Synthesis of Ruthenium‑Graphene Quantum Dots Artificial Oxidase and Its Application in Colorimetric Detection of Phoxim in Carrots

doi:10.19894/j.issn.1000-0518.210353

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (8): 1285-1293.DOI: 10.19894/j.issn.1000-0518.210353

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Synthesis of Ruthenium‑Graphene Quantum Dots Artificial Oxidase and Its Application in Colorimetric Detection of Phoxim in Carrots

Wen-Dong WANG, Zai-Jun LI()

School of Chemistry and Materials Engineering，Jiangnan University，Wuxi 214125，China

Received:2021-07-21 Accepted:2021-12-07 Published:2022-08-01 Online:2022-08-04
Contact: Zai-Jun LI
About author:zaijunli@jiangnan.edu.cn
Supported by:
the National Key Research and Development Program of China(2018YFC1603001)

Abstract

Abstract:

The histidine functionalized graphene quantum dots （His-GQDs） react with ruthenium trichloride to form a stable ruthenium complex. This complex is treated in a N₂ atmosphere at 600 ℃ for 1 h to obtain a ruthenium-graphene quantum dot composite （Ru-His-GQD）. The results of scanning electron microscopy （SEM） and transmission electron microscopy （TEM） analysis demonstrate that Ru-His-GOD has one three-dimensional structure. The diameter of ruthenium nanoparticles is between 40 and 60 nm. Ru-His-GQD is rich in functional groups and has high oxidase-like activity. Based on Ru-His-GQD catalyzed oxidation of 3，3′，5，5′-tetramethylbenzidine （TMB） to produce blue compounds， a photometric method for the determination of phoxim in carrots is established. Phoxim can inhibit the activity of Ru-His-GQD oxidase， resulting in a decrease in the absorbance of the blue compound. When the concentration of phoxim is between 30～240 μg/L， the absorbance of the oxidation product of TMB at 652 nm decreases linearly with the increase of phoxim concentration. The detection limit of the method reaches 7.33 μg/L （S/N=3）， and the sensitivity is higher than those in literature. It has been successfully applied to the detection of phoxim in carrots.

Key words: Pesticide detection, Functionalized graphene quantum dots, Ruthenium nanoparticles, Phoxim, Colorimetric sensor

CLC Number:

O655

Wen-Dong WANG, Zai-Jun LI. Synthesis of Ruthenium‑Graphene Quantum Dots Artificial Oxidase and Its Application in Colorimetric Detection of Phoxim in Carrots[J]. Chinese Journal of Applied Chemistry, 2022, 39(8): 1285-1293.

Figures/Tables 8

Fig.1 SEM image （A）， TEM image （B）， XRD pattern （C） and FT-IR spectrum （D） of Ru-His-GQD

Fig.2 （A） Total XPS energy spectrum of Ru-His-GQD；（B， C and D） high-resolution C1s， N1s and Ru3p XPS energy spectra of Ru-His-GQD

Fig.3 （A） Ultraviolet-visible absorption spectra of the reaction system in the presence of Ru-His-GQD（a）， Ru nanoparticle （b） or His-GQD（c）；（B） Ultraviolet-visible absorption spectra of Ru-His-GQD+TMB （a） and Ru-His-GQD+TMB+ phoxim reaction systems

Fig.4 （A） The absorbance at 652 nm for different pH media；（B） The absorbance at 652 nm for different reaction times

Fig.5 （A） Ultraviolet-visible absorption spectra of the color reaction system in the presence of 0， 30， 60， 90， 120， 150， 180， 210 and 240 μg/L；（B） Relationship curve of the absorbance of the color reaction system with the phoxim concentration

Table 1 Comparison of the different colorimetric methods for detection of organophosphorus pesticides

催化剂 Catalyst	线性范围 Linear range/（μg·L^-1）	检出限 The detection limit/（μg·L^-1）	检测样品 Test sample	文献 Ref.
CDs?AgNPs	30～30000	12	辛硫磷 Phoxim	25
Ag₃PO₄ NPs		9970	毒死蜱 Chlorpyrifos	26
PAA?CeO₂		8.62	敌敌畏 Dichlorvos	27
Ag₃PO₄/UiO?66	8.3～5333	7.5	马拉硫磷 Malathion	28
Ru?His?GQD	30～240	7.33	辛硫磷 Phoxim	本工作 This work

Fig.6 （A） The absorbance of the color reaction system using the Ru-His-GQD samples with different storage periods；（B） The absorbance of color reaction system in the presence of different interfering substances of 150 μg/L

Table 2 The results for detection of phoxim in carrot samples （n=5）

样品 Sample	样品添加标准浓度 Sample addition standard concentration/ （ng·mL^-1）	用建立的检测方法检测浓度 Use the established detection method to detect the concentration/（ng·mL^-1）	回收率 Recovery/%
胡萝卜1 Carrot 1	0.0	No found
胡萝卜1 Carrot 1	20.0	19.26±0.06	96.3
胡萝卜2 Carrot 2	0.0	No found
胡萝卜2 Carrot 2	20.0	19.52±0.02	97.6
胡萝卜3 Carrot 3	0.0	No found
胡萝卜3 Carrot 3	20.0	20.36±0.04	101.8
胡萝卜4 Carrot 4	0.0	2.2±0.05
胡萝卜4 Carrot 4	20.0	21.83±0.04	98.2
胡萝卜5 Carrot 5	0.0	3.6±0.03
胡萝卜5 Carrot 5	20.0	24.12±0.07	102.3

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Synthesis of Ruthenium‑Graphene Quantum Dots Artificial Oxidase and Its Application in Colorimetric Detection of Phoxim in Carrots

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