Nickel metal-organic framework 2D nanosheets with enhanced peroxidase nanozyme activity for colorimetric detection of H2O2

doi:10.1016/j.talanta.2018.06.075

Talanta

Volume 189, 1 November 2018, Pages 254-261

https://doi.org/10.1016/j.talanta.2018.06.075 Get rights and content

Highlights

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Two-dimensional Ni-MOF nanosheets were synthesized using a one-step solvent-thermal method.
•
Ni-MOF nanosheet was used as a peroxidase mimetic to catalyze oxidation of TMB in the presence of H₂O₂.
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The H₂O₂ colorimetric sensor deserves a low detection limit, high sensitivity and wide linear range.
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The H₂O₂ colorimetric sensor showed excellent performance in practical sample analysis.

Abstract

A two-dimensional (2D) Ni based metal-organic framework (MOF) nanosheets were synthesized using a one-step solvent-thermal method. The as-prepared nanosheets were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and energy disperse spectroscopy (EDS) mapping. Ni-MOF nanosheet was first time found to used as a peroxidase mimetic with catalytic activities and could catalyze the oxidation of the substrate 3,3,5,5-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂). Catalytic mechanism analysis suggested the enzymatic kinetics of Ni-MOF nanosheets followed typical Michaelis-Menten theory and Ni-MOF nanosheets possess a higher affinity for two substrates (TMB and H₂O₂) than horseradish peroxidase (HRP). Furthermore, Ni-MOF nanosheet was applied to establish an H₂O₂ colorimetric sensor which deserves a wide linear range of 0.04 ~ 160 μM and a low detection limit of 8 nM. Also the application of this sensor for H₂O₂ detection in human serum and disinfectant was demonstrated and satisfactory results were obtained. Thus, the simple and sensitive Ni-MOF/TMB/H₂O₂ colorimetric system has great promising applications in clinical medicine and food environment analysis.

Graphical abstract

Introduction

Ultrathin two-dimensional layered nanomaterials are attracting remarkable attentions in recent years. Compared with other nanomaterials, 2D ultrathin nanomaterials hold some great unique characteristics. For instance, ultrathin thickness enables ultrathin 2D nanomaterials deserve greatly compelling electronic properties due to the electron confinement without interlayer interactions [1]. Moreover, the large lateral size of ultrathin 2D nanosheets endow them with ultrahigh specific surface area [2]. 2D MOF nanosheets as a new member of ultrathin 2D nanomaterials family have also generated great interest [3]. MOFs are crystalline porous material derived from metallic centers bonded by polytopic organic ligands. The metallic centers are inorganic units which can be metal ions or clusters. The change of metal ions, organic ligands, or structural motifs can realize the specific functionality of MOFs [4]. MOFs are characterized by tunable and highly ordered structures. What's more, like other 2D nanosheets, MOF nanosheets possess many highly exposed active sites and electrons can quickly transfer on their surface, which could be significant for the gas storage, sensing, separation and catalytic applications [5], [6], [7], [8], especially, they have been widely used to catalyze organic reactions [9].

H₂O₂ is an incompletely reduced metabolite of oxygen, almost all oxidases in mitochondria can produce H₂O₂·H₂O₂ can diffuse out freely through membranes between various cellular compartments and has a diversified physiological and pathological effects within living cells [10], [11]. Thus, maintaining H₂O₂ at a proper level plays an important role in intracellular signaling transduction and normal cell functions [12], [13]. While imbalances production of H₂O₂ are able to damage tissue and organ systems and also cause complications of many diseases, especially diabetes, cardiovascular and neurodegenerative diseases, as well as cancer [14], [15]. Because H₂O₂ is one of the reactive oxygen species (ROS) and generates free hydroxyl radicals [16], which cause oxidative damage to the tissue components such as lipids, proteins and DNA [17]. The higher the concentration, the greater the impact. So, in order to better understanding the biological effects of H₂O₂, it is critically important to carry out the rapid, sensitive and accurate determination of H₂O₂ in biological environment.

For the measurement of H₂O₂ in biochemical analysis, several sensitive methods have been developed for this purpose, such as liquid chromatography [18], chemiluminescence [19], [20], fluorescence [21], [22], electrochemical techniques [23], [24], and colorimetric assay [25]. Among these analytical techniques, colorimetric assay has drawn huge attention due to its pretty simplicity, low cost as well as practicality. In addition, this colorimetric method for the detection of analytes can be interpreted by naked eyes to realize visual detection without any instrumentation [25]. The activity of natural enzyme is destined to suffer from various environmental factors [26]. Moreover, compared with natural enzymes, artificial enzymes have great advantages, such as better design flexibility, high efficiency and substrate specificity, especially their excellent stability. Therefore, it is very important for scientists to pay more efforts to develop effective mimetic enzymes based on colorimetric methods for biosensing and pharmaceutical processes.

In this work, we synthesized ultrathin 2D Ni-MOF nanosheets by a simple solvothermal method and the nanosheet showed remarkable peroxidase-like activity owing to its ultrahigh specific surface area and numerous active sites. The obtained Ni-MOF nanosheets possess good dispersity and stability. Thus, we employed Ni-MOF nanosheet as a peroxidase mimetic to develop a colorimetric detection

method of H₂O₂ with TMB as peroxidase substrate (Scheme 1). Ni-MOF nanosheets can rapidly catalyze oxidization of TMB into a blue product in the presence of H₂O₂ which can be observed by the naked eye. The Ni-MOF nanosheets were demonstrated to have high affinity to the peroxidase substrate (TMB). The simple Ni-MOF nanosheets based colorimetric platform exhibited good sensitivity and high selectivity for H₂O₂ detection. Furthermore, the colorimetric method was applied to the detection of H₂O₂ levels in human serum and disinfectant samples with satisfactory results, suggesting its great potential for biocatalysis and bioassays in the future.

Section snippets

Reagents and apparatus

TMB were commercially available from Sigma-Aldrich. All other reagents were purchased from Sinopharm Chemical Reagent Shanghai Co., Ltd., All aqueous solution was prepared by deionized water throughout the experiments.

Apparatus and characterization

Field emission scanning electron microscopy (FESEM) images and transmission electron microscopy (TEM) images of the Ni-MOF nanosheet were obtained by a Zeiss, Supra 55 instrument and JEM-2100 instrument (operated at an acceleration voltage of 200 kV), respectively. Tecnai G² F30

Characterization of Ni-MOF nanosheet

The morphology and microstructure of Ni-MOF nanosheet were characterized with SEM and TEM. From Fig. 1, it can be seen that the structure of Ni-MOF was loosely packed nanosheets. The high-magnification SEM image (Fig. 1B) further revealed that the surface of Ni-MOF nanosheet was uniform and smooth. The fact that the synthesized product was composed of nanosheets was proved by a detailed examination with high-resolution TEM (Fig. 1D), and the nanosheets were very transparent.

As shown in Fig. 2B,

Conclusion

In summary, we synthesized 2D Ni-MOF nanosheets by a simple solvothermal method. The as-prepared Ni-MOF nanosheets showed high catalytic activity for TMB oxidation in presence of H₂O₂. Catalytic mechanism analysis indicated the enzymatic kinetics of Ni-MOF nanosheets follow typical Michaelis−Menten theory. Furthermore, the catalytic activity of Ni-MOF was strongly dependent on pH and temperature. On this basis, a simple, highly selective and sensitive colorimetric sensor for detection of H₂O₂

Acknowledgements

We gratefully acknowledge the financial support from the NSFC (Nos. 21705141, 21275124, 21275125, 21575124 and 21675140), Jiangsu Planned Projects for Postdoctoral Research Funds (1601075C), Postdoctoral Science Foundation of China (2016M601897), PAPD and TAPP of Jiangsu Higher Education Institutions, the High-end Talent Project of Yangzhou University, the 14th Six talent peaks project in Jiangsu Province (SWYY-085), Higher Education Outstanding Scientific and Technological Innovation Team of

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Nickel metal-organic framework 2D nanosheets with enhanced peroxidase nanozyme activity for colorimetric detection of H2O2

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Reagents and apparatus

Apparatus and characterization

Characterization of Ni-MOF nanosheet

Conclusion

Acknowledgements

Chin. Chem. Lett.

J. Biol. Chem.

Int. J. Pharm.

Talanta

Sensor Actuat. B-Chem.

Sens. Actuat. B-Chem.

Biotechnol. Adv.

Anal. Chim. Acta

Biosens. Bioelectron.

Electrochim. Acta

Talanta

J. Nanopart. Res.

Sens. Actuat. B-Chem.

Sens. Actuat. B-Chem.

Mat. Sci. Eng. C.-Mater.

Sensor Actuat. B-Chem.

Ultrathin two-dimensional nanomaterials

ACS Nano

Ultrathin nickel-cobalt phosphate 2D nanosheets for electrochemical energy storage under aqueous/solid-state electrolyte

Adv. Funct. Mater.

Metal–organic framework nanosheets in polymer composite materials for gas separation

Nat. Mater.

The chemistry and applications of metal-organic frameworks

Science

Ultrathin 2D metal-organic framework nanosheets

Adv. Mater.

Hydrogen storage in microporous metal-organic frameworks with exposed metal sites

Angew. Chem.

Ni and NiO nanoparticles decorated metal–organic framework nanosheets: facile synthesis and high-performance nonenzymatic glucose detection in human serum

ACS Appl. Mat. Inter.

Applications of metal-organic frameworks in heterogeneous supramolecular catalysis

Chem. Soc. Rev.

Dumbbell-like PtPd-Fe3O4 nanoparticles for enhanced electrochemical detection of H2O2

Nano Lett.

Nickel metal-organic framework 2D nanosheets with enhanced peroxidase nanozyme activity for colorimetric detection of H₂O₂

Dumbbell-like PtPd-Fe₃O₄ nanoparticles for enhanced electrochemical detection of H₂O₂