Electrochemical Characterization and Electroanalytical Aplications of RGO_AuNPs Hybrids

A novel synthetic route for the synthesis of gold nanoparticles (AuNPs) modified graphene electrodes has been developed: Reduced Graphene Oxide (RGO) sheets are functionalized with pyrene linkers acting as growing sites for gold nanoparticles (AuNPs) of different dimensions (approximatively 5, 10 and 20 nm). The Au surface is functionalized with oleylamine or 3,4-dimethylbenzenethiol as capping agents. The hybrid material is deposited onto Carbon Screen Printed Electrodes (C-SPEs) for a deep physico-chemical and electrochemical characterization, using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) measurements. The role played by every single hybrid counterpart has been investigated, showing a synergistic effect, which is responsible of the enhancement of the system properties. The charge transfer from gold nanoparticles to graphene, assisted and stimulated by the pyrene linker, seems to be the key point to understand the peculiarities of this innovative material. The as prepared RGO-AuNPs hybrids have been used in the electroanalytical detection of both inorganic and organic species (arsenic, H2O2, dopamine), showing promising results in terms of sensitivities and detection limits. In particular, regarding the detection of the neurotransmitter dopamine by means of Differential Pulse Voltammetry in Phosphate Buffer Solution, a LOD of (3.3 \ub1 0.2) ppb has been reached, comparable with other electroanalytical results in the literature and in accordance with the benchmark for this molecule [1]. For arsenic detection, the hybrid devices show increased performances in comparison with bare gold or gold NPs, also allowing speciation between arsenic (III) and (V), appropriately adjusting the experimental conditions. In the case of H2O2, the hybrid devices display high electrocatalytic activity and fast electron-transfer kinetics, representing an ideal platform for developing oxidoreductase-based electrochemical biosensors as well as for detecting H2O2 in real samples. [1] J.A. Ribeiro, P.M.V. Fernandes, C.M. Pereira, F. Silva, Talanta 160 (2016) 653-679

Enhanced performances of RGO-AuNPs hybrids towards electroanalytical applications

In recent years, lot of attention has been devoted to understanding the properties of hybrid nanocomposites, \u201cbrave new materials\u201d made of two or more organic and inorganic components. These systems show enhanced or novel physico-chemical properties with respect to the single components, resulting not only from the sum of the precursors\u2019 ones, but also from interactions occurring at their interface, the so-called \u201cheterojunction\u201d. However, a remaining challenge is to understand in depth the phenomena here originating. In the present work, to start fulfilling this gap, a deep electrochemical study of hybrids made of Reduced Graphene Oxide (RGO) and Au nanoparticles (NPs) is performed, analysing carefully the role played by each single component of the material on the electrochemical properties. In more details, RGO platforms are surface functionalized with 1-aminopyrene or 1-pyrene carboxylic acid that act as heteronucleation and growing sites of the amine- or thiol-coated Au NPs of different dimensions (from 3 to 20 nm). At first, Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) measurements are carried out in order to characterize the different hybrids. Then, the materials are applied as electroanalytical sensors for both organic and inorganic molecules (dopamine and As, respectively) with very promising results, comparable or even better than analogous systems reported in literature. Moreover, preliminary tests on H2O2 detection open the venue to the application of these materials in biosensor applications. The properties of the hybrid nanocomposite, enhanced with respect to those of the single components, are ascribed to charge transfer occurring at the heterojunction from the Au NPs to the RGO, assisted and channelled by the pyrene linker

Ascorbic acid-sensitized Au nanorods-functionalized nanostructured TiO2 transparent electrodes for photoelectrochemical genosensing

Au nanorods (NRs) modified nanostructured TiO2/ITO electrodes have been fabricated and characterized in order to develop a biosensing platform for the photoelectrochemical determination of microRNAs. The proposed method is based on the use of thiolated DNA capture-probes (CPs) immobilized onto Au NR surface. The Au NRs are chemically bound at the surface of TiO2/ITO electrodes by means of the mercaptosuccinic acid linker. Subsequently, the DNA CPs are bound to the Au NR surface through the thiolate group, and reacted with the target RNA sequence. Finally, the obtained biosensing platform is incubated with alkaline phosphatase and l-ascorbic acid 2-phosphate (AAP) enzymatic substrate, for the in situ generation of ascorbic acid (AA). Such AA molecule, coordinating to surface Ti atoms, generates a charge transfer complex, that results in a shift of the UV absorption threshold toward the visible spectral region of the nanostructured TiO2 forming the electrode and, hence, in the occurrence of an absorption band centered at 450\u202fnm. The photoelectrochemical monitoring of the formation of the AA-TiO2 complex, under the visible light of a commercial LED light source, allows the selective and quantitative detection of the target microRNA strands

Electroanalysis may be used in the Vanillin Biotechnological Production

This study shows that electroanalysis may be used in vanillin biotechnological production. As a matter of fact, vanillin and some molecules implicated in the process like eugenol, ferulic acid, and vanillic acid may be oxidized on electrodes made of different materials (gold, platinum, glassy carbon). By a judicious choice of the electrochemical method and the experimental conditions the current intensity is directly proportional to the molecule concentrations in a range suitable for the biotechnological process. So, it is possible to imagine some analytical strategies to control some steps in the vanillin biotechnological production: by sampling in the batch reactor during the process, it is possible to determine out of line the concentration of vanillin, eugenol, ferulic acid, and vanillic acid with a gold rotating disk electrode, and low concentration of vanillin with addition of hydrazine at an amalgamated electrode. Two other possibilities consist in the introduction of electrodes directly in the batch during the process; the first one with a gold rotating disk electrode using linear sweep voltammetry and the second one requires three gold rotating disk electrodes held at different potentials for chronoamperometry. The last proposal is the use of ultramicroelectrodes in the case when stirring is not possible

Alkaline-phosphatase-based nanostructure assemblies for electrochemical detection of microRNAs

Different nanoarchitectures, rich in enzyme labels, are herein investigated for signal amplification in the electrochemical detection of nucleic acids and in particular of microRNAs. Dendritic amplification, accomplished by the use of streptavidin and biotinylated alkaline phosphatase, and enzymedecorated liposomes are used as labels to amplify the microRNA-sensing, by their association to the probe-microRNA hybrid generated onto a gold transducer. Differential pulse voltammetry and faradaic impedance spectroscopy were employed to characterize these different amplification routes

Electrochemical and photoelectrochemical biosensors for biomarker detection

A rapid and accurate medical diagnosis is essential in order to determine the health status of a patient. Nowadays, most of the clinical analyses are performed in specialized laboratory, which required specific instrumentation and trained personal, resulting in an increase of analysis costs and time. In this context, biosensors represent ideal tools capable to provide a specific and fast response together with low cost, easy use and portable size features. This work attempts to provide a review of the research progresses of electrochemical and photoelectrochemical biosensor platforms in clinical applications that have been published in recent years. Special emphasis will be devoted to discuss examples for breast cancer biomarker detection, because breast cancer, is considered the leading cause of cancer-related deaths worldwide in women, representing 15% of all cancer related amongst women, with a 6% mortality rate (based on overall cancer deaths). The manuscript is focused on aptamer-based biosensors, because, due to their stability and their relatively low cost, they have been successfully applied in many biosensor formats for breast cancer biomarker detection

Label-free impedimetric determination of miRNA using biotinylated conducting polymer modified carbon electrodes

Preliminary results are reported on label-free miRNA determination with faradaic electrochemical impedance spectroscopy (EIS) measurements on glassy carbon electrodes (GCEs) and screen-printed carbon electrodes (SPCEs). These electrodes were coated with films of functionalized conducting polymers. For that, bis(2,2\u2032-bithien-5-yl)-(4-hydroxyphenyl)methane biotin ester was used as the functional monomer. This monomer was potentiodynamically electropolymerized to result in deposition of thin polymer films on the electrodes. Next, streptavidin, and then the biotinylated DNA capture probe were immobilized via streptavidin\u2013biotin interactions. Detectability of the resulting biosensor with respect to the complementary miRNA was well below 100 pM

Electrochemical bioassay for the detection of TNF-a using magnetic beads and disposable screen-printed array of electrodes

In this study we have developed an electrochemical bioassay for the analysis of TNF-a, coupling magnetic beads with disposable electrochemical platforms. TNF-a is a pro inflammatory cytokine that participates in the regulation of immune defense against various pathogens and the recovery from injury. It plays a central role in the development of many inflammatroy diseases. The bioassay was based on a sandwich format using alkaline phosphatase as an enzymatic label and an eight -sensor screen-printed array as an electrochmical transducer.Bettazzi, F.; Enayati, L.; Campos Sánchez, I.; Motaghed, R.; Mascini, M.; Palchetti, I. (2013). Electrochemical bioassay for the detection of TNF-a using magnetic beads and disposable screen-printed array of electrodes. Bioanalysis. 5(1):11-19. doi:10.4155/BIO.12.293S11195