organic compounds (VOCs) via carrier-doping mechanism. Record-low LOD of 0.12 parts per billion was achieved in M-TTF-spin (M = cobalt, zinc, and cadmium) MOFs, which also demonstrates exceptional selectivity over typical nitrogen oxides (NO) and VOCs. This work opens up a distinct sensing platform for radical-like analytes through strategic design of spin-immobilized molecular functional motifs toward the spintronic device configurations.
呼出气体中气态自由基的精确量化，如呼出一氧化氮分数，是一种非常宝贵的非侵入性临床诊断方法，尤其在辨别各种呼吸系统疾病方面。迄今为止，开发与现代电子设备兼容的高性能一氧化氮传感器仍然面临着根本性的挑战。我们报告称，具有配体自旋固定化的金属有机框架（MOF）对一氧化氮表现出卓越的化学自旋电子敏感性和选择性。MOF晶格中的四硫富瓦烯自由基阳离子（TTF·）通过自旋交换相互作用显著增强了对一氧化氮的识别，与通过载流子掺杂机制检测挥发性有机化合物（VOC）相比，检测限（LOD）降低了五个数量级。在M-TTF-自旋（M = 钴、锌和镉）MOF中实现了创纪录的低至0.12十亿分之一的检测限，其对典型氮氧化物（NO）和VOC也表现出卓越的选择性。这项工作通过针对自旋电子器件配置对自旋固定化分子功能基序进行策略性设计，为类自由基分析物开辟了一个独特的传感平台。
