One-step fabrication of trimetallic alloy nanozyme catalyzer for luminol-H2O2 chemiluminescence and its application for miRNA-21 detection coupled with miRNA walking machine
Introduction
Noble metals, such as gold (Au), silver (Ag), palladium (Pd) and platinum (Pt) have been applied in oxygen reduction reaction catalysts [1], surface-enhanced Raman spectroscopy [2], fuel cells catalysts [3] and sensors [4] due to their unique catalytic and biocompatible properties. Pt nanomaterial, a typical noble-metal, has been extensively investigated in the application of methanol oxidation reaction [5] and hydrogen oxidation reaction [6] of fuel cells. Although Pt has been considered as a relatively common and effective nanomaterial in the field of catalysis, the sky-rocketing price, limited supply and low durability impedes its widespread practical application [7].
To reduce the cost and maintain the stability of Pt catalyst, many strategies have been used to explore novel Pt catalytic materials with low Pt contents. The one commonly adopted strategy is adjusted the morphologies of Pt catalyst which including nanotubes [8], nanoshells [9], nanoparticles [10], nanoclusters [11] et al. For example, nanotubes modified with Pt nanoparticles [12] or Pt monolayer [13] can decrease the amount of Pt effectively, which improving the utilization of Pt and obtaining a high catalytic activity. And the other strategies are introduced a second or third low-cost nonprecious metals to synthesize Pt-based multimetallic alloys. Compared with their monometallic components, Pt-based multimetallic alloys exhibit low consumption, high stability and catalytic activity simultaneously because of synergistic and electronic coordination effect [14]. At present, a great many of Pt-based alloys have been fabricated and extensively explored. For example, Pt-based alloys, including Pt-Ni [15], Pt-Co [16], Pt-Cu [17], Pt-Fe-Co [18], Pt-Ni-Co [19] and Pt-Cu-Co-Ni [20] and so on, have been proved to be promising alternatives to pure Pt catalysts. Impressively, due to their unique properties, Pt-based alloys have been considered as a promising alternative to pure Pt catalyst for enhancing the catalytic properties especially.
Benefiting from their unique simple operation, low background, wide dynamic range, fast response, high sensitivity and no need of light excitation, chemiluminescence (CL) as a valuable analytical tool has been attracted considerable attention and widely used in modern analytical chemistry especially bioassays [[21], [22], [23], [24], [25]]. Despite its superiority, luminol-H2O2 as a typically CL system usually demands the enzymes to enhance the CL efficiency. Therefore, extensive efforts have been dedicated to explore appropriate enzymes, including horseradish peroxidase, peroxidase mimetics and nanozyme for luminol-H2O2 CL system [26,27]. Compared with those native enzymes, nanozyme catalyzer has not only intrinsic peroxidase-like activity but also higher sensitivity and stability for enhancing luminol-H2O2 CL system [28,29].
Because the abnormal expression levels of microRNAs (miRNAs) often foreshadows the occurrence of disease, miRNAs act as critical effects in early clinical diagnosis and cancer therapy [30,31]. Therefore, it is significant to detect miRNAs in early prediction. However, it is still a challenge for the detection of miRNAs sensitively and accurately because of short size and low abundance in cells and serum [23,32,33]. For example, the miRNA-21 is at very low concentrations (∼fM to nM) in serum samples [34].
Up to now, various signal amplification methods have been developed to detect miRNAs, including rolling circle amplification [35], cyclic enzymatic amplification method [36] and bicyclic cascade signal amplification [37] et al. In most cases, these signal amplification methods are involved enzyme to assist. Compared with the enzyme-assisted approach, the method of enzyme-free possesses unique advantages containing simple and cheap feature and the elimination of complex enzyme reaction in signal amplification. Therefore, researchers have aimed to design different walker with enzyme-free approaches for signal amplification at the gene level, and it provided an avenue for the development of gene detection [[38], [39], [40]]. For example, two-legged walker had been reported. However, the catalyst dissociation increased when the substrate of microparticle combining with two-legged walker was exhausted. To overcome this difficulty, a simpler single-legged walker with a “cleat” had been designed to prevent the walker dissociating and ensure the walker moving [41,42].
Inspired by the above ideas, a simple, facile, efficient one-step synthesis strategy was used to fabricate PtCuCo trimetallic alloys (PtCuCo-TAs). The Co and Cu as an introduced nonprecious metals with excellent catalytic property were to fabricate Pt-based multimetal alloys. Pt, Cu, Co metal nanomaterials were also respectively synthesized. PtCuCo-TAs gave the best catalyzing for luminol-H2O2 system. A CL assay based on PtCuCo-TAs-luminol-H2O2 CL system was fabricated for miRNAs detection coupling single-legged walker strategy. To our best knowledge, this is the first time that the PtCuCo-TAs was applied for catalyzing luminol-H2O2 CL system for miRNAs detection.
Section snippets
Chemicals and reagents
Potassium chloroplatinate (K2PtCl6) was provided by Sigma-Aldrich. Cobalt (II) chloride hexahydrate (CoCl2·6H2O) and Copper (II) chloride dihydrate (CuCl2·2H2O) were obtained from J&K Chemical Co., Ltd (Beijing, China). Sodium borohydride (NaBH4) and ascorbic acid were bought from Aladdin Chemistry Co., Ltd (Beijing, China). Tris-(2-carboxyethyl)-phosphine (TCEP) and Luminol (C8H7N3O2) were purchased from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Streptavidin-coated magnetic beads
Principle of the assay for the detection of miRNA-21
The principle of miRNA-21 detection was shown in Scheme 1. In this assay, H1-MB was prepared firstly. In the presence of the walker of miRNA-21, the toehold domain (black and red part) at 3′ terminus of miRNA-21 bound to the domain (black and red part) at 5′ terminus of H1 to open H1 stem portion and formed M1. Thus, the newly formed ssDNA region (blue and purple part) within H1 was exposed and then interacted with the toehold domain (blue part) of H2 when H2 was added into the solution of M1,
Conclusions
In summary, we have constructed a single-legged walker with a “cleat” on the surface of MB using miRNA-21 as trigger, which was used as an effective assay to sensitively detect target miRNA-21. Furthermore, a facile and fast method was used to synthesize PtCuCo-TAs acting as nanozyme, which had not only intrinsic peroxidase-like activity but also higher stability for enhancing luminol-H2O2 CL system. By taking advantage of both the single-legged walker and the PtCuCo-TAs nanozyme, a
CRediT authorship contribution statement
Shuyu Mei: Conceptualization, Methodology, Writing - review & editing, Formal analysis, Funding acquisition. Bingru Liu: Methodology, Data curation, Writing - original draft, Conceptualization. Xiaoli Xiong: Visualization, Investigation. Xu Hun: Supervision, Validation, Writing - review & editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declared that they have no conflicts of interest to this work.
Acknowledgments
This work was supported by National Natural Science Foundation of China (21575073, 81372810), Applied Basic Research Plan Project of Datong City, China (2018158), Laoshan Scholar Program of Qingdao University of Science and Technology (201802685), Shanxi Province University Science and Technology Innovation Project (751), Shanxi Province Innovation and Entrepreneurship Training Program for College Students (2019446), National Innovation and Entrepreneurship Training Program for College Students
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