化学学报 ›› 2019, Vol. 77 ›› Issue (4): 365-370.DOI: 10.6023/A18120484 上一篇    下一篇

研究论文

一种可用于直接检测空气中异氰酸酯的比率型荧光探针

陈凯, 韩百川, 嵇思鑫, 孙瑾, 高振忠, 侯贤锋   

  1. 华南农业大学 材料与能源学院木材科学与工程系 广州 510640
  • 投稿日期:2018-12-04 发布日期:2019-01-31
  • 通讯作者: 高振忠, 侯贤锋 E-mail:zzgaoscau@163.com;xfhou@scau.edu.cn
  • 基金资助:

    项目受广东省自然科学基金(No.2018A030310348)和广州市科技计划(No.201803030031)资助.

A Ratiometric Fluorescence Probe for Detecting Gaseous Isocyanates Directly

Chen Kai, Han Baichuan, Ji Sixin, Sun Jin, Gao Zhenzhong, Hou Xianfeng   

  1. South China Agricultural University, College of Material and Energy, Guangzhou 510640
  • Received:2018-12-04 Published:2019-01-31
  • Contact: 10.6023/A18120484 E-mail:zzgaoscau@163.com;xfhou@scau.edu.cn
  • Supported by:

    Project supported by the Natural Science Foundation of Guangdong Province, China (No. 2018A030310348), and the Guangzhou Science and Technology Plan (No. 201803030031).

异氰酸酯是一类广泛使用的化工原料,但容易挥发到空气中对人体健康造成危害.因此,建立一种快速、方便检测空气中异氰酸酯的方法具有重要的意义.合成了一种荧光探针(N-正丁基-4-羟基-1,8萘二酰亚胺),能与异氰酸酯快速反应,从而使探针的荧光颜色由黄绿色转变为蓝色,实现对异氰酸酯的比率型荧光检测.同时,该探针对异氰酸酯的响应具有灵敏性和选择性.反应机理研究表明,探针萘环4位上的羟基与异氰酸酯基(-NCO)反应生成了氨基甲酸酯基团.为了直接检测空气中的异氰酸酯,制备了一种基于该探针的检测试纸,实现对空气中异氰酸酯高灵敏性、高选择性的检测.该方法对空气中异氰酸酯的检测具有实际意义,同时也为挥发性有机物的检测提供了参考.

关键词: 异氰酸酯, 荧光探针, 试纸

Isocyanates is a widely-used chemical in many manufacturing industries, such as polymer industry, pharmaceutical production and production of a variety of agricultural chemicals. However, it is harmful to human health due to the volatility. Therefore, it is necessary to develop methods to detect isocyanates quickly and conveniently, especially to gaseous isocyanates. In this work, a novel fluorescent probe, N-buty-4-hydroxy-1,8naphthalimide, was developed for detection of isocyanates. This fluorescence probe can be synthesized by a simple three-steps synthetic route, and the overall yield of the whole synthesizing process reached 75%. In the absence of isocyanate, the probe solution displays an emission centering at 596 nm when excited at 370 nm, which is yellow to the naked eye. Once isocyanate is added, the fluorescence of solution changes from yellow to blue, and the process finishes in 4 min. The detecting limit of this probe to isocyanates is calculated to be 112 nmol·L-1. It is also proved that this probe possesses excellent selectivity for isocyanate and distinct anti-interference to common organic volatilized compounds. In addition, the reaction mechanism between the probe and isocyanate were proved by HPLC, NMR and ESI-MASS. Results show that the hydroxy group on the 4th position of naphthalene ring of probe reacts with isocyanate group (-NCO) of isocyanate, and resulting in carbamates, which alter 4th substituent group of probe molecule and lead to change of fluorescence. In order to detect the gaseous isocyanates directly, test paper are developed based on N-buty-4-hydroxy-1,8naphthalimide. When the test paper exposed to isocyanates vapor, the yellow fluorescence fade away gradually and a blue fluorescence appear in 6 min. And the test paper possesses excellent selectivity for gaseous isocyanate and distinct anti-interference to common VOCs. In conclusion, this strategy is an efficient way to detect gaseous isocyanates, and it may provide a referable approach for directly monitoring the volatile organic compounds in air.

Key words: isocyanates, fluorescence probe, testing paper