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使用掺杂有BODIPY发射体的荧光和比色微粒及聚合物薄膜的氨和温度传感应用。

Ammonia and temperature sensing applications using fluorometric and colorimetric microparticles and polymeric films doped with BODIPY-emitters.

作者信息

Cugnasca Beatriz S, Duarte Frederico, Santos Hugo M, Capelo-Martínez José Luis, Bértolo Emilia, Dos Santos Alcindo A, Lodeiro Carlos

机构信息

Institute of Chemistry, Department of Fundamental Chemistry, University of São Paulo, São Paulo, SP, 05508-000, Brazil.

BIOSCOPE Research Group, LAQV-REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, FCT NOVA, NOVA University Lisbon, Caparica, 2829-516, Portugal.

出版信息

Mikrochim Acta. 2024 Nov 17;191(12):746. doi: 10.1007/s00604-024-06814-2.

Abstract

Four functionalized BODIPY derivatives (BDP1 to BDP4) were synthesized and their optical properties investigated both in solution and when incorporated into a solid matrix. Recognizing the versatility of BODIPY derivatives and the increasing interest in developing new luminescent organic dyes embedded in polymers, the BODIPY derivatives were dispersed into two types of polymeric matrices: Poly(methyl methacrylate) (PMMA) and Thermoplastic Polyurethane (TPU), both as films and microparticles. This resulted in eight new BODIPY-doped polymer films and eight types of BODIPY-doped polymeric microparticles for use in aqueous solutions. The integration of the BODIPY dyes into the polymeric matrices combines the unique properties of the polymer films, such as porosity, flexibility, and elasticity, with the excellent photophysical characteristics of the BODIPYs. Importantly, the dispersion minimized issues such as aggregation-caused quenching commonly observed in solid-state luminescent materials. The thermometric responses of all polymer films were evaluated by studying their solid-state emission spectra in the 25-200 °C temperature range. The reversibility of these temperature-induced changes was also assessed, revealing excellent recovery of luminescence. These promising results suggest these materials could have applications as fluorescent thermometric sensors. Furthermore, we explored the potential of the brominated (BDP3) and chalcogenated (BDP4) BODIPY derivatives as ammonia sensors. The two derivatives produced yellow fluorescent products upon interaction with the analyte. Kinetic studies using solid-state emission spectra of BDP4@TPU and BDP4@PMMA showed significant differences in reaction rates (minutes for BDP4@TPU and hours in the case of BDP4@PMMA) attributable to the higher permeability of TPU when compared with PMMA. Detection and quantification of ammonia concentration were conducted by means of simple photographic analysis, measuring the "R" (red) and "G" (green) components of RGB color parameters. The results from the photographic method correlated well with the results from fluorimetric spectroscopy studies. The photographic analysis is straightforward, portable, and does not require expensive equipment. Finally, we successfully applied polymeric microparticles doped with BODIPYs to detect ammonia in water, demonstrating their effectiveness without the need for organic solvents. This highlights their potential for environmental monitoring and other applications requiring sensitive and selective detection methods.

摘要

合成了四种功能化的硼二吡咯衍生物(BDP1至BDP4),并研究了它们在溶液中和掺入固体基质时的光学性质。认识到硼二吡咯衍生物的多功能性以及对开发嵌入聚合物中的新型发光有机染料的兴趣与日俱增,将硼二吡咯衍生物分散到两种类型的聚合物基质中:聚甲基丙烯酸甲酯(PMMA)和热塑性聚氨酯(TPU),制成薄膜和微粒。这产生了八种新型的硼二吡咯掺杂聚合物薄膜和八种用于水溶液的硼二吡咯掺杂聚合物微粒。将硼二吡咯染料整合到聚合物基质中,将聚合物薄膜的独特性能(如孔隙率、柔韧性和弹性)与硼二吡咯优异的光物理特性结合在一起。重要的是,这种分散最大限度地减少了固态发光材料中常见的诸如聚集导致的猝灭等问题。通过研究所有聚合物薄膜在25至200°C温度范围内的固态发射光谱来评估它们的温度响应。还评估了这些温度诱导变化的可逆性,结果显示发光具有出色的恢复性。这些有前景的结果表明这些材料可作为荧光温度传感器应用。此外,我们探索了溴化(BDP3)和硫属元素化(BDP4)硼二吡咯衍生物作为氨传感器的潜力。这两种衍生物与分析物相互作用时会产生黄色荧光产物。使用BDP4@TPU和BDP4@PMMA的固态发射光谱进行的动力学研究表明,由于TPU与PMMA相比具有更高的渗透性导致反应速率存在显著差异(BDP4@TPU为几分钟,BDP4@PMMA为几小时)。通过简单的摄影分析,测量RGB颜色参数的“R”(红色)和“G”(绿色)分量来进行氨浓度的检测和定量分析。摄影方法的结果与荧光光谱研究的结果相关性良好。摄影分析简单、便携,且不需要昂贵的设备。最后,我们成功地应用掺杂硼二吡咯的聚合物微粒来检测水中的氨,证明了它们无需有机溶剂即可有效检测。这突出了它们在环境监测和其他需要灵敏且选择性检测方法的应用中的潜力。

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