酶-二维MXene复合材料的制备及其电化学检测H2O2的应用

doi:10.15541/jim20190139

摘要/Abstract

摘要：

本研究合成了具有垂直栅栏结构的二维MXene材料, 与辣根过氧化物酶进行固定, 构筑了过氧化氢电化学酶传感器。合成的MXene纳米栅栏具有大的比表面积, 优良的电子传导特性和在水溶液中的良好分散特性; 固定化在酶电极上的辣根过氧化物酶分子表现出了优良的过氧化氢催化效果。结果表明HRP@MXene/chitosan/GCE酶电化学传感器在过氧化氢浓度为5~1650 μmol/L范围内表现出很好的线性关系, 最低检测限为0.74 μmol/L, 且具有很好的操作稳定性, 该生物传感器被成功地应用于固态与液态食品中过氧化氢残留检测。

关键词: 辣根过氧化物酶, MXene纳米片, 生物传感器, 过氧化氢

Abstract:

Two-dimensional MXene nanosheets with vertical junction structure was employed for easy immobilization of horse radish peroxidase enzymes to fabricate the electrochemical hydrogen peroxide (H₂O₂) biosensor. The synthesized MXene nanosheets exhibited large specific area, excellent electronic conductivity and good dispersion in aqueous phase. Horse Radish Peroxidase (HRP) enzymes molecules immobilized on MXene/chitosan/GCE electrode demonstrated good electrocatalytic activity toward reduction of H₂O₂. The fabricated HRP@MXene/chitosan/GCE biosensor exhibited a wide linear range from 5 to 1650 μmol?L ^-1, a limit of detection of 0.74 μmol?L ^-1 and good operation stability. The fabricated biosensor was successfully employed for detection of trace level of H₂O₂ in both solid and liquid food.

Key words: horse radish peroxidase, MXene nanosheets, biosensor, hydrogen peroxide

中图分类号:

TS207

马保凯, 李勉, 张绫芷, 翁新楚, 沈彩, 黄庆. 酶-二维MXene复合材料的制备及其电化学检测H₂O₂的应用[J]. 无机材料学报, 2020, 35(1): 131-138.

MA Bao-Kai, LI Mian, CHEONG Ling-Zhi, WENG Xin-Chu, SHEN Cai, HUANG Qing. Enzyme-MXene Nanosheets: Fabrication and Application in Electrochemical Detection of H₂O₂[J]. Journal of Inorganic Materials, 2020, 35(1): 131-138.

图/表 11

Fig. 1 Schematic illustration for fabrication of HRP@MXene (Graphite/TiC/Ti3C2)/chitosan/GCE and H2O2 sensing principle of HRP@MXene/chitosan/GCE

Fig. 2 XRD patterns of G/TiC/Ti3AlC2 and G/TiC/Ti3C2 (A); FT-IR spectra of the MXene, HRP and HRP@MXene (B); SEM images of the MXene G/TiC (C) and Ti3C2 (D)

Fig. S1 EIS of various electrodes in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4-: Chit (pH 5.0)/GCE (curve b, red line), Chit (pH 6.0)/GCE (curve c, blue line) , Chit (pH 6.5)/GCE (curve d, green line), Chit (pH 7.0)/GCE (curve e, pink line) (A); CV curves of Chit (pH 5.0)/GCE (curve b, red line), Chit (pH 6.0)/GCE (curve c, blue line) , Chit (pH 6.5)/GCE (curve d, green line) , Chit (pH 7.0)/GCE (curve e, pink line) electrodes cycled in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4-: (potential window: -0.1-0.5 V vs. SCE) (B)

Fig. 3 EIS of Chit(chitosan)/GCE(a), MXene/Chit/GCE(b), HRP@MXene/Chit/GCE (c) electrodes cycled in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4- (A); CV curves of Chit/GCE (a), MXene/Chit/GCE (b), HRP@MXene/Chit/GCE (c) electrodes cycled in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4-: (potential window: -0.1-0.5 V vs. SCE) (B)

Fig. 4 CV curves of Chit/GCE (curve a, black line), MXene/ Chit/GCE (curve b, red line), HRP/Chit/GCE (curve c, pink line), HRP@MXene/Chit/GCE (curve d, blue line) electrodes cycled in N2-saturated 0.1 mol?L-1 PBS (pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2 at a scanning rate of 50 mV?s-1 (potential window: -0.8-0.8 V vs. SCE).

Fig. S2 CV curves of HRP@MXene/Chit/GCE electrodes cycled in N2-saturated 0.1 mol?L-1 PBS (pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2 at a different scanning rates (20-500 mV?s-1) (A); Plot of cathodic and anodic peak current for HRP@MXene/Chit/GCE versus scanning rate (B); Inset: Plots of anodic peak potential and cathodic peak potential for HRP@MXene/Chit/GCE electrode versus the logarithm of scan rate

Fig.S3 Effects of PBS buffer’s pH (A) and concentration of MXene (B) on the cathodic peak current of enzyme biosensor cycled in N2-saturated 0.1 mol?L-1 PBS ( pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2; Effects of PBS buffer’s pH (C) and concentration of MXene (D) on the DPV response of enzyme biosensor cycledin N2-saturated 0.1 mol?L-1 PBS (pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2

Fig. 5 Amperometric responses of HRP@MXene/Chit/ GCE at -0.1 V upon successive additions of H2O2 in astirred 0.1 mol?L-1 PBS (pH 7.5) (A); Calibration curve of amperometric responses at different H2O2 concentrations (B); Amperometric responses of HRP@MXene/Chit/ GCE at -0.1 V upon successive additions of solutions extracted from milk sample (C) and dried scallop (D) spiked with different H2O2 under stirred 0.1 mol?L-1 PBS (pH 7.5)

Table S1 Comparison of the performance of present work with other published electrodes for hydrogen peroxide detection

Electrode	Linear range/(mmol?L^-1)	LOD/(mmol?L^-1)	Ref.
HRP-CTAB-Au/GCE	0.50-105	0.23	[1]
HRP/GO/GCE	0.002-0.5	1.6	[2]
HRP/TB/CCB	0.429-455	0.17	[3]
HRP-BMIM·BF4/SWCNTs	0.49 to 10.2	0.13	[4]
HRP/PGN/GCE	2.77-835	2.67 ×10^-4	[5]
Hb-MXene-GO/Au foil	2-1×10³	1.95	[6]
MXene/GCE	-	0.7×10^-3	[7]
Hb-naf-MXene/GCE	0.1-260	0.02	[8]
TiO₂-Hb-naf-MXene/GCE	0.1-380	1.4×10^-2	[9]
HRP@MXene/Chitosan/GCE	5-1.65×10³	0.74	This work

Table 1 Detection of hydrogen peroxide in real food sample

Sample	Added H₂O₂/ (mmol?L^-1)	Found H₂O₂/ (mmol?L^-1)	Recovery /%	RSD /%
Milk	12.5	13.037	104.30	5.88
Milk	50	52.57	105.14	1.12
Milk	125	136.5	109.20	3.33
Dried scallop	0	66.56	-	-
Dried scallop	12.5	77.84	90.24	6.97
Dried scallop	50	120.08	107.04	1.46
Dried scallop	125	189.11	98.04	8.39

Fig.S4 Amperometric response of HRP@MXene/Chit/GCE in 0.1 mol?L-1 pH 7.5 PBS containing 100 mmol?L-1 of ascorbic acid, glucose, uric acid and H2O2 (Applied potential: -0.1 V) (A); Reduction peak currents of HRP@MXene/Chit/GCE stored in 50 mmol?L-1 PBS (pH 7.5) at 4 for 10 d (B)

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酶-二维MXene复合材料的制备及其电化学检测H₂O₂的应用

Enzyme-MXene Nanosheets: Fabrication and Application in Electrochemical Detection of H₂O₂

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