具有高类氧化酶活性的铂-金枝状纳米粒子用于检测抗坏血酸

doi:10.15541/jim20200005

无机材料学报 ›› 2020, Vol. 35 ›› Issue (10): 1169-1176.DOI: 10.15541/jim20200005 CSTR: 32189.14.10.15541/jim20200005

所属专题：生物材料论文精选(2020)；【虚拟专辑】生物检测与成像(2020~2021)

具有高类氧化酶活性的铂-金枝状纳米粒子用于检测抗坏血酸

程琴¹^,²(), 杨勇²(), 杨莉莉²

^1. 上海大学上海应用辐射研究所, 上海 201800
^2. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050

收稿日期:2020-01-05 修回日期:2020-02-03 出版日期:2020-10-20 网络出版日期:2020-10-20
通讯作者: 杨勇, 研究员. E-mail:yangyong@mail.sic.ac.cn
作者简介:程琴(1994-), 女, 硕士研究生. E-mail: cq18817206957@163.com

Pt-Au Dendritic Nanoparticles with High Oxidase-like Activity for Detection of Ascorbic Acid

CHENG Qin¹^,²(), YANG Yong²(), YANG Lili²

^1. Shanghai Applied Radiation Institute, Shanghai University, Shanghai 201800, China
^2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2020-01-05 Revised:2020-02-03 Published:2020-10-20 Online:2020-10-20
Contact: YANG Yong, professor. E-mail: yangyong@mail.sic.ac.cn.
About author:CHENG Qin(1994-). female, Master candidate. E-mail: cq18817206957@163.com.
Supported by:
National Key Research and Development Project(2017YFB0310600);Shanghai International Science and Technology Cooperation Fund(17520711700);Shanghai International Science and Technology Cooperation Fund(18520744200)

摘要/Abstract

摘要：

具有类酶活性的无机纳米材料因其高稳定性和高灵敏度而具有广阔的应用前景, 因而调节其类酶活性对于促进纳米酶的发展具有重要意义。本研究通过简单的液相还原法合成了具有良好均匀性和稳定性的Pt-Au枝状纳米颗粒(Pt-Au DNPs), 研究了动力学参数与纳米颗粒结构之间的关系, 发现Pt-Au DNPs的组成和结构对其类氧化酶活性有很大影响。同时利用其类氧化酶活性催化TMB(3,3′,5,5′-四甲基联苯胺)氧化来比色检测抗坏血酸(AA)。对AA的定量分析结果显示, 在1~15 μmol/L范围存在良好的线性关系, 检出限为78 nmol/L。同时, 发现虽然连续反应会降低Pt-Au DNP的催化性能, 但其仍具有重复使用的潜力, 这在可视化检测AA中并不常见。这项研究不仅提出了合成Pt-Au DNPs的方法, 而且还显示了其在生物样品中进行AA含量分析的潜在应用前景。

关键词: Pt-Au DNPs, 类氧化酶活性, 比色法, 检测抗坏血酸

Abstract:

Due to high stability and sensitivity, inorganic nanomaterials with enzyme-like activity have brilliant application prospects. Tuning the enzyme-like activity plays great significance for promoting the development of nanozymes. In this work, Pt-Au dendritic nanoparticles (Pt-Au DNPs) with good uniformity and stability were synthesized by a simple liquid phase reduction method, and used to colorimetrically detect ascorbic acid (AA) by using their oxidase-like activity to catalyze the oxidation of TMB (3,3′,5,5′-tetramethylbenzidine). The oxidase-like activity was found to be highly influenced by the composition and structure of Pt-Au dendritic nanoparticles, and the relationship between kinetic parameters and nanoparticle structure was investigated. Quantitative analysis of ascorbic acid in the 1-15 μmol/L range was performed with good linear relationship, and the detection limit was 78 nmol/L. At the same time, it’s found that continuous reaction would reduce the catalytic performance of Pt-Au DNPs, but still has the potential to be reused, which is not common. Data from this research not only suggests a method for synthesizing Pt-Au DNPs, but also shows its potential for AA analysis in biological samples.

Key words: Pt-Au dendritic nanostructure, oxidase-like activity, colorimetric method, ascorbic acid

中图分类号:

TQ174

程琴, 杨勇, 杨莉莉. 具有高类氧化酶活性的铂-金枝状纳米粒子用于检测抗坏血酸[J]. 无机材料学报, 2020, 35(10): 1169-1176.

CHENG Qin, YANG Yong, YANG Lili. Pt-Au Dendritic Nanoparticles with High Oxidase-like Activity for Detection of Ascorbic Acid[J]. Journal of Inorganic Materials, 2020, 35(10): 1169-1176.

图/表 22

Fig. 1 (a) SEM and (b) TEM images of the as-synthesized Pt-Au DNPs (after 20 min reaction); (c) HRTEM image, (d) STEM image and EDS mapping for Au, Pt elements distribution of one single Pt-Au nanoparticle (d-1: Au and d-2:Pt)

Fig. 2 TEM images of Pt-Au DNPs prepared for at (a) 5, (b) 10, (c) 20, and (d) 40 min

Fig. 3 TEM images of Pt-Au DNPs obtained by adding different concentrations of HCl (a) 0wt%; (b) 18.5wt%; (c) 37%wt%

Fig. 4 TEM images of Pt-Au DNPs obtained with different concentrations of PVP (a) 0.0187 mol/L; (b) 0.0375 mol/L; (c) 0.0750 mol/L

Fig. 5 UV-visible absorption spectra of different systems

Fig. 6 Effects of different experimental conditions on the oxidase-like activity of Pt-Au DNPs. The Absorbance spectra and visual color changes of TMB in presence of different (a) Pt-Au DNPs concentration, (b) pH, (c) time, (d) temperature, respectively, with insets showing the corresponding photos of the reaction solutions

Fig. 7 (a) Michaelis-Menten curve and (b) Lineweaver-Burk plots of Pt-Au DNPs with TMB concentration ([TMB])

Fig. 8 Time-dependent absorbance for (a) Pt-Au DNPs catalyzed TMB oxidation in the presence of different concentrations of AA and (b) ox-TMB reduced by AA

Fig. 9 (a) Dose-response curve for different concentrations of AA standard solutions, with inset showing the linear calibration plot for AA, and (b) interference of different interfering substances in the AA detection, all interfering substances were at a concentration of 25 μmol/L

Fig. S1 EDS elemental analysis of Pt-Au DNPs

Fig. S2 XRD pattern Pt-Au DNPs

Fig. S3 Color change of the solution with different concentration of HCl after reaction for 5 min

Fig. S4 FT-IR spectra of Pt-Au DNPs

Fig. S5 TMB oxidation catalyzed by different NPs

Fig. S6 TMB oxidation catalyzed by Pt-Au NPs with different Au/Pt ratio

Fig. S7 Effect of preparation conditions on values of Michaelis constant for TMB oxidation

Fig. S8 (a) Pt-Au DNPs continuously catalyzed the oxidation of TMB (each time incubation for 10 min after reducing ox-TMB by AA, with the fourth time showing the result of centrifugal washing of Pt-Au DNPs before incubation), and (b) linear calibration curve for AA after 20 min of TMB second oxidation

Fig. S9 Evolutions of the absorption of AA at 264 nm over time with and without Pt-Au DNPs

Fig. S10 Linear calibration plot for AA of Pt-Au NPs

Table S1 Detection of AA in real juice sample

Sample	Added/(μmol·L^-1)	Found/(μmol·L^-1)	Recovery/%	RSD/(%, n=3)
Juice	0	5.53	-	4.1
	3.12	8.86	103.71	3.2
	6.25	12.01	103.68	3.4

Table S2 Comparative table of steady-state kinetic parameter for Pt-Au DNPs and other materials

Catalyst	Substrate	K_m/(mmol·L^-1)	Ref.
BiW₉Cu₃	TMB	0.29	[1]
CeO₂		0.8-3.8	[2]
Hg^2+/Citrate-AgNPs		0.23	[3]
N-CQDs		0.515	[4]
Cu-Ag/rGO		0.634	[5]
Cu NPs		1.047	[6]
Lysozyme-PtNPs		0.63	[7]
Fe₃O₄@C		0.38	[8]
Pt-Au DNPs		0.22	This work

Table S3 Comparison of earlier reports for the AA detection.

Catalyst	Linear range/(μmol·L^-1)	LOD/(μmol·L^-1)	Ref.
FeCo NPs@PNC	0.5-28	0.38	[9]
N-CQDs	5-40	1.773	[4]
Cu-Ag/rGO	1-30	3.6	[4]
Cu NPs	1-10	0.68	[6]
LaF₃:Ce,Tb	8-10	2.4	[10]
CuO/Pt	1-600	0.796	[11]
MIL-88	2.57-10.1	1.03	[12]
Pt-Au DNPs	1-15	0.078	This work

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具有高类氧化酶活性的铂-金枝状纳米粒子用于检测抗坏血酸

Pt-Au Dendritic Nanoparticles with High Oxidase-like Activity for Detection of Ascorbic Acid

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