MoS2中空纳米球的制备及在超灵敏microRNA电化学生物传感器中的应用

doi:10.7503/cjcu20160488

摘要/Abstract

摘要：

采用模板法制备了二硫化钼中空球纳米材料, 利用扫描电子电子显微镜、 X射线衍射仪和Raman光谱仪对材料的形貌和结构进行表征. 将适配体固定在金纳米粒子和二硫化钼共同修饰的电极上构建了一种新型的微小核糖核酸(microRNA) 电化学生物传感器, 采用循环伏安、微分脉冲伏安和电化学阻抗等技术对构筑的传感器进行表征. 结果表明, microRNA浓度在1.0×10^-10 ~1.0×10^-16 mol/L范围内峰电流(I)与microRNA浓度的负对数(-lgc)呈良好的线性, 目标miRNA的检出限为0.55×10^-16 mol/L. 构建出的传感器具备选择性好、灵敏度高、稳定性强等特性, 具有广阔的应用前景.

关键词: 二硫化钼中空球, 微小核糖核酸, 电化学生物传感器, 信号放大

Abstract:

Molybdenum disulfide hollow sphere nanomaterial was synthesized through template-assisted method, the morphological structure was characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) and Raman spectroscopy. A novel microRNA electrochemical biosensor was constructed by immobilizing of aptamer on the electrode that was modified with Au nanoparticles and MoS₂. The electrochemical behavior of the modified electrode was tested by cyclic voltammograms, differential pulse voltammetric and electrochemical impedance. The results indicate that the as-prepared biosensor shows a good linear relationship between the current variation and logarithm of the miRNA concentration ranging from 1.0×10^-10 mol/L to 1.0×10^-16 mol/L. The detection limit was estimated to be 0.055×10^-16 mol/L. The constructed sensor shows good selectivity, high sensitivity, strong stability characteristics and has a broad application prospect.

Key words: Molybdenum disulfide hollowsphere, MicroRNA, Electrochemical biosensor, Signal amplification

中图分类号:

O657

TrendMD:

刘仁植, 李晓严. MoS₂中空纳米球的制备及在超灵敏microRNA电化学生物传感器中的应用. 高等学校化学学报, 2017, 38(3): 383.

LIU Renzhi, LI Xiaoyan. Preparation of MoS₂ Hollow Nanospheres and Application in Ultrasensitive Electrochemical Biosensing Platform for Micro-RNA Detection^†. Chem. J. Chinese Universities, 2017, 38(3): 383.

图/表 13

Scheme 1 Schematic illustration of preparation process of biosensor for miRNA detection based on hollow MoS2 sphere coupling with enzyme-amplification

Fig.1 SEM images of MnCO3(A, B), MnS@MoS2(C), intact MoS2 sphere(D), cracked MoS2 sphere(E) and the high-resolution MoS2 sphere(F)

Fig.2 Raman spectra of MnCO3(A), MnS@MoS2 and MoS2(B)

Fig.3 XRD patterns of MnCO3(A), MnS@MoS2 and MoS2(B)

Fig.4 CVs(A,B) and EIS(C,D) of different electrodes (A), (C) a. GCE; b. MoS2/GCE; c. AuNPs/MoS2/GCE; (B),(D) a. AuNPs/MoS2/GCE; b. capture probe/AuNPs/MoS2/GCE; c. MCH/capture probe/AuNPs/MoS2/GCE; d. miRNA/MCH/capture probe/AuNPs/MoS2/GCE; e. signal probe/miRNA/MCH/capture probe/AuNPs/MoS2/GCE; f. SA-ALP/signal probe/miRNA/MCH/Capture probe/AuNPs/MoS2/GCE.

Fig.5 Q-t curves(A) and Q-t1/2 curves(B) of the bare GCE(a) and AuNPs/MoS2/GCE(b) in PBS containing 0.1 mmol/L K3[Fe(CN)6] and 1.0 mol/L KCl

Fig.6 DPVs of SA-ALP/signal probe/miRNA/MCH/capture probe/AuNPs/GCE(a) and SA-ALP/signal probe/miRNA/MCH/capture probe/AuNPs/MoS2/GCE(b) in 10 mmol/L PBS(pH=7.0) containing 5 mmol/L TCEP and 2 mmol/L FCM

Fig.7 Experimental conditions optimization (A) Deposition time of AuNPs; (B) incubation time of target miRNA; (C) incubation time of signal probe.

Fig.8 Schematic diagram of enzyme signal amplification system

Fig.9 DPVs of various target miRNA concentrations c(miRNA)/(mol·L-1) from a to j: 0, 1.0×10-16, 1.0×10-15, 1.0×10-14, 5.0×10-13, 1.0×10-13, 5.0×10-12, 1.0×10-12, 1.0×10-11, 1.0×10-10. Inset: the calibration plots of the DPV current versus the logarithm concentration of target miRNA.

Table 1 Comparison between the as-prepared sensor and other sensors for miRNA detection

Electrode	Analytical technique	Linear range/(pmol·L^-1)	LOD/(fmol·L^-1)	Ref.
Os(bpy)₂(API)Cl-activated GO	Amperometric current-time curve	0.008—10	4	[30]
HRP/TMB/gold GCE	Amperometric current-time curve	0.01—1000	10	[31]
HRP/AuNPs/graphene	DPV	0.001—700	6	[32]
AuNPs/ALP/redox cycling	Amperometric current-time curve	0.001—5	3	[33]
QDs/RP/GODPS/GCE	Fluorescence dots	0.05—1	5	[34]
IgG-ALP/AuNPs/GCE	DPV	0.0005—0.5	0.4	[35]
SA-ALPs/gold GCE	Mperometric current-time curve	0.0005—1	0.2	[36]
AuNPs/MoS₂/GCE	DPV	0.0001—100	0.055	This work

Fig.10 Selectivity of the sensor hybridized to different miRNA sequences a. Non-complementary sequence; b. three-based mismatch sequence; c. single-based mismatch sequence; d. target miRNA.

Table 2 Result of detection of directly adding target miRNA in serum samples(n=3)

Added miRNA/(fmol·L^-1)	Found miRNA/(fmol·L^-1)	RSD^*(%)	Recovery(%)
10	9.1	5.2	91.0
100	98.6	3.8	98.6
1000	1054	2.7	105.4
10000	9784	2.8	97.8
100000	105248	4.6	105.3

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MoS₂中空纳米球的制备及在超灵敏microRNA电化学生物传感器中的应用

Preparation of MoS₂ Hollow Nanospheres and Application in Ultrasensitive Electrochemical Biosensing Platform for Micro-RNA Detection^†

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