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用于选择性荧光识别羟基硝基芳香族化合物的铝基金属有机凝胶

Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds.

作者信息

Guo Mao Xia, Yang Liu, Jiang Zhong Wei, Peng Zhe Wei, Li Yuan Fang

机构信息

Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.

Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2017 Dec 5;187:43-48. doi: 10.1016/j.saa.2017.05.057. Epub 2017 May 27.

Abstract

The novel class of luminescent Al-based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2':6',2″-terpyridine]-4'-ylbenzoic acid (Hcptpy) with Al under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0μM with a detection limit of 4.64μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA.

摘要

通过在温和条件下将4-[2,2':6',2″-三联吡啶]-4'-基苯甲酸(Hcptpy)与铝混合,开发出了新型的发光铝基金属有机凝胶(Al-MOGs)。所制备的Al-MOGs不仅具有多种刺激响应特性,还能选择性识别羟基硝基芳香化合物,这些化合物能淬灭Al-MOGs的荧光,而其他无羟基取代的硝基芳香类似物则不能。苦味酸(PA)能严重淬灭Al-MOGs在467nm处的荧光,其最低未占分子轨道(LUMO)能级低于其他三种羟基硝基芳香化合物,包括4-硝基苯酚(4-NP)、3,5-二硝基水杨酸(3,5-DNTSA)和2,4-二硝基苯酚(2,4-DNP)。因此,在最佳条件下选择PA作为模型化合物,Al-MOGs的相对荧光强度与PA浓度在5.0 - 320.0μM范围内成正比,检测限为4.64μM。此外,还研究了荧光淬灭机制,结果表明淬灭归因于内滤效应(IFE)以及Al-MOGs与PA之间的电子转移(ET)。

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