Ruthenium-biocarbon Mimic Enzyme: Synthesis and Application in Colorimetric Detection of Pesticide Chlorpyrifos

doi:10.15541/jim20210365

Abstract

Abstract:

Metal nanomaterials as mimic enzyme have been widely used for biosensor and catalysis due to their high stability and low cost. Here, [1-methyl-3-ethylimidazole][dicyandiamide] ionic liquid ([EMIM][DCA]) reacted with ruthenium chloride to form [EMIM]₃[Ru(DCA)₆] ionic liquid. Silk was dissolved in the above ionic liquid and then carbonized at high temperature to obtain Ru-biomass carbon composite. The results show that Ru-biomass carbon offers excellent dispersion, small Ru nanoparticles with an average diameter of 7.5 nm which were uniformly dispersed on the surface of carbon sheets, and high oxidase-like activity. Based on the inhibition of chlorpyrifos on catalytic activity of Ru-biomass carbon, a method was established for colorimetric determination of chlorpyrifos. Chlorpyrifos obviously inhibits the catalytic activity of Ru-biochar carbon, leading to a reduced absorbance of blue product. When the concentration of chlorpyrifos was in the range from 10 to 80 ng/mL, the peak absorbance decreases linearly with the increase of chlorpyrifos concentration, giving a detection limit of about 6.5 ng/mL. The as-proposed method provides higher sensitivity and stability compared with present methods, and has successfully applied to detection of chlorpyrifos in peach samples.

Key words: metal ionic liquid, Ru nanomaterial, oxidase-like enzyme, organophosphorus insecticides, colorimetric detection

CLC Number:

TQ174

CAO Zhijun, LI Zaijun. Ruthenium-biocarbon Mimic Enzyme: Synthesis and Application in Colorimetric Detection of Pesticide Chlorpyrifos[J]. Journal of Inorganic Materials, 2022, 37(5): 554-560.

Figures/Tables 8

Fig. 1 SEM (A), TEM (B), HRTEM images (C), and elemental mappings of Ru (D) and N (E) elements and XRD pattern (F) of the as-prepared Ru-biomass carbon composite

Fig. 2 Total XPS spectrum (A), high-resolution C1s (B), Ru3p (C) and N1s (D) XPS spectra of Ru-biomass carbon composite

Fig. 3 Absorption spectra of the reaction system catalysis by Ru-biomass carbon composite (a), CuO/Pt composite (b), Ru nanoparticles (c), and biomass carbon (d)

Fig. 4 Absorbances at 665 nm of the N2, air and O2 saturated TMB solutions with catalysis by Ru-biomass carbon composite

Fig. 5 Relationship curves of pH (A), reaction time (B), reaction temperature (C), and catalyst amount (D) with the absorbance of the reaction system

Fig. 6 Absorption spectra of the reaction system in the presence of 0, 10, 20, 30, 40, 50, 60, 70 and 80 ng/mL chlorpyrifos (A) and calibration plot of the absorbance at 665 nm varied with the chlorpyrifos concentration (B)

Table 1 Comparison of colorimetric methods with different nanozyme materials for detection of organophosphorus pesticides

Chromogenic system	Analysis time/min	Linear range/(ng·mL^-1)	Detection limit/(ng·mL^-1)	Ref.
Gold nanoclusters	40	1500-45000	6000	[23]
Acetylcholine	55	10000-140000	4000	[24]
Cu-Ag/rGO	30	300-9000	1080	[25]
Hemin regulated by oligonucleotide	62	2000-100000	600	[26]
CuO/Pt	50	300-180000	238.8	[19]
Fe-N-C	76	100-10000	97	[27]
Cu NPs	10	300-3000	20.4	[28]
Ru-biomass carbon composite	20	5-80	6.57	This work

Table 2 Results for detection of chlorpyrifos in peach (n=5)

Sample	Chlorpyrifos added /(ng·mL^-1)	Chlorpyrifos detected by proposed method/(ng·mL^-1)	Chlorpyrifos founded by GC-MS/(ng·mL^-1)	Recovery/%
Honey peach	0	(5.9±0.15)	(6.02±0.12)
Honey peach	10.0	(16.2±0.18)	(16.05±0.10)	101.8
Nectarine	0	(9.98±0.07)	(9.95±0.07)
Nectarine	10.0	(19.91±0.27)	(20.1±0.27)	99.6
Peento	0	(4.96±0.11)	(5.07±0.05)
Peento	10.0	(15.2±0.19)	(15.07±0.25)	101.6

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