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通过具有堵塞表面的金属-有机骨架纳米粒子在水介质中稳定镧系配合物的光致发光。

Stable photoluminescence of lanthanide complexes in aqueous media through Metal-Organic Frameworks Nanoparticles with plugged surface.

机构信息

Key Laboratory of Biorheological Science and Technology, Ministry of Education, College of Bioengineering, Chongqing University, No. 174 Shazheng Road, Chongqing 400044, China.

Key Laboratory of Biorheological Science and Technology, Ministry of Education, College of Bioengineering, Chongqing University, No. 174 Shazheng Road, Chongqing 400044, China.

出版信息

J Colloid Interface Sci. 2018 Oct 1;527:68-77. doi: 10.1016/j.jcis.2018.05.025. Epub 2018 May 17.

Abstract

The photoluminescence stability of lanthanide complex in aqueous media is a prerequisite for diagnostics probes. The combination of building blocks working in concert to facilitate host-guest structures is now considered state of the art in surpassing this roadblock, yet there still remains a tremendous challenge. Here, a stable, highly-luminescent system was developed through trapping anionic complexes sensitized by tridentate pyridine-tetrazolate (pytz) ligands within the rigid framework of ZIF-8 (zeolitic imidazolate framework-8) particles (∼60 nm in size). The key to maintaining the stable luminescence of lanthanide complexes inside ZIF-8 frameworks is a stopcock design, i.e. stopper molecules (an imidazolium based ionic liquid) selectively plugged on the pore entrances located at the exterior surface of the ZIF-8 host, which protect both the host and the guests from deteriorations by surrounding ions/water molecules. Remarkably, the obtained Ln complex encapsulated ZIF-8 particles (Ln = terbium, europium) particles possessed high quantum yields (23.2% and 8.5%), large absorption cross-section (∼10 cm), and long luminescence lifetimes (1.9 and 3.0 ms) in PBS buffer. In addition, the system can realize single/multi-color encoding by altering the loading amounts and the weight ratios of complexes emitting at different wavelengths.

摘要

镧系配合物在水相中的光致发光稳定性是诊断探针的前提条件。通过组合协同作用的构建基块来促进主体-客体结构,现在被认为是克服这一障碍的最新技术,然而仍然存在巨大的挑战。在这里,通过将由三齿吡啶-四唑(pytz)配体敏化的阴离子配合物捕获在 ZIF-8(沸石咪唑酯骨架-8)颗粒的刚性骨架中(尺寸约为 60nm),开发了一种稳定的、高发光的体系。保持镧系配合物在 ZIF-8 骨架内稳定发光的关键是一个旋塞设计,即止回阀分子(基于咪唑鎓的离子液体)选择性地阻塞位于 ZIF-8 主体外部表面的孔入口,从而保护主体和客体免受周围离子/水分子的恶化。值得注意的是,所得的镧系配合物封装的 ZIF-8 颗粒(Ln=铽,铕)在 PBS 缓冲液中具有高量子产率(23.2%和 8.5%)、大吸收截面(~10cm)和长荧光寿命(1.9 和 3.0ms)。此外,通过改变不同波长发射的配合物的装载量和重量比,可以实现单/多色编码。

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