Pain-Free Alpha-Synuclein Detection by Low-Cost Hierarchical Nanowire Based Electrode.

Analytical methods for the early detection of the neurodegenerative biomarker for Parkinson's disease (PD), α-synuclein, are time-consuming and invasive, and require skilled personnel and sophisticated and expensive equipment. Thus, a pain-free, prompt and simple α-synuclein biosensor for detection in plasma is highly demanded. In this paper, an α-synuclein electrochemical biosensor based on hierarchical polyglutamic acid/ZnO nanowires decorated by gold nanoparticles, assembled as nanostars (NSs), for the determination of α-synuclein in human plasma is proposed. ZnO NSs were prepared by chemical bath deposition (CBD) and decorated with electrodeposited Au nanoparticles (Au NPs). Then, electro-polymerized glutamic acid was grown and functionalized with anti-α-synuclein. A synergistic enhancement of electrode sensitivity was observed when Au NPs were embedded into ZnO NSs. The analytical performance of the biosensor was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), using the Fe(II)(CN)64-/Fe(III)(CN)63- probe. The charge transfer resistance after α-synuclein recognition was found to be linear, with a concentration in the range of 0.5 pg·mL-1 to 10 pg·mL-1, a limit of detection of 0.08 pg·mL-1, and good reproducibility (5% variation) and stability (90%). The biosensor was also shown to reliably discriminate between healthy plasma and PD plasma. These results suggest that the proposed biosensor provides a rapid, quantitative and high-sensitivity result of the α-synuclein content in plasma, and represents a feasible tool capable of accelerating the early and non-invasive identification of Parkinson's disease.

Model of Chronoamperometric Response towards Glucose Sensing by Arrays of Gold Nanostructures Obtained by Laser, Thermal and Wet Processes.

Non-enzymatic electrochemical glucose sensors are of great importance in biomedical applications, for the realization of portable diabetic testing kits and continuous glucose monitoring systems. Nanostructured materials show a number of advantages in the applications of analytical electrochemistry, compared to macroscopic electrodes, such as great sensitivity and little dependence on analyte diffusion close to the electrode-solution interface. Obtaining electrodes based on nanomaterials without using expensive lithographic techniques represents a great added value. In this paper, we modeled the chronoamperometric response towards glucose determination by four electrodes consisting of nanostructured gold onto graphene paper (GP). The nanostructures were obtained by electrochemical etch, thermal and laser processes of thin gold layer. We addressed experiments obtaining different size and shape of gold nanostructures. Electrodes have been characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and chronoamperometry. We modeled the current-time response at the potential corresponding to two-electrons oxidation process of glucose by the different nanostructured gold systems. The finest nanostructures of 10-200 nm were obtained by laser dewetting of 17 nm thin and 300 °C thermal dewetting of 8 nm thin gold layers, and they show that semi-infinite linear diffusion mechanism predominates over radial diffusion. Electrochemical etching and 17 nm thin gold layer dewetted at 400 °C consist of larger gold islands up to 1 µm. In the latter case, the current-time curves can be fitted by a two-phase exponential decay function that relies on the mixed second-order formation of adsorbed glucose intermediate followed by its first-order decay to gluconolactone.

Alkaline Electro-Sorption of Hydrogen Onto Nanoparticles of Pt, Pd, Pt80Pd20 and Cu(OH)2 Obtained by Pulsed Laser Ablation.

Recently, hydrogen evolution reaction (HER) in alkaline media has received a renewed interest both in the fundamental research as well as in practical applications. Pulsed Laser Ablation in Liquid (PLAL) has been demonstrated as a very useful technique for the unconventional preparation of nanomaterials with amazing electro-catalyst properties toward HER, compared to those of nanomaterials prepared by conventional methods. In this paper, we compared the electro-sorption properties of hydrogen in alkaline media by Pt, Pd, Pt80Pd20, and Cu(OH)2 nanoparticles (NPs) prepared by PLAL. The NPs were placed onto graphene paper (GP). Noble metal particles have an almost spherical shape, whereas Cu(OH)2 presents a flower-bud-like shape, formed by very thin nanowalls. XPS analyses of Cu(OH)2 are compatible with a high co-ordination of Cu(II) centers by OH and H2O. A thin layer of perfluorosulfone ionomer placed onto the surface of nanoparticles (NPs) enhances their distribution on the surface of graphene paper (GP), thereby improving their electro-catalytic properties. The proposed mechanisms for hydrogen evolution reaction (HER) on noble metals and Cu(OH)2 are in line with the adsorption energies of H, OH, and H2O on the surfaces of Pt, Pd, and oxidized copper. A significant spillover mechanism was observed for the noble metals when supported by graphene paper. Cu(OH)2 prepared by PLAL shows a competitive efficiency toward HER that is attributed to its high hydrophilicity which, in turn, is due to the high co-ordination of Cu(II) centers in very thin Cu(OH)2 layers by OH- and H2O. We propose the formation of an intermediate complex with water which can reduce the barrier energy of water adsorption and dissociation.

Electro-Sorption of Hydrogen by Platinum, Palladium and Bimetallic Pt-Pd Nanoelectrode Arrays Synthesized by Pulsed Laser Ablation.

Sustainable and renewable production of hydrogen by water electrolysers is expected to be one of the most promising methods to satisfy the ever-growing demand for renewable energy production and storage. Hydrogen evolution reaction in alkaline electrolyte is still challenging due to its slow kinetic properties. This study proposes new nanoelectrode arrays for high Faradaic efficiency of the electro-sorption reaction of hydrogen in an alkaline electrolyte. A comparative study of the nanoelectrode arrays, consisting of platinum or palladium or bimetallic nanoparticles (NPs) Pt80Pd20 (wt.%), obtained by nanosecond pulsed laser ablation in aqueous environment, casted onto graphene paper, is proposed. The effects of thin films of perfluoro-sulfonic ionomer on the material morphology, nanoparticles dispersion, and electrochemical performance have been investigated. The NPs-GP systems have been characterized by field emission scanning electron microscopy, Rutherford backscattering spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge cycles. Faradaic efficiency up to 86.6% and hydrogen storage capacity up to 6 wt.% have been obtained by the Pt-ionomer and Pd/Pt80Pd20 systems, respectively.

Fabrication of Cu(II) oxide-hydroxide nanostructures onto graphene paper by laser and thermal processes for sensitive nano-electrochemical sensing of glucose.

Glucose electrochemical sensors based on nanostructures of CuO/Cu(OH)2onto graphene paper were prepared by thermal (solid) and nanosecond pulsed laser (molten phase) dewetting of a CuO layer 6 nm thin deposited by sputtering. Dewetted systems, obtained without the use of any binder, act as array of nanoelectrodes. Solid state and molten phase dewetting produce nanostructures of copper oxide-hydroxide with different average size, shape and surface composition. Molten phase dewetting originates particles with size below 100 nm, while solid state dewetting produces particles with average size of about 200 nm. Moreover, molten phase dewetting produce drop-shaped nanostructures, conversely nanostructures derived from solid state dewetting are multifaceted. X-ray photoelectron spectroscopy (XPS) characterization revealed that the surface of nanostructures is formed by a copper(II) species CuO and Cu(OH)2. Shape of anodic branch of the cyclic voltammograms of glucose in alkali solution evidenced a convergent diffusion mechanism. Analytical performances in amperometric mode are as good as or better than other sensors based on copper oxide. Amperometric detection of glucose was done at potential as low as 0.4 V versus saturated calomel electrode by both types of electrodes. Linear range from 50µM to 10 mM, sensitivity ranging from 7 to 43µA cm-2mM-1and detection limit of 7µM was obtained. Good analytical performances were obtained by laser dewetted electrodes with a low copper content up to 1.2 by atoms percentage of the surface. Analytical performance of the proposed electrodes is compliant for the determination of glucose both in blood serum, saliva or tear.

Disposable and Low-Cost Electrode Based on Graphene Paper-Nafion-Bi Nanostructures for Ultra-Trace Determination of Pb(II) and Cd(II).

There is a huge demand for rapid, reliable and low-cost methods for the analysis of heavy metals in drinking water, particularly in the range of sub-part per billion (ppb). In the present work, we describe the preparation, characterization and analytical performance of the disposable sensor to be employed in Square Wave Anodic Stripping Voltammetry (SWASV) for ultra-trace simultaneous determination of cadmium and lead. The electrode consists of graphene paper-perfluorosulfonic ionomer-bismuth nano-composite material. The electrode preparation implies a key step aimed to enhance the Bi3+ adsorption into nafion film, prior to the bismuth electro-deposition. Finely dispersed bismuth nanoparticles embedded in the ionomer film are obtained. The electrode was characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). The electrode shows a linear response in the 5-100 ppb range, a time-stability tested up to almost three months, and detection limits up to 0.1 ppb for both Pb2+ and Cd2+. The electrode preparation method is simple and low in cost and the obtained analytical performance is very competitive with the state of art for the SWASV determination of Pb2+ and Cd2+ in solution.

Dewetted Gold Nanostructures onto Exfoliated Graphene Paper as High Efficient Glucose Sensor.

Non-enzymatic electrochemical glucose sensing was obtained by gold nanostructures on graphene paper, produced by laser or thermal dewetting of 1.6 and 8 nm-thick Au layers, respectively. Nanosecond laser annealing produces spherical nanoparticles (AuNPs) through the molten-phase dewetting of the gold layer and simultaneous exfoliation of the graphene paper. The resulting composite electrodes were characterized by X-ray photoelectron spectroscopy, cyclic voltammetry, scanning electron microscopy, micro Raman spectroscopy and Rutherford back-scattering spectrometry. Laser dewetted electrode presents graphene nanoplatelets covered by spherical AuNPs. The sizes of AuNPs are in the range of 10-150 nm. A chemical shift in the XPS Au4f core-level of 0.25-0.3 eV suggests the occurrence of AuNPs oxidation, which are characterized by high stability under the electrochemical test. Thermal dewetting leads to electrodes characterized by faceted not oxidized gold structures. Glucose was detected in alkali media at potential of 0.15-0.17 V vs. saturated calomel electrode (SCE), in the concentration range of 2.5µM-30 mM, exploiting the peak corresponding to the oxidation of two electrons. Sensitivity of 1240 µA mM-1 cm-2, detection limit of 2.5 µM and quantifications limit of 20 µM were obtained with 8 nm gold equivalent thickness. The analytical performances are very promising and comparable to the actual state of art concerning gold based electrodes.

Self-organization and nanostructural control in thin film heterojunctions.

In spite of more than two-decades of studies of molecular self-assembly, the achievement of low cost, easy-to-implement and multi-parameter bottom-up approaches to address the supramolecular morphology in three-dimensional (3D) systems is still missing. In the particular case of molecular thin films, the 3D nanoscale morphology and function are crucial for both fundamental and applied research. Here we show how it is possible to tune the 3D film structure (domain size, branching, etc.) of thin film heterojunctions with nanoscale accuracy together with the modulation of their optoelectronic properties by employing an easy two-step approach. At first we prepared multi-planar heterojunctions with a programmed sequence of nanoscopic layers. In a second step, thermal stimuli have been employed to induce the formation of bulk heterojunctions with bicontinuous and interdigitated phases having a size below the exciton diffusion length. Importantly, the study of luminescence quenching of these systems can be considered as a useful means for the accurate estimation of the exciton diffusion length of semiconductors in nanoscale blends. Finally, nearly a thousand times lower material consumption than spin coating allows a drastic reduction of material wasting and a low-cost implementation, besides the considerable possibility of preparing thin film blends also by employing materials soluble in different solvents.

From monolayer to multilayer N-channel polymeric field-effect transistors with precise conformational order.

Monolayer field-effect transistors based on a high-mobility n-type polymer are demonstrated. The accurate control of the long-range order by Langmuir-Schäfer (LS) deposition yields dense polymer packing exhibiting good injection properties, relevant current on/off ratio and carrier mobility in a staggered configuration. Layer-by-layer LS film transistors of increasing thickness are fabricated and their performance compared to those of spin-coated films.

A supramolecular heteropolyoxopalladate {Pd15} cluster host encapsulating a {Pd2} dinuclear guest: [Pd(II)2⊂{H7Pd(II)15O10(PO4)10}](9-).

A high-nuclearity polyoxopalladate compound, [Pd(II)(2)⊂{H(7)Pd(II)(15)O(10)(PO(4))(10)}](9-) {Pd(II)(17)}, comprising a {Pd(15)} host occupied by a {Pd(2)} guest and the parent pristine "empty" [H(7)Pd(II)(15)O(10)(P(V)O(4))(10)](13-) {Pd(15)} cluster have both been prepared and characterized by single-crystal X-ray crystallography, (31)P NMR, CSI-MS, and XPS. The encapsulated {Pd(2)} has a short Pd(II)-Pd(II) distance within the {Pd(15)} host. Solution studies indicate that the empty host and filled guest complex are in equilibrium with each other, and UV titrations revealed a binding constant of ca. 10(3) for the guest Pd(II) ions, with a binding stoichiometry of almost 2.

Feasibility studies on si-based biosensors.

The aim of this paper is to summarize the efforts carried out so far in the fabrication of Si-based biosensors by a team of researchers in Catania, Italy. This work was born as a collaboration between the Catania section of the Microelectronic and Microsystem Institute (IMM) of the CNR, the Surfaces and Interfaces laboratory (SUPERLAB) of the Consorzio Catania Ricerche and two departments at the University of Catania: the Biomedical Science and the Biological Chemistry and Molecular Biology Departments. The first goal of our study was the definition and optimization of an immobilization protocol capable of bonding the biological sensing element on a Si-based surface via covalent chemical bonds. We chose SiO(2) as the anchoring surface due to its biocompatibility and extensive presence in microelectronic devices. The immobilization protocol was tested and optimized, introducing a new step, oxide activation, using techniques compatible with microelectronic processing. The importance of the added step is described by the experimental results. We also tested different biological molecule concentrations in the immobilization solutions and the effects on the immobilized layer. Finally a MOS-like structure was designed and fabricated to test an electrical transduction mechanism. The results obtained so far and the possible evolution of the research field are described in this review paper.

XPS and AFM characterization of the enzyme glucose oxidase immobilized on SiO(2) surfaces.

A process to immobilize the enzyme glucose oxidase on SiO2 surfaces for the realization of integrated microbiosensors was developed. The sample characterization was performed by monitoring, step by step, oxide activation, silanization, linker molecule (glutaraldehyde) deposition, and enzyme immobilization by means of XPS, AFM, and contact angle measurements. The control of the environment during the procedure, to prevent silane polymerization, and the use of oxide activation to obtain a uniform enzyme layer are issues of crucial importance. The correct protocol application gives a uniform layer of the linker molecule and the maximum sample surface coverage. This result is fundamental for maximizing the enzyme bonding sites on the sample surface and achieving the maximum surface coverage. Thin SiO2 layers thermally grown on a Si substrate were used. The XPS Si 2p signal of the substrate was monitored during immobilization. Such a signal is not completely shielded by the thin oxide layer and it is fully suppressed after the completion of the whole protocol. A power spectral density analysis on the AFM measurements showed the crucial role of both the oxide activation and the intermediate steps (silanization and linker molecule deposition) to obtain uniform immobilized enzyme coverage. Finally, enzymatic activity measurements confirmed the suitability of the optimized protocol.

Immobilization of the Enzyme Glucose Oxidase on Both Bulk and Porous SiO2 Surfaces.

Silicon dioxide surfaces, both bulk and porous, were used to anchor the enzyme glucose oxidase. The immobilization protocol was optimized and the samples characterized using X-ray Photoelectron Spectroscopy, Energy Dispersive X-rays coupled to scanning electron microscopy and enzymatic activity measurements. We show that a uniform layer was obtained by activating the oxide before immobilization. X-ray Photoelectron Spectroscopy measurements carried out on bulk oxide showed that the silicon substrate signal was fully screened after the enzyme deposition showing the absence of uncovered surface regions. The enzyme presence was detected monitoring both the C 1s and N 1s signals. Finally, enzymatic activity measurements confirmed that the glucose oxidase activity was preserved after immobilization and maintained after three months of shelf life if the sample was properly stored. The importance of using porous silicon oxide to maximize the surface area was also evidenced.