Synthesis of Benzothiazole Fluorescent Probe for Detection of N2H4·H2O and HSO3-†

doi:10.7503/cjcu20190159

Abstract

Abstract:

Based on benzothiazole as fluorophore, ethyl cyanoacetate as recognition group, a new fluorescent probe 3-(2-hydroxy-benzothiazole)-2-cyano-ethyl acrylate(HBT-CN) with dual detection ability for hydrazine hydrate and bisulfite was designed and synthesized. In DMSO/PBS(1：4, volume ratio) buffered condition, the probe displayed good selectivity towards hydrazine and bisulfite with approximate 5.6 times(500 nm) and 7.5 times(458 nm) fluorescence enhancement at 500 and 458 nm, respectively. ¹H NMR, ¹³C NMR and HRMS results showed that during the detection process, HBT-CN undergoed a reduction-condensation reaction with N₂H₄·H₂O, which form a aldehyde hydrazone and emited pale yellow fluorescent signal at 500 nm. And HBT-CN under went a nucleophilic addition reaction with bisulfite and emited blue fluorescent signal at 458 nm. So, differential qualitative and quantitative detection of N₂H₄·H₂O and HS $O 3 -$ can be achieved.

Key words: Fluorescent probe, Benzothiazole, Hydrazine hydrate, Bisulfite

CLC Number:

O626

TrendMD:

WANG Jinjin,QI Shaolong,DU Jianshi,YANG Qingbiao,SONG Yan,LI Yaoxian. Synthesis of Benzothiazole Fluorescent Probe for Detection of N₂H₄·H₂O and HS $O 3 - †$ [J]. Chem. J. Chinese Universities, 2019, 40(7): 1397.

Figures/Tables 11

Scheme 1 Synthesis of the probe HBT-CN

Fig.1 Photographs of color change(A) and fluorescence response(B) of HBT-CN(5.0×10-6 mol/L) after adding HSO3-(2.5×10-4 mol/L), N2H4·H2O(1×10-3 mol/L) and other analytes(2.5×10-3 mol/L)V(DMSO)：V(PBS)=1：4.

Fig.2 Time-dependent fluorescence intensity changes of HBT-CN(5×10-6 mol/L) in the presence of N2H4·H2O(1×10-3 mol/L, λex=399 nm, λem=500 nm, slits: 2.5 nm/5 nm)(A) and HSO3-(1×10-3 mol/L, λex=399 nm, λem=458 nm, slits: 2.5 nm/5 nm)(B)

Fig.3 Fluorescence intensity of HBT-CN(5×10-6 mol/L) changes with different pH valuesa. HBT-CN; b. HBT-CN+HSO3-; c. HBT-CN+N2H4·H2O.

Fig.4 Fluorescence intensity of HBT-CN(5×10-6 mol/L) changes upon gradual addition of N2H4·H2O(0—1.2×10-3 mol/L)(A) and linear relationship between fluorescence intensity(500 nm) of HBT-CN and concentrations of N2H4·H2O(0—1.05×10-3 mol/L)[V(DMSO)：V(PBS)=1：4; λex=399 nm, slit: 5 nm/5 nm](B)

Fig.5 Fluorescence intensity of HBT-CN(5 μmol/L) changes upon gradual addition of HSO3-(0—3×10-4 mol/L)(A) and linear relationship between fluorescence intensity of HBT-CN and concentrations of HSO3-(0—1.2×10-4 mol/L) at 458 nm[V(DMSO)：V(PBS)=1：4, λex=399 nm, slit: 5 nm/5 nm](B)

Fig.6 Fluorescence spectra of HBT-CN(5.0×10-6 mol/L) in the presence of HSO3-, N2H4·H2O and other analytes

Fig.7 Fluorescence response of HBT-CN(5×10-6 mol/L) in the presence of HSO3-+anions(A) and N2H4·H2O+others(B)Black bars represent the fluorescent intensity(458 nm) of HBT-CN(5×10-6 mol/L) in the presence of anions after adding HSO3-; red bars represent the fluorescent intensity(458 nm) of HBT-CN(5×10-6 mol/L) in the presence of anions in the absence of HSO3-. (A) a. HSO3-; b. CO32-; c. S2O32-; d. S2-; e. SO42-; f. H2PO4-; g. C2O42-; h. AcO-; i. N3-; j. SCN-; k. F-; l. Cl-; m. Br-; n. I-; o. NO3-; p. NO2-. (B) a. N2H4·H2O; b.GSH; c. Cys; d. Hcy; e. H2NCONH2; f. C6H8N2; g. NH(CH3)2; h. CH3CH2NH2; i. K+; j. Na+; k. NH4+; l. Mg2+; m. Ba2+.

Scheme 2 Proposed sensing mechanism of HBT-CN for N2H4·H2O and HSO3-

Fig.8 1H NMR spectra of HBT-CN(A) , HBT-N2H4(B) and HBT-HSO3-(C)

Fig.9 13C NMR spectra of HBT-CN(a) and HBT-N2H4(b)

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Synthesis of Benzothiazole Fluorescent Probe for Detection of N₂H₄·H₂O and HS $O 3 - †$

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