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在包含聚合物包埋铕配合物的水性介质中进行高效单线态氧监测。

Efficient Singlet Oxygen Monitoring in Aqueous Media Comprising a Polymer-embedded Eu-Complex.

作者信息

Dinga Daniel K, Cappellari María V, Strassert Cristian A, Kynast Ulrich H

机构信息

Institute for Optical Technologies, Muenster University of Applied Sciences, 48565, Steinfurt, Germany.

Institute for Inorganic und Analytical Chemistry, University of Münster, Corrensstraße 28/30, 48149, Münster, Germany.

出版信息

Chemistry. 2025 Jun 23;31(35):e202500943. doi: 10.1002/chem.202500943. Epub 2025 May 22.

DOI:10.1002/chem.202500943
PMID:40353392
Abstract

Singlet dioxygen (O) plays a pivotal role as the active agent in photodynamic therapy (PDT) for cancer treatment, as well as in the photo-inactivation of antibiotic-resistant microbes (antimicrobial photodynamic therapy, aPDT). The ability to sensitively monitor the production and behavior of ¹O₂ following its photo-catalytic generation is crucial for developing effective therapeutic strategies. Optical sensor molecules that respond to ¹O₂ through changes in absorption or, more sensitively, fluorescence, are suitable choices. While most monitors report O via altered absorption spectra, only few compounds respond by the onset of fluorescence, even fewer based on lanthanide luminescence. By embedding a novel lanthanide complex (Eu) into polystyrene nanoparticles (beads), we achieved close to a 500-fold emission intensity boost in the presence of O, very long decay times of up to 879 µs and unprecedented stability in acidic and basic media. Furthermore, the beads present a high-surface charge (>+30 mV), yielding stable aqueous dispersions, which we exploited in a preliminary "proof of principle" staining experiment of (negatively charged) bacterial surfaces. The straightforward synthesis circumvents intricate preparative steps and restrictive costs. The decay characteristics furthermore pave the road to time-gated measurements, that is, to the suppression of interfering autofluorescence from biological samples.

摘要

单线态氧(O)作为活性物质在用于癌症治疗的光动力疗法(PDT)以及对抗生素耐药微生物的光灭活(抗菌光动力疗法,aPDT)中发挥着关键作用。在光催化产生¹O₂后,灵敏地监测其产生和行为的能力对于制定有效的治疗策略至关重要。通过吸收变化,或者更灵敏地通过荧光变化来响应¹O₂的光学传感器分子是合适的选择。虽然大多数监测器通过改变的吸收光谱来报告O,但只有少数化合物通过荧光的出现来响应,基于镧系元素发光的更少。通过将一种新型镧系配合物(Eu)嵌入聚苯乙烯纳米颗粒(珠子)中,我们在存在O的情况下实现了近500倍的发射强度增强、长达879微秒的极长衰减时间以及在酸性和碱性介质中前所未有的稳定性。此外,这些珠子具有高表面电荷(>+30 mV),产生稳定的水分散体,我们在(带负电荷的)细菌表面的初步“原理验证”染色实验中利用了这一点。这种简单的合成方法避免了复杂的制备步骤和高昂的成本。衰减特性还为时间分辨测量铺平了道路,即抑制生物样品中干扰性的自发荧光。

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本文引用的文献

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High brightness red emitting polymer beads for immunoassays: Comparison between trifluoroacetylacetonates of Europium.用于免疫测定的高亮度红色发光聚合物微珠:铕的三氟乙酰丙酮化物之间的比较
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Design and Mechanism of Rare-Earth Singlet Oxygen Sensing: An Experimental and Quantum Chemical Approach.稀土单线态氧传感的设计与机理:一种实验与量子化学方法
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Ratiometric Singlet Oxygen Sensor Based on BODIPY-DPA Dyad.
基于 BODIPY-DPA 偶联物的比率型单线态氧传感器。
Molecules. 2022 Dec 19;27(24):9060. doi: 10.3390/molecules27249060.
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Pharmaceutics. 2021 Aug 25;13(9):1332. doi: 10.3390/pharmaceutics13091332.
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Singlet Oxygen: Discovery, Chemistry, C -Sensitization.单线态氧:发现、化学性质与 C 敏化作用
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Oxidative post-translational modification of EXECUTER1 is required for singlet oxygen sensing in plastids.质体中用于单线态氧感应的 EXECUTER1 的氧化后翻译修饰是必需的。
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