Gabriella Sanzò

Beyond graphene : Electrochemical sensors and biosensors for biomarkers detection

Graphenes success has stimulated great interest and research in the synthesis and characterization of graphene-like 2D materials, single and few-atom-thick layers of van der Waals materials, which show fascinating and technologically useful properties. This review presents an overview of recent electrochemical sensors and biosensors based on graphene and on graphene-like 2D materials for biomarkers detection. Initially, we will outline different electrochemical sensors and biosensors based on chemically derived graphene, including graphene oxide and reduced graphene oxide, properly functionalized for improved performances and we will discuss the various strategies to prepare graphene modified electrodes. Successively, we present electrochemical sensors and biosensors based on graphene-like 2D materials, such as boron nitride (BN), graphite-carbon nitride (g-C3N4), transition metal dichalcogenides (TMDs), transition metal oxides and graphane, outlining how the new modified 2D nanomaterials will improve the electrochemical performances. Finally, we will compare the results obtained with different sensors and biosensors for the detection of important biomarkers such as glucose, hydrogen peroxide and cancer biomarkers and highlight the advantages and disadvantages of the use of graphene and graphene-like 2D materials in different sensing platforms.

Fast synthesis of platinum nanopetals and nanospheres for highly-sensitive non-enzymatic detection of glucose and selective sensing of ions

Novel methods to obtain Pt nanostructured electrodes have raised particular interest due to their high performance in electrochemistry. Several nanostructuration methods proposed in the literature use costly and bulky equipment or are time-consuming due to the numerous steps they involve. Here, Pt nanostructures were produced for the first time by one-step template-free electrodeposition on Pt bare electrodes. The change in size and shape of the nanostructures is proven to be dependent on the deposition parameters and on the ratio between sulphuric acid and chloride-complexes (i.e., hexachloroplatinate or tetrachloroplatinate). To further improve the electrochemical properties of electrodes, depositions of Pt nanostructures on previously synthesised Pt nanostructures are also performed. The electroactive surface areas exhibit a two order of magnitude improvement when Pt nanostructures with the smallest size are used. All the biosensors based on Pt nanostructures and immobilised glucose oxidase display higher sensitivity as compared to bare Pt electrodes. Pt nanostructures retained an excellent electrocatalytic activity towards the direct oxidation of glucose. Finally, the nanodeposits were proven to be an excellent solid contact for ion measurements, significantly improving the time-stability of the potential. The use of these new nanostructured coatings in electrochemical sensors opens new perspectives for multipanel monitoring of human metabolism.

Bubble electrodeposition of gold porous nanocorals for the enzymatic and non-enzymatic detection of glucose.

Au nanocorals are grown on gold screen-printed electrodes (SPEs) by using a novel and simple one-step electrodeposition process. Scanning electron microscopy was used for the morphological characterization. The devices were assembled on a three-electrode SPE system, which is flexible and mass producible. The electroactive surface area, determined by cyclic voltammetry in sulphuric acid, was found to be 0.07±0.01cm(2) and 35.3±2.7cm(2) for bare Au and nanocoral Au, respectively. The nanocoral modified SPEs were used to develop an enzymatic glucose biosensor based on H2O2 detection. Au nanocoral electrodes showed a higher sensitivity of 48.3±0.9μA/(mMcm(2)) at +0.45V vs Ag|AgCl compared to a value of 24.6±1.3μA/(mMcm(2)) at +0.70V vs Ag|AgCl obtained with bare Au electrodes. However, the modified electrodes have indeed proven to be extremely powerful for the direct detection of glucose with a non-enzymatic approach. The results confirmed a clear peak observed by using nanocoral Au electrode even in the presence of chloride ions at physiological concentration. Amperometric study carried out at +0.15V vs Ag|AgCl in the presence of 0.12M NaCl showed a linear range for glucose between 0.1 and 13mM.

A new surface plasmon resonance immunosensor for triazine pesticide determination in bovine milk: a comparison with conventional amperometric and screen-printed immunodevices

A detailed comparison was made of the analytical features of a new Surface Plasmon Resonance (SPR) immunodevice for triazine pesticide determination with those of two other amperometric (conventional and screen-printed) immunosensors and the advantages and disadvantages of the SPR method were thoroughly investigated. For conventional amperometric and screen-printed devices, “competitive” assays were used; conversely, the SPR transduction technique allowed a “direct” measurement format to be used. As far as the main analytical data are concerned, the SPR method does not seem to offer substantial advantages. Nevertheless the measurement time is much shorter and the measurement itself much easier to perform. Lastly several applications and recovery tests were carried out on bovine milk samples, before and after spiking, to check for triazine pesticides in the samples, obtaining satisfactory results.

A Flow SPR Immunosensor Based on a Sandwich Direct Method

In this study, we report the development of an SPR (Surface Plasmon Resonance) immunosensor for the detection of ampicillin, operating under flow conditions. SPR sensors based on both direct (with the immobilization of the antibody) and competitive (with the immobilization of the antigen) methods did not allow the detection of ampicillin. Therefore, a sandwich-based sensor was developed which showed a good linear response towards ampicillin between 10−3 and 10−1 M, a measurement time of ≤20 min and a high selectivity both towards β-lactam antibiotics and antibiotics of different classes.

Platinum nanopetal-based potassium sensors for acute cell death monitoring

Growing interest in the role of ions as cell death regulators has led to the consideration of K+, which plays a major role in events such as necrosis, apoptosis and osmotic shock. These mechanisms induce effluxes of K+, which can be measured to monitor such cellular events. In this work, we present a fast and simple template-free electrodeposition method for modifying electrodes on microfabricated Si-based platforms with Pt nanopetals. K+-selective electrodes were constructed by coupling such newly obtained Pt nanopetals, which were used as a solid contact, with PVC (polyvinyl chloride) K+-selective membranes. The drift over time was reduced by three orders of magnitude from several mV h−1 for bare electrodes to tens of μV h−1 when Pt nanopetals were used as an intermediate layer between the electrode and the selective membrane. The improved potential stability is comparable to the best values obtained by using solid-contact ion-selective electrodes based on other nanomaterials. The sensors exhibited near-Nernstian behavior and high selectivity for K+. By studying cell viability in relation to K+ measurements, we established a new correlation between the level of ions and the cell viability upon exposure to both osmotic shock and treatment with acetaminophen. The present method for the continuous and non-invasive monitoring of cell death in a bioreactor has potential applications in various biomedical domains.

A bimetallic nanocoral Au decorated with Pt nanoflowers (bio)sensor for H 2 O 2 detection at low potential

In this work, we have developed for the first time a method to make novel gold and platinum hybrid bimetallic nanostructures differing in shape and size. Au-Pt nanostructures were prepared by electrodeposition in two simple steps. The first step consists of the electrodeposition of nanocoral Au onto a gold substrate using hydrogen as a dynamic template in an ammonium chloride solution. After that, the Pt nanostructures were deposited onto the nanocoral Au organized in pores. Using Pt (II) and Pt (IV), we realized nanocoral Au decorated with Pt nanospheres and nanocoral Au decorated with Pt nanoflowers, respectively. The bimetallic nanostructures showed better capability to electrochemically oxidize hydrogen peroxide compared with nanocoral Au. Moreover, Au-Pt nanostructures were able to lower the potential of detection and a higher performance was obtained at a low applied potential. Then, glucose oxidase was immobilized onto the bimetallic Au-Pt nanostructure using cross-linking with glutaraldehyde. The biosensor was characterized by chronoamperometry at +0.15V vs. Ag pseudo-reference electrode (PRE) and showed good analytical performances with a linear range from 0.01 to 2.00mM and a sensitivity of 33.66µA/mMcm2. The good value of Kmapp (2.28mM) demonstrates that the hybrid nanostructure is a favorable environment for the enzyme. Moreover, the low working potential can minimize the interference from ascorbic acid and uric acid as well as reducing power consumption to effect sensing. The simple procedure to realize this nanostructure and to immobilize enzymes, as well as the analytical performances of the resulting devices, encourage the use of this technology for the development of biosensors for clinical analysis.

Comparison between a Direct-Flow SPR Immunosensor for Ampicillin and a Competitive Conventional Amperometric Device: Analytical Features and Possible Applications to Real Samples

In this research, we developed a direct-flow surface plasmon resonance (SPR) immunosensor for ampicillin to perform direct, simple, and fast measurements of this important antibiotic. In order to better evaluate the performance, it was compared with a conventional amperometric immunosensor, working with a competitive format with the aim of finding out experimental real advantages and disadvantages of two respective methods. Results showed that certain analytical features of the new SPR immunodevice, such as the lower limit of detection (LOD) value and the width of the linear range, are poorer than those of a conventional amperometric immunosensor, which adversely affects the application to samples such as natural waters. On the other hand, the SPR immunosensor was more selective to ampicillin, and measurements were more easily and quickly attained compared to those performed with the conventional competitive immunosensor.

One-step rapid synthesis of Au-Pt nanofems for electrochemical sensing and biosensing

Novel Au-Pt nanofern-like structures have been obtained with a fast and one-step electrodeposition process. The compositional characterization revealed that the Pt/Au ratio is equal to 0.25. The synergic effect between Au and Pt was confirmed by the considerable lowering of the detection voltage towards the direct detection of glucose and hydrogen peroxide. As a consequence of the low detection potentials, the prepared electrodes displayed a high selectivity for both glucose and hydrogen peroxide over biological interfering species including both electroactive endogenous compounds (e.g., ascorbic acid and dopamine) and exogenous ones (e.g., acetaminophen) in addition to providing advantages in circuit design.

Ampicillin Measurement Using Flow SPR Immunosensor and Comparison with Classical Amperometric Immunosensor

An analytical comparison of a flow SPR immunosensor method and a conventional amperometric immunosensor has been carried out. Different formats were used, respectively, main analytical data have been checked and affinity constant values evaluated and compared.