基于黄酮的ESIPT型荧光探针检测三苯基膦

doi:10.7517/j.issn.1674-0475.2017.04.014

摘要/Abstract

摘要：

三苯基膦（PPh₃）是一种重要的有机化合物，具有亲核性和还原性，已被广泛用于有机合成和有机金属化合物配位中。然而PPh₃的过量使用不可避免地会引起环境的污染，并且对人体的健康也具有潜在威胁。因此我们迫切需要一种方便而高效的检测PPh₃的方法。已有检测方法在便捷性和灵敏性等方面不如人意，而小分子荧光探针因其灵敏度高、选择性好、检测简单等优点受到广泛关注。受生物标记领域常用的无痕Staudinger连接反应的启发，本文设计合成了一个类似Staudinger连接反应，以能够具有固态发光性质的激发态分子内质子转移（ESIPT）特性的3-羟基黄酮荧光染料为母核，以邻叠氮苯乙酸酯为识别基团，用于检测PPh₃的荧光增强型的探针分子。通过叠氮与PPh₃反应，经过氮杂叶立德中间体，进行快速的分子内酰胺化，释放3-羟基黄酮染料并恢复荧光发射，从而实现在溶液中及滤纸上快速检测PPh₃的目的。该探针在定量和定性检测PPh₃方面具有潜在应用价值。

关键词: 黄酮, 荧光探针, ESIPT, 三苯基膦, Staudinger连接

Abstract:

Triphenylphosphine is an important organic substance with nucleophilicity and reducing character for a lone pair of electrons on phosphine. Nowadays it has been widely used in the synthesis of organic and organometallic compounds, such as Wittig reaction, Mitsunobu reaction, Appel reaction and Staudinger reaction. The massive use of PPh₃ is unavoidable to cause phosphorous pollution into the environment that would pose potential threat to human health. An effective and convenient detection method of PPh₃ is fairly urgent. At present, small-molecule fluorescence probes, due to their high sensitivity, concise detection procedure and easy-to-manipulate detection facility, have been recognized as one of the most attractive method to monitor and visualize analytes. Here a new Flavone-based turn-on fluorescent probe was constructed for detecting triphenylphosphine through the Staudinger ligation. The design concept was to use a 2-azidophenylacetic ester of a hydroxyl-containing fluorophore to react with PPh₃ to undergo a rapid intramolecular acyl transfer through aza-ylide intermediate to release the fluorophore after hydrolysis, which showed high selectivity and sensitivity to the detection of PPh₃ over other compounds in the dilute solution as well as in filter papers. The simple probe is potentially useful for qualitative and quantitative analysis of PPh₃.

Key words: flavone, fluorescent probe, ESIPT, triphenylphosphine, Staudinger ligation

张健, 吕明环, 张维娟, 赵伟利. 基于黄酮的ESIPT型荧光探针检测三苯基膦[J]. 影像科学与光化学, 2017, 35(4): 526-535.

ZHANG Jian, LÜ Minghuan, ZHANG Weijuan, ZHAO Weili. Flavone-based ESIPT Fluorescent Probe for Determination of Triphenylphosphine[J]. Imaging Science and Photochemistry, 2017, 35(4): 526-535.

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