The construction and application of biosensor based on gold nanoparticles loaded SiO2-nanoflowers

doi:10.11949/0438-1157.20221413

Abstract

Abstract:

Dispersed gold nanoparticles-modified amino-silica composites (Au@NH₂-SiO₂) were prepared by in situ reduction using wrinkled silica nanoflowers (SiO₂ NFs). Au@NH₂-SiO₂ NFs nanomaterials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier-infrared spectroscopy (FT-IR) and elemental mapping. The AChE/Au@NH₂-SiO₂ NFs/GCE biosensor was constructed based on Au@NH₂-SiO₂ NFs composite material. The detection performance of biosensor was investigated by two organophosphorus pesticides, malathion and chlorpyrifos. Separately, the prepared biosensor exhibited wide linear ranges of (1.00×10^-11)—(1.00×10^-5) mol/L with the LOD of 2.92×10^-12 mol/L for malathion and (1.00×10^-13)—(1.00×10^-7) mol/L with a LOD of 5.60×10^-14 mol/L for chlorpyrifos. The AChE/Au@NH₂-SiO₂ NFs/GCE biosensor was also used to detect real samples getting the recovery rate of 90.7%—107.0%. The AChE/Au@NH₂-SiO₂ NFs/GCE biosensor has outstanding stability and sensitivity.

Key words: acetylcholinesterase, composites, biosensor, electrochemistry, organophosphorus pesticides

摘要：

利用褶皱状二氧化硅纳米花（SiO₂ NFs），通过原位还原法制备分散的金纳米颗粒修饰的氨基二氧化硅复合材料（Au@NH₂-SiO₂ NFs）。利用扫描电镜（SEM）、透射电镜（TEM）、X射线光电子能谱（XPS）、X射线衍射（XRD）、傅里叶红外光谱仪（FT-IR）和元素分析（elemental mapping）对Au@NH₂-SiO₂ NFs纳米材料进行表征。基于Au@NH₂-SiO₂ NFs构建AChE/Au@NH₂-SiO₂ NFs/GCE生物传感器。选择马拉硫磷和毒死蜱两种有机磷农药为代表，考察生物传感器的检测性能，其中马拉硫磷的检测范围是（1.00×10^-11）~（1.00×10^-5） mol/L，检测限为2.92×10^-12 mol/L；毒死蜱的检测范围是（1.00×10^-13）~（1.00×10^-7） mol/L，检测限为5.60×10^-14 mol/L。AChE/Au@NH₂-SiO₂ NFs/GCE电极在实际样品检测中的回收率在90.7%~107.0%之间，并展现出良好的抗干扰性、储藏稳定性和重现性。

关键词: 乙酰胆碱酯酶, 复合材料, 生物传感器, 电化学, 有机磷农药

CLC Number:

O 657.14

Ruiqi LIU, Xitong ZHOU, Yue ZHANG, Ying HE, Jing GAO, Li MA. The construction and application of biosensor based on gold nanoparticles loaded SiO₂-nanoflowers[J]. CIESC Journal, 2023, 74(3): 1247-1259.

刘瑞琪, 周栖桐, 张悦, 贺莹, 高静, 马丽. 基于金纳米颗粒修饰二氧化硅纳米花的生物传感器构建及应用[J]. 化工学报, 2023, 74(3): 1247-1259.

Figures/Tables 12

Fig.1 TEM images of SiO2 NF (a), Au-15@NH2-SiO2 NFs (b), Au-30@NH2-SiO2 NFs (c) , and Au-45@NH2-SiO2 NFs (d); HRTEM image of Au-30@NH2-SiO2 NFs (e)

Fig.2 SEM image (a) and particle size distribution (b) of SiO2 NFs; SEM image of Au-30@NH2-SiO2 NFs (c)

Fig.3 CV curves of bare GCE and different modified GCE

Fig.4 HAADF-STEM image (a) and elemental mappings [(b)—(e)] of Au@NH2-SiO2 NFs

Fig.5 XPS spectra of the SiO2 NFs and Au@NH2-SiO2 NFs (a); the Au 4f core-level peaks of the Au@NH2-SiO2 NFs (b); wide-angle XRD patterns of the SiO2 NFs and Au@NH2-SiO2 NFs (c); FT-IR spectra of SiO2 NFs, NH2-SiO2 NFs， and Au@NH2-SiO2 NFs (d)

Fig.6 CV curves at a scan rate of 50 mV/s (a) and Nyquist plots (b) of the bare GCE and Au@NH2-SiO2 NFs/GCE; CV responses from the bare GCE, Au@NH2-SiO2 NFs/GCE， and AChE/Au@NH2-SiO2 NFs/GCE at a scan rate of 50 mV/s (c); CV curves of AChE/Au@NH2-SiO2 NFs/GCE at 60—160 mV/s (d); plots of oxidation peak current vs scan rate (e)

Fig.7 The effects of pH of PBS (a), concentration of ATCl (b), amount of Au@NH2-SiO2 NFs (c)， and amount of AChE (d) on oxidation peak currents of ATCl

Fig.8 Current-time plot of AChE/Au@NH2-SiO2 NFs/GCE (a) and calibration curves for ATCl determination (b)

Fig.9 Effect of incubation time on inhibition of AChE/Au@NH2-SiO2 NFs/GCE biosensor after inhibition with malathion (a) and chlopyrifos (b); DPV of AChE/Au@NH2-SiO2 NFs/GCE after inhibition with various concentrations of malathion for 500 s (c) and chlopyrifos for 300 s (d); the relationship between inhibition and concentration of malathion (e) and chlopyrifos (f) malathion concentration (0)—(7): 0, 1.00×10-11, 1.00×10-10, 1.00×10-9, 1.00×10-8, 1.00×10-7, 1.00×10-6, and 1.00×10-5 mol/L (c); chlopyrifos concentration (0)—(7): 0, 1.00×10-13, 1.00×10-12, 1.00×10-11, 1.00×10-10, 1.00×10-9, 1.00×10-8, and 1.00×10-7 mol/L (d)

Table 1 Comparison of the analytical characteristics of the AChE electrochemical biosensors for OPs

检测目标	电极	检测范围/(mol/L)	检测限/(mol/L)	文献
马拉硫磷	AChE-CS/3DG-CuO NFs/GCE	(4.67×10^-12)~(3.00×10^-8)	9.20×10^-11	[37]
	poly(FBThF)/Ag-rGO-NH₂/AChE/GCE	(3.00×10^-10)~(3.00×10^-8)	9.69×10^-11	[38]
	AChE-CS/rGO-TEPA-CuO NWs/GCE	(3.00×10^-12)~(6.00×10^-8)	1.20×10^-12	[39]
	AChE/COF@MWCNTs/ GCE	(1.00×10^-9)~(1.00×10^-5)	5.00×10^-10	[40]
	AChE/Au@NH₂-SiO₂ NFs/GCE	(1.00×10^-11)~(1.00×10^-5)	2.92×10^-12	本文
毒死蜱	AChE/CHIT-SnS₂/GCE	(2.00×10^-11)~(1.00×10^-5)	2.00×10^-11	[41]
	AChE/OMC-CS/ATO-CS/SPCE	(2.85×10^-11)~(2.85×10^-6)	2.85×10^-11	[42]
	AChE-CS/GP-AuNP-PEDOT:PSS/SPCE	(1.00×10^-10)~(1.00×10^-8)	7.00×10^-11	[43]
	CD-AChE/GO	(7.10×10^-9)~(2.85×10^-7)	4.10×10^-10	[44]
	BSA/AChE/GA/CIS/rGO-9/SPCE	(1.42×10^-9)~(1.34×10^-6)	6.56×10^-11	[45]
	AChE/Au@NH₂-SiO₂ NFs/GCE	(1.00×10^-13)~(1.00×10^-7)	5.60×10^-14	本文

Fig.10 Influence of different interfering substances on the amperometric response to ATCl (a); Influence of different interfering substances on oxidation peak current of chlorpyrifos (b); the storage stability of AChE/Au@NH2-SiO2 NFs/GCE (c)

Table 2 Detection of chlopyrifos in spiked samples using AChE/Au@NH2-SiO2 NFs/GCE

相对标准偏差

(n=3)

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The construction and application of biosensor based on gold nanoparticles loaded SiO₂-nanoflowers

基于金纳米颗粒修饰二氧化硅纳米花的生物传感器构建及应用

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