Mechanism research of organic pesticides detection by rich electronic LMOF

doi:10.11949/0438-1157.20191568

Abstract

Abstract:

A blue fluorescent electron-rich metal organic framework LMOF-a was used to realize fast and efficient luminescence detection of organic pesticides chlorothalonil, herbicide, trifluralin and 2,6-dichloro-4-nitroaniline. Spectral analysis and density functional theory calculations indicated that the detection mechanism of nitrofen by LMOF-a is attributed to charge transfer while the detection mechanisms of trifluralin, chlorothalonil, and 2,6-dichloro-4-nitroaniline by LMOF-a are attributed to charge transfer and fluorescence resonance energy transfer. The Stern-Volmer equation was applied to fit the detection data. LMOF-a demonstrated the highest detection efficiency of 2,6-dichloro-4-nitroaniline with K_SV up to (4.778±0.590) L/mmol, and the minimum detection limit down to 0.014 mmol/L. This research provides theoretical reference and technical support for the development of fast and high-efficiency detection of organic pesticides.

Key words: metal-organic framework, fluorescent probe, organic pesticide, density functional theory, detection mechanism

摘要：

利用1例蓝色荧光的富电子金属有机骨架LMOF-a实现对有机农药百菌清、除草醚、氟乐灵及2,6-二氯-4-硝基苯胺快速、高效的发光检测。光谱分析及密度泛函理论计算表明，LMOF-a对除草醚的检测机理为电荷转移机理，而对百菌清、氟乐灵及2,6-二氯-4-硝基苯胺的检测机理同时包含电荷转移机理及荧光共振能量转移机理。经Stern-Volmer方程拟合检测数据，LMOF-a对2,6-二氯-4-硝基苯胺具有最高的检测效率，K_SV值达(4.778±0.590) L/mmol，检测限低至0.014 mmol/L。研究为开发快速、高效的有机农药检测技术提供理论参考及技术支持。

关键词: 金属有机骨架, 荧光探针, 有机农药, 密度泛函理论, 检测机理

CLC Number:

X 592

Ling DI, Fang CHEN, Rongrong FU, Chen YANG, Yang XING, Xiaoning WANG. Mechanism research of organic pesticides detection by rich electronic LMOF[J]. CIESC Journal, 2020, 71(8): 3830-3838.

狄玲, 陈放, 付荣荣, 杨辰, 邢杨, 王晓宁. 富电子LMOF对有机农药的检测机理研究[J]. 化工学报, 2020, 71(8): 3830-3838.

Figures/Tables 9

Fig.1 Structure of organic ligand(a); SEM image of LMOF-a(b); the coordination environments of binuclear Zn(Ⅱ) center(c) and the organic ligand(d) in LMOF-a; topological structure of LMOF-a(e)

Fig. 2 Theoretical and experimental PXRD spectra of LMOF-a(a); FT-IR spectra of organic ligand and LMOF-a(b)

Fig.3 Structures of organic pesticides GPHS, CPR, TZP, CTL, NF, TFL and DCN(a); fluorescent responses of LMOF-a to seven organic pesticides with addition concentration of 2.0, 6.0 and 10.0 mmol/L(b)

Fig.4 Concentration-dependent fluorescence responses of LMOF-a to organic pesticides

Fig.5 Fluorescence quenching efficiency histograms of organic pesticides NF, CTL, TFL, and DCN to LMOF-a

Fig.6 Electron density isosurfaces (0.02 a.u.) and energy levels of frontier molecular orbitals of the ligand and organic pesticides

Fig.7 Overlaps between UV-vis spectra of organic pesticides CTL, NF, TFL, DCN and fluorescent spectrum of LMOF-a

Fig.8 Stern-Volmer plots of LMOF-a for fluorescent detection of organic pesticides NF, CTL, TFL and DCN

Table 1 Fitting parameters for organic pesticides detection by LMOF-a

Pesticides	K_SV/(L/mmol)	Standard	f₁	f₂	r²
CTL	0.322	0.035	0.845	0.155	0.993
NF	0.335	0.015	1.049	-0.049	0.998
TFL	3.025	0.156	1.133	-0.133	0.997
DCN	4.778	0.590	1.181	-0.181	0.991

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