Regular ArticleGold nanoparticles-decorated silver-bipyridine nanobelts for the construction of mediatorless hydrogen peroxide biosensor
Graphical abstract
Introduction
Electrochemical enzyme biosensors are widely employed as highly selective analytical tools for biomedical, food quality assurance, clinical diagnosis and environmental monitoring [1], [2]. In general, most of these biosensors devices need the use of electrochemical mediators to act as artificial electron transferring agents between the enzyme redox centre and the electrode surface. These mediators allow reduction of the overpotential and, accordingly, minimization of potential interferences during measurement [3], [4]. However, the use of electrochemical mediators implies somewhat complex electrode architectures, or even worse, the addition of these mediators to the measuring solution. Therefore, the design of novel nanostructured 3D transducer elements with improved electron transfer and electrocatalytic properties is a key factor to assemble simple, reliable and cost-effective third-generation enzyme biosensors.
Gold nanoparticles (AuNP) have been extensively employed in the preparation of electrochemical enzyme biosensors due to their unique characteristics such as high electroconductivity, surface energy and surface-to-volume ratio, electrocatalytic properties, ability to decrease proteins-metal particles distance, and the possibility to act as electroconductive wires between the electrode surface and the enzyme active site allowing direct electron transfer through a tunnelling mechanism [5]. In addition, tailor-made combination of AuNP with other micro- and nanosized materials has provided a large variety of advanced hybrid nanomaterials and nanocomposites with new and synergic properties for biosensing purposes [6], [7], [8].
AuNP have been directly employed as transducer elements in enzyme biosensor by modification of the electrode surface via covalent attachment, electrodeposition, electrostatic adsorption, electropolymerization or supramolecular association [9], [10], [11], [12]. On the other hand, a great variety of functional biosensor interfaces has been designed by combining gold nanoparticles with carbon nanotubes [6], [13], graphene derivatives [14], [15], electroconductive polymers [7], dendrimers [16], metal and metal oxide nanostructures [12], [17], [18], polysaccharides [19], etc.
In this work we describe the synthesis of original bi-functionalized AuNP capped with 4-mercaptopyridine and 6-mercapto-1-hexanol residues, and its further use to prepare novel AuNP-decorated coordination polymer nanobelts by reaction with 4,4′-bipyridine and Ag+ ions. This nanohybrid was successfully employed as wiring material for horseradish peroxidase (HRP, EC 1.11.1.7) to construct a highly sensitive mediatorless enzyme biosensor for hydrogen peroxide. The rational of this research is supported by the well-known electrocatalytic properties of AuNP [20], [21] and silver:bipyridine coordination polymers-based nanostructures [22], allowing us to envision a synergic electrocatalytic capacity for the resulting nanohybrid.
On the other hand, hydrogen peroxide was selected as target analyte due to its function as essential mediator in biology, medicine and chemistry, as well as its environmental impact as industrial waste. In addition, H2O2 is a by-product of highly selective oxidases commonly employed in enzyme biosensor design [23].
Section snippets
Reagents and apparatus
Horseradish peroxidase (HRP, Type II, 105 U/mg), HAuCl4, NaBH4, AgNO3, 4-mercaptopyridine, 6-mercapto-1-hexanol and 4,4′-bipyridine were purchased from Sigma (USA). All other chemicals were of analytical grade.
Transmission electron microscopy (TEM) and high resolution field emission scanning electron microscopy (FE-SEM) were performed with JEOL JEM 2100 and JEOL JSM-6335F microscopes, respectively (JEOL Ltd., Japan). X-ray photoelectron spectroscopy (XPS) analysis was performed with a SPECS GmbH
Results and discussion
The steps involved in the preparation of the hybrid nanomaterial and the HRP enzyme electrode is illustrated in Scheme 1. Gold colloids were first grown in the presence of two different thiol ligands, 4-mercaptopyridine and 6-mercapto-1-hexanol, yielding dark red1 and water soluble nanoparticles. The bi-functionalized AuNP particles showed spherical geometry with an average diameter of 2.7 ± 0.9 nm,
Conclusions
A novel hybrid nanomaterial based on silver:bipyridine nanobelts decorated with bi-functionalized AuNP was prepared. In contrast to previously reported non-doped nanomaterial [22], this nanohybrid showed interesting fern-like fractal morphology. The electrocatalytic activity toward H2O2 was also noticeably improved, and accordingly, this new nanohybrid was employed to construct a mediatorless enzyme biosensor able to detect the analyte at picomolar levels. The biosensor exhibited a superior
Acknowledgements
Financial support from the Spanish Ministry of Economy and Competitiveness CTQ2014-58989-P, CTQ2015-71936-REDT, CTQ2015-64402-C2-1-R and Comunidad de Madrid S2013/MIT-3029, Programme NANOAVANSENS is gratefully acknowledged.
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