原位激活型近红外二区聚集诱导发光探针应用于肿瘤中过氧化氢的高灵敏成像

In situ Activating NIR-II AIE Probe for Highly Sensitive Hydrogen Peroxide Imaging in Tumor

摘要

原位高灵敏精准肿瘤传感技术对于癌症的早期诊断与治疗具有重大意义. 其中， 基于肿瘤标志物的荧光传感凭借其灵敏度高、 操作简便及原位实时检测等优势受到广泛关注. 实现高质量的肿瘤荧光成像从根本上依赖于高性能的发光探针， 而开发具有优异组织穿透深度和超高响应灵敏度的近红外二区(NIR-II)荧光探针为此提供了一条极具前景的解决路径. 本文报道了一种具有聚集诱导发光特性的近红外二区荧光探针4,4'-{6,7-二(噻吩-2-基)-[1,2,5]噻二唑并[3,4-g]喹喔啉-4,9-二基}双{N,N-二甲基-N-[4-(4,4,5,5-四甲基-1,3,2-二氧杂硼杂环戊烷-2-基)苄基]苯胺鎓}（TQT-Bpin）， 其能够特异性响应肿瘤内过表达的过氧化氢， 从而原位激活近红外二区荧光发射. 该探针展现出卓越的灵敏度与特异性， 能够实现对肿瘤区域过氧化氢的实时、 原位、 响应性传感与成像， 并表现出超大的斯托克斯位移(320 nm)、 良好的选择性(检出限低至3.6 μmol/L)及优异的稳定性. 这种集深度组织穿透、 高灵敏度及原位响应能力于一体的近红外二区探针为肿瘤早期检测提供了新策略.

Abstract

In situ highly sensitive and accurate tumor sensing is of great significance for early cancer diagnosis and treatment. Fluorescence sensing of tumor biomarkers has attracted considerable attention due to its advantages of high sensitivity， operational simplicity， and capability for real-time in situ detection. Achieving high-quality tumor fluorescence imaging fundamentally depends on high-performance luminescent probes， and developing near-infrared-II（NIR-II） fluorescent probes with excellent tissue penetration depth and ultra‑high response sensitivity provides a highly promising solution path for this. Herein， we report a NIR-II fluorescent probe， 4，4'-｛6，7-di（thiophen-2-yl）-［1，2，5］thiadiazolo［3，4-g］quinoxaline-4，9-diyl｝bis｛N，N-dimethyl-N-［4-（4，4，5，5- tetramethyl-1，3，2-dioxaborolan-2-yl）benzyl］benzenaminium｝（TQT-Bpin）， featuring aggregation-induced emission（AIE） characteristics. This probe can specifically respond to the hydrogen peroxide overexpressed in the tumor region， thereby in situ activating NIR-II fluorescence emission. It exhibits exceptional sensitivity and specificity， enabling real-time and responsive sensing and imaging of hydrogen peroxide in tumor areas， with advantages including an ultra-large Stokes shift（320 nm）， excellent selectivity（limit of detection down to 3.6 μmol/L）， and superior stability. Such an NIR-II probe， which integrates deep tissue penetration， high sensitivity， and in situ responsiveness， provides a novel strategy for early diagnosis of tumors.

关键词

荧光探针 / 近红外二区 / 聚集诱导发光 / 过氧化氢 / 原位激活

Key words

Fluorescent probe / NIR-II region / Aggregation-induced emission / Hydrogen peroxide / In situ activating