Received Date:
04 December 2018 Available Online:
15 April 2019
Fund Project:
Project supported by the Natural Science Foundation of Guangdong Province, China (No. 2018A030310348), and the Guangzhou Science and Technology Plan (No. 201803030031)
Abstract:
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.
Figure 1.
(A) The fluorescence response of probe to isocyanate; (B) The absorbance spectrum of probe (black line) and the fluorescence spectrum of probe (blue line); (C) Fluorescence spectra of probe response to different isocyanate at different concentrations (Excitation wavelength is 370 nm, reacting time is 4 min); (D) The fluorescence emission ratio (I420/I540) as a function of EIC concentration. Excitation wavelength is 370 nm
Figure 2.
(A) Schematic illustration of reaction mechanism between probe and EIC; (B) HPLC figure of probe (line a, blue), product (line c, red) and reacting solution (line b, black); (C) ESI-MASS spectra of reacting solution (reacting time is 2 min, the concentration of EIC is 50 μmol/L)
Figure 3.
(A) The fluorescence response to gaseous EIC of test paper at 0.5, 1, 2, 3, 4, 5, 6 min, and the excitation wavelength is 365 nm (#8 is blank); (B) The appearance of test paper in natural light when exposed in gaseous EIC at 0.5, 1, 2, 3, 4, 5, 6 min (#8 is blank)
Figure 4.
(A) The response to different VOC of test paper (1 acetone, 2 methylbenzene, 3 chloroform, 4 diethyl ether, 5 ethyl acetate, 6 propylene, 7 formaldehyde, 8 ethyl isocyanate, the excitation wavelength is 365 nm. And the reacting time is 6 min); (B) The response to different isocyanates of test paper (1 2, 4-TDI, 2 2, 6-TDI, 3 MDI, 4 HDI, 5 IPDI and 6 EIC. The excitation wavelength is 365 nm and the reacting time is 6 min)
Figure 1
(A) The fluorescence response of probe to isocyanate; (B) The absorbance spectrum of probe (black line) and the fluorescence spectrum of probe (blue line); (C) Fluorescence spectra of probe response to different isocyanate at different concentrations (Excitation wavelength is 370 nm, reacting time is 4 min); (D) The fluorescence emission ratio (I420/I540) as a function of EIC concentration. Excitation wavelength is 370 nm
Figure 2
(A) Schematic illustration of reaction mechanism between probe and EIC; (B) HPLC figure of probe (line a, blue), product (line c, red) and reacting solution (line b, black); (C) ESI-MASS spectra of reacting solution (reacting time is 2 min, the concentration of EIC is 50 μmol/L)
Figure 3
(A) The fluorescence response to gaseous EIC of test paper at 0.5, 1, 2, 3, 4, 5, 6 min, and the excitation wavelength is 365 nm (#8 is blank); (B) The appearance of test paper in natural light when exposed in gaseous EIC at 0.5, 1, 2, 3, 4, 5, 6 min (#8 is blank)
Figure 4
(A) The response to different VOC of test paper (1 acetone, 2 methylbenzene, 3 chloroform, 4 diethyl ether, 5 ethyl acetate, 6 propylene, 7 formaldehyde, 8 ethyl isocyanate, the excitation wavelength is 365 nm. And the reacting time is 6 min); (B) The response to different isocyanates of test paper (1 2, 4-TDI, 2 2, 6-TDI, 3 MDI, 4 HDI, 5 IPDI and 6 EIC. The excitation wavelength is 365 nm and the reacting time is 6 min)
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