Cobalt-doped MoS2 nanocomposite with NADH oxidase mimetic activity and its application in colorimetric biosensing of NADH
Graphical abstract
Introduction
Enzyme, as a protein with specific catalysis and high efficiency, is involved in almost all metabolic reactions in vivo and controls substance metabolism mainly through the regulation of enzymatic activity [1,2]. However, for most enzymes, they experience in-stability, low repeatability and high-cost [[3], [4], [5]]. In 2007, Yan et al. discovered that Fe3O4 nanoparticles can simulate peroxidase [1,6]. Since then, a great deal of work has begun to investigate nanomaterials to simulate natural enzymes [7,8], which have been applied in detection [9,10,79], pollution control and cancer therapy [[11], [12], [13]]. Most nanozyme designs are based on the active center of natural enzymes [14]. Nanozymes have become research hotspot, because they have high catalytic activity and stable characteristics as well as scale-up synthesis [4,15,16]. To date, a wide range of nanozymes, for example, noble metals including gold nanoparticles (NPs) [[17], [18], [19], [20]], AgNPs [21] and PtNPs [22], gold nanoplates [19] and Au@Ag heterogeneous nanorods [23], metal oxide NPs (Co3O4 NPs [24,25], V2O3 NPs [26], NiO NPs [27], MnO2 [[28], [29], [30]], Copper-based nanoclusters [31,32]), functionalized porous carbon [33,34] and nanocomposites [35] were reported. Nanozymes can be roughly divided into oxidordeuctase (e.g., peroxidase [36,38], oxidase [39], superoxide dismutase (SOD) [40,41]and catalase [42]), hydrolase (e.g., phosphatase [43]) and lyase (photolyase [44]) as well as synthetase [45].
Nicotinamide adenine dinucleotide (NAD+) is an important redox cofactor that participates in a variety of biotransformation systems and drive decomposition and synthesis reactions. The catabolism of main nutrients (sugar, fat and protein) is inseparable from NAD+. On one hand, it requires NAD+ (polyadenylate-ribosylation) to repair DNA damage. Thus, the bioactive NAD+ regeneration is of great value to most dehydrogenase mediated reactions [20,[46], [47], [48], [49], [50], [51], [52], [53]]. The higher NAD(H) (the reduced form of nicotinamide adenine dinucleotide) or NADH/NAD+ ratio indicates that the cell respiration consumes more oxygen and is in a state of peroxidation. A higher ratio of NADH/NAD+ can also inhibit glycolysis and tricarboxylic acid cycling. On the other hand, many diseases are closely related to NADH levels. Therefore, the detection NADH holds significance. The traditional colorimetric NADH detection method, based on the characteristic peak wavelength at 340 nm, has great limitations, which is vulnerable to the interference from similar substances with ultraviolet absorption in the sample solution [54]. NADH detection kits are convenient and rapid, nevertheless, they are relatively expensive. To date, a variety of nanocomposites based electrochemical sensors have realized the detection of NADH [[55], [56], [57], [58], [59]], however, they are time-consuming. To this end, it has great potential to develop nanozymes based colorimetric sensor for NADH.
NADH oxidase (NOX) is an oxidoreductase that can catalyze the oxidation of NADH [60]. In the presence of O2, the NOX is capable of catalyzing the oxidation of NADH to NAD+ and reducing O2 to H2O or H2O2 [[61], [62], [63]]. That is, NOX could be an important target for regulating the proportion of NADH/NAD+ [[64], [65], [66]]. Natural NOX is widely present in lactic acid bacteria [67,68]. Nevertheless, the process of isolation and purification NOX from microorganisms is complex and cost-ineffective. To overcome this challenge, it is of great advantage to simulate NOX activity by simple synthesizing nanozyme. MoS2 nanoparticles can mimics peroxidase [69,70]. The doping of P, Al, Ni and other elements in MoS2 was reported to enhance the activity of mimic enzymes [71,72]. Further, MoS2 is an excellent catalyst for hydrogen evolution reaction [73]. However, there is no report on cobalt-doped MoS2 (Co-MoS2) nanomaterials exhibiting NADH oxidase activity.
In this work, we report on the Co-MoS2 nanocomposite to simulate NADH oxidase. In addition, the catalytic mechanism of the nanozyme is investigated in detail. Finally, by conjugating cascade reaction of NOX mimics and horseradish peroxidase (HRP), a sensitive and selective colorimetric sensor for NADH is proposed based on the characteristic peak of 652 nm.
Section snippets
Chemicals
NAD+, NADH, FAD+ (flavin adenine dinucletide), NADP+ (nicotinamide adenine dinucleotide phosphate), NADPH (the reduced form of NADP+) were obtained from Solarbio Bioscience &Technology Co., Ltd (Shanghai, China). Glucose, ascorbic acid (AA), uric acid (UA), H2O2 (30 % wt in water), glycine (Gly), serine (Ser), methionine (Met), lysine (Lys) and glutathione (GSH) were bought from Sinopharm Chemical Co., Ltd (Shanghai, China). SOD and HRP were bought from Biozyme Laboratories.
Preparation and characterization of Co-MoS2
Co-MoS2 was synthesized by simple hydrothermal method. The morphology of Co-MoS2 was characterized by SEM, as shown in Fig. 1A. The synthesized particles presented an irregular structure with the average particle size of ∼ 400 nm. The elemental mapping verified the presence of all of the expected elements (Co, Mo and S), and also showed that all the elements were distributed evenly on the nanoparticle, as seen in Fig. 1B–F.
In addition, XPS was made a qualitative analysis of the chemical
Conclusion
In summary, we used the simple hydrothermal method to prepare Co-MoS2 nanocomposite, which exhibited simulating NADH oxidase activity with good stability and resuability. The catalytic mechanism of the nanozyme is that O2 participates in the process of the NADH oxidation reaction mediated by Co-MoS2, which generates O2.− intermediate, finally becomes H2O2. Furthermore, the colorimetric NADH sensor was established by using the cascade reaction of NADH oxidase combined with HRP, which showed
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work was financially supported by National Natural Science Foundation of China (Nos. 81673172, 51502036) and Natural Science Foundation of Distinguished Young Scholars for Fujian Province (2019J06015).
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2022, Journal of Electroanalytical ChemistryCitation Excerpt :To address these issues, researchers have used various means to modify the electrode surface to reduce the overpotential for NADH oxidation. For example, various nanomaterials have been developed for the electrocatalytic oxidation of NADH, including Nanostructure TiO2 [7], nitrogen-doped carbon quantum dots/tin oxide (NCQDs/SnO2) nanocomposite [8], WS2 Nanosheets [9], Cobalt-doped MoS2 nanocomposite [10]. However, these studies have high NADH oxidation overpotential.