Platinum Nanoelectrodes Research Articles

Enzyme-modified Pt nanoelectrodes for glutamate detection.

We present here a glutamate oxidase (GluOx)-modified platinum (Pt) nanoelectrode with a planar geometry for glutamate detection. The Pt nanoelectrode was characterized using electrochemistry and scanning electron microscopy (SEM). The radius of the Pt nanoelectrode measured using SEM is ∼210 nm. GluOx-modified Pt nanoelectrodes were generated by dip coating GluOx on the Pt nanoelectrode in a solution of 0.9% (wt%) bovine serum albumin (BSA), 0.126% (wt%) glutaraldehyde, and 100 U mL-1 GluOx. An increase in current was observed at +0.7 V vs. Ag/AgCl/1 M KCl with adding increasing concentrations of glutamate. Two-sample t-test results showed that there is a significant difference for current at +0.7 V between the blank and the added lowest glutamate concentration, as well as between adjacent glutamate concentrations, confirming that the increase in current is related to the increased glutamate concentration. The experimental current-concentration curve of glutamate detection fitted well to the theoretical Michaelis-Menten curve. At the low concentration range (50 μM to 200 μM), a linear relationship between the current and glutamate concentration was observed. The Michaelis-Menten constants of Imax and Km were calculated to be 1.093 pA and 0.227 mM, respectively. Biosensor efficiency (the ratio of glutamate sensitivity to H2O2 sensitivity) is calculated to be 57.9%. Enzact (Imax/H2O2 sensitivity, an indicator of the amount of enzyme loaded on the electrode) of the GluOx-modified Pt nanoelectrode is 0.243 mM. We further compared the sensitivity of a GluOx-modified Pt nanoelectrode with a GluOx-modified carbon fiber microelectrode (7 μm diameter and a sensing length of ∼350 μm). Glutamate detection on the GluOx-modified carbon fiber microelectrode fitted well to a Michaelis-Menten like response. Based on the fitting, the GluOx-modified carbon fiber microelectrode exhibited an Imax of 0.689 nA and a Km of 301.2 μM towards glutamate detection. The best linear range of glutamate detection on the GluOx-modified carbon fiber microelectrode is from 50 μM to 150 μM glutamate. The GluOx-modified carbon fiber microelectrode exhibited a higher potential requirement for glutamate detection compared to the GluOx-modified Pt nanoelectrode.

Scanning Ion-Conductance Microscopy for Studying β-Amyloid Aggregate Formation on Living Cell Surfaces.

β-Amyloid aggregation on living cell surfaces is described as responsible for the neurotoxicity associated with different neurodegenerative diseases. It is suggested that the aggregation of β-amyloid (Aβ) peptide on neuronal cell surface leads to various deviations of its vital function due to myriad pathways defined by internalization of calcium ions, apoptosis promotion, reduction of membrane potential, synaptic activity loss, etc. These are associated with structural reorganizations and pathologies of the cell cytoskeleton mainly involving actin filaments and microtubules and consequently alterations of cell mechanical properties. The effect of amyloid oligomers on cells' Young's modulus has been observed in a variety of studies. However, the precise connection between the formation of amyloid aggregates on cell membranes and their effects on the local mechanical properties of living cells is still unresolved. In this work, we have used correlative scanning ion-conductance microscopy (SICM) to study cell topography, Young's modulus mapping, and confocal imaging of Aβ aggregate formation on living cell surfaces. However, it is well-known that the cytoskeleton state is highly connected to the intracellular level of reactive oxygen species (ROS). The effect of Aβ leads to the induction of oxidative stress, actin polymerization, and stress fiber formation. We measured the reactive oxygen species levels inside single cells using platinum nanoelectrodes to demonstrate the connection of ROS and Young's modulus of cells. SICM can be successfully applied to studying the cytotoxicity mechanisms of Aβ aggregates on living cell surfaces.

Nano-Electrochemical Characterization of a 3D Bioprinted Cervical Tumor Model.

Current cancer research is limited by the availability of reliable in vivo and in vitro models that are able to reproduce the fundamental hallmarks of cancer. Animal experimentation is of paramount importance in the progress of research, but it is becoming more evident that it has several limitations due to the numerous differences between animal tissues and real, in vivo human tissues. 3D bioprinting techniques have become an attractive tool for many basic and applied research fields. Concerning cancer, this technology has enabled the development of three-dimensional in vitro tumor models that recreate the characteristics of real tissues and look extremely promising for studying cancer cell biology. As 3D bioprinting is a relatively recently developed technique, there is still a lack of characterization of the chemical cellular microenvironment of 3D bioprinted constructs. In this work, we fabricated a cervical tumor model obtained by 3D bioprinting of HeLa cells in an alginate-based matrix. Characterization of the spheroid population obtained as a function of culturing time was performed by phase-contrast and confocal fluorescence microscopies. Scanning electrochemical microscopy and platinum nanoelectrodes were employed to characterize oxygen concentrations-a fundamental characteristic of the cellular microenvironment-with a high spatial resolution within the 3D bioprinted cervical tumor model; we also demonstrated that the diffusion of a molecular model of drugs in the 3D bioprinted construct, in which the spheroids were embedded, could be measured quantitatively over time using scanning electrochemical microscopy.

Nucleation behavior and kinetics of single hydrogen nanobubble in ionic liquid system

Bubbles generated on the electrode surface have been considered one of important factors limiting the efficiency of hydrogen evolution reaction (HER). However, the bubble formation behaviors have not been clearly defined, especially nanobubbles in ionic liquid system. In this work, single H2 nanobubbles generation characters are well investigated using platinum nanoelectrodes in ionic liquid (IL) during HER. The crucial factors (i.e., critical condition, geometry, and nucleation rapid of the H2 nanobubbles) are quantitatively conducted from the voltammograms. The results reveal that the H2 nanobubbles have a small contact angle (from 152° to 160°) and large bubble height (0.5–1.1 nm), which are favorable for subsequent detachment from nanoelectrode surface. Moreover, higher nucleation energy (7.5–15.3 kT) indicates that IL can suppress bubble formation. This work has gained a fundamental insight into the dynamic formation behaviors of H2 nanobubble in IL, which can guide us to study H2 bubbles in the HER influenced by various factors.

Voltammetric examination of carbon and platinum nanoelectrodes under mixed diffusion – migration mass transport conditions

The majority of electroanalytical experiments are performed with supporting electrolytes to minimize the migration of electroactive ions and other unwanted effects of the low conductivity of the system. Microelectrodes and nanoelectrodes allow for voltammetric measurements in solutions of substantial resistivity, however, their application in non-supported electrolytes is vaguely studied in detail. This work demonstrates the employment of carbon and platinum nanoelectrodes in solutions of ionic and neutral ferrocene derivatives in the presence and absence of supporting electrolyte. The ferrocene derivatives of various charges served as redox probes for the studies of diffusion-migration transport to nanoelectrodes. The obtained results are confronted with the theoretical predictions derived for microelectrodes. An addition of a supporting electrolyte stabilizes the voltammetric signal. It makes the voltammetric waves at nanoelectrodes well developed irrespective of the type of the redox system examined. The results revealed that the migration of electroactive species to nanoelectrodes in the absence of a supporting electrolyte does not introduce significant changes to the voltammetric signal recorded with a supporting electrolyte as much as for bigger microelectrodes. In many cases, the complete elimination of supporting electrolyte led to the poor development of the voltammetric waves at nanoelectrodes, possibly due to the breakdown of the electroneutrality in the region adjacent to the nanoelectrode, since the electrical double layer for nanoelectrodes may occupy a significant fraction of the transport depletion layer. The uncertainty in the concentrations of ionic impurities (that determine the actual ionic strength) in the layer adjacent to the electrode is another factor that may produce unpredictable and, to some extent, random voltammetric behavior of charged redox probes at nanoelectrodes in the absence of supporting electrolyte.

High-density individually addressable platinum nanoelectrodes for biomedical applications

3-D vertical nanoelectrode arrays (NEAs) have found applications in several biomedical and sensing applications, including high-resolution neuronal excitation and measurement and single-molecule electrochemical biosensing. There have been several reports on high-density nanoelectrodes in recent years, with the filling ratio of electrodes reaching close to 0.002 (assuming the electrode diameter of 200 nm and pitch of 4 μm). Still, it is well below the nanowire filling ratio required to form interconnected neuronal networks, i.e., more than 0.14 (assuming the electrode diameter of 200 nm and pitch of 1.5 μm). Here, we employ a multi-step, large-area electron beam lithography procedure along with a targeted, focused ion beam based metal deposition technique to realize an individually addressable, 60-channel nanoelectrode chip with a filling ratio as high as 0.16, which is well within the limit required for the formation of interconnected neuronal networks. Moreover, we have designed the NEA chip to be compatible with the commercially available MEA2100-System, which can, in the future, enable the chip to be readily used for obtaining data from individual electrodes. We also perform an in-depth electrochemical impedance spectroscopy characterization to show that the electrochemical behavior and the charge transfer mechanism in the array are significantly influenced by changing the thickness of the SU-8 planarization layer (i.e., the thickness of the exposed platinum surface). In addition to neural signal excitation and measurement, we propose that these NEA chips have the potential for other future applications, such as high-resolution single-molecule level electrochemical and bio-analyte sensing.

Single DNA Translocation and Electrical Characterization Based on Atomic Force Microscopy and Nanoelectrodes.

Precision DNA translocation control is critical for achieving high accuracy in single molecule-based DNA sequencing. In this report, we describe an atomic force microscopy (AFM) based method to linearize a double-stranded DNA strand during the translocation process and characterize the electrical properties of the moving DNA using a platinum (Pt) nanoelectrode gap. In this method, λDNAs were first deposited on a charged mica substrate surface and topographically scanned. A single DNA suitable for translocation was then identified and electrostatically attached to an AFM probe by pressing the probe tip down onto one end of the DNA strand without chemical functionalizations. Next, the DNA strand was lifted off the mica surface by the probe tip. The pulling force required to completely lift off the DNA agreed well with the theoretical DNA adhesion force to a charged mica surface. After liftoff, the captured DNA was translocated at varied speeds across the substrate and ultimately across the Pt nanoelectrode gap for electrical characterizations. Finally, finite element analysis of the effect of the translocating DNA on the conductivity of the nanoelectrode gap was conducted, validating the range of the gap current measured experimentally during the DNA translocation process.

Theoretical Investigation of Design Methodology, Optimized Molecular Geometries, and Electronic Properties of Benzene-Based Single Molecular Switch with Metal Nanoelectrodes

Understanding the electronic properties at the single molecular level is the first step in designing functional electronic devices using individual molecules. This paper proposes a simulation methodology for the design of a single molecular switch. A single molecular switch has two stable states that possess different chemical configurations. The methodology is implemented for 1,4-benzene dithiol (BDT) molecule with gold, silver, platinum, and palladium metal nanoelectrodes. The electronic properties of the designed metal-molecule-metal sandwich structure have been investigated using density functional theory (DFT) and Hartree-Fock (HF) method. It has been perceived that the DFT and HF values are slightly different as HF calculation does not include an electron-electron interaction term. Computation of the switching ratio gives the insight that BDT with gold has a high switching ratio of 0.88 compared with other three metal nanoelectrodes. Further, calculations of quantum chemical descriptors, analysis of the density of states (DOS) spectrum, and frontier molecular orbitals for both the stable states (i.e., ON and OFF state geometries) have been carried out. Exploring the band gap, ionization potential, and potential energy of two stable states reveals that the ON state molecule shows slightly higher conductivity and better stability than the OFF state molecule for every chosen electrode in this work. The proposed methodology for the single molecular switch design suggests an eclectic promise for the application of these new materials in novel single molecular nanodevices.

Prolonged oxygen depletion in microwounded cells of Chara corallina detected with novel oxygen nanosensors.

Primary physicochemical steps in microwounding of plants were investigated using electrochemical nano- and microprobes, with a focus on the role of oxygen in the wounding responses of individual plant cells. Electrochemical measurements of cell oxygen content were made with carbon-filled quartz micropipettes with platinum-coated tips (oxygen nanosensors). These novel platinum nanoelectrodes are useful for understanding cell oxygen metabolism and can be employed to study the redox biochemistry and biology of cells, tissues and organisms. We show here that microinjury of Chara corallina internodal cells with the tip of a glass micropipette is associated with a drastic decrease in oxygen concentration at the vicinity of the stimulation site. This decrease is reversible and lasts for up to 40 minutes. Membrane stretching, calcium influx, and cytoskeleton rearrangements were found to be essential for the localized oxygen depletion induced by cell wall microwounding. Inhibition of electron transport in chloroplasts or mitochondria did not affect the magnitude or timing of the observed response. In contrast, the inhibition of NADPH oxidase activity caused a significant reduction in the amplitude of the decrease in oxygen concentration. We suggest that the observed creation of localized anoxic conditions in response to cell wall puncture might be mediated by NADPH oxidase.

Nanomole Silver Detection in Chloride-Free Phosphate Buffer Using Platinum and Gold Micro- and Nanoelectrodes

The electrochemical determination of ultra-low concentrations of silver requires reliable, reproducible measurements using sensitive analytical techniques. To date, the electrochemical determination of silver in biological buffers and pH neutral media has not been successful in terms of reproducibility. In this work, we report on the determination of ultra-low concentrations of silver in chloride-free phosphate buffer solution (PB, pH 7.4). Detection was conducted at gold and platinum micro and nanoelectrodes using anodic stripping voltammetry (ASV). The micro and nanoelectrodes were fabricated using a Sutter P-2000 laser puller, with physical and electrochemical characterization revealing flat disk-shaped working surfaces of 10–15 μm (microelectrode) and 10–100 nm (nanoelectrodes) in radius. These dimensions were calculated from steady-state limiting currents and confirmed using FE-SEM. The laser pulled electrodes exhibit excellent electrochemical activity when characterized using ferrocene, without the addition of supporting electrolyte, and reproducible stripping voltammetric profiles for the determination of silver, with a LoD of 1.3 pM (1.8%) were obtained in 0.1 M chloride-free phosphate at platinum nanoelectrode. Determination of ultra-low concentrations of silver in chloride-free PB provides the scope to explore the mechanism of action of bioinorganic silver-based anti-bacterial, anti-fungal and anti-cancer drugs in cell media for in vitro and, potentially, in vivo analysis.

Detecting reactive oxygen species in biological fluids by platinum nanoelectrode applying amperometric method

Reactive oxygen species (ROS) are vital metabolites in numerous biological functions. Disorders of cellular mechanisms can cause overproduction of ROS and, subsequently, oxidative damage to DNA, proteins, cells and tissues, which is associated with the pathogenesis of a number of neurodegenerative and inflammatory diseases. Development of highly sensitive, relatively simple and fast-to-implement innovative methods to detect oxidative stress requires understanding of how such disorders relate to the level of ROS. This research aimed to apply the biological fluids' ROS detection method we have developed (using the stable platinum nanoelectrode that allows assessing the level of hydrogen peroxide (H2O2) down to 1 μM) and determine the level of H2O2 in lacrimal and intraocular fluids of rabbits, as well as to investigate how the level of H2O2 changes under the influence of antioxidant therapy. The effect superoxide dismutase (SOD) nanoparticles produce on biological fluids' ROS level was shown. The level of H2O2 in lacrimal fluid increased 10 and 30 min after instillation of SOD nanoparticles. As for the intraocular fluid, H2O2 concentration starts to grow only 30 min after instillation of SOD nanoparticles, which suggests that the they penetrate the internal structures of the eye gradually. The method seems to be of value in the context of eye diseases diagnosing and treatment.

Hopping mode SECM imaging of redox activity in ionic liquid with glass-coated inlaid platinum nanoelectrodes prepared using a heating coil puller

Major difficulties in nanoscale scanning electrochemical microscopy (SECM), resulting from the short tip-to-sample distance, are tilt misalignment and vertical thermal drift. This renders constant height mode nanoscale electrochemical imaging experimentally problematic. Nanoscale SECM also requires application of reliable nanoprobes. Although SECM nanotips are commercially available, they are rather disposable, fragile and their shelf-life is limited. Many SECM laboratories employ self-prepared nanoprobes, fabricated using advanced apparatus. In this paper, we employ a hopping mode approach to nanoscale electrochemical imaging, which resolves the mentioned common difficulties. The applied platinum nanoelectrodes, insulated with borosilicate glass, were prepared using affordable equipment and materials. They were applied for nanoscale mapping of redox mediator regeneration at a model interdigitated microsensor, composed of Pt microband electrodes, in a solution of ferrocene in viscous hydrophobic room temperature ionic liquid (RTIL) – 1-butyl-3-methylimidazoliumbis(trifluoro-methylsulfonyl)imide (C4mim N(Tf)2). The presented nanosensors were also characterized with cyclic voltammetry in aqueous electrolyte containing hexamineruthenium (III) chloride as redox mediator.

Imaging Dynamic Collision and Oxidation of Single Silver Nanoparticles at the Electrode/Solution Interface.

The electrochemical interface is an ultrathin interfacial region between the electrode surface and the electrolyte solution and is often characterized by numerous dynamic processes, such as solvation and desolvation, heterogeneous electron transfer, molecular adsorption and desorption, diffusion, and surface rearrangement. Many of these processes are driven and modulated by the presence of a large interfacial potential gradient. The study and better understanding of the electrochemical interface is important for designing better electrochemical systems where their applications may include batteries, fuel cells, electrocatalytic water splitting, corrosion protection, and electroplating. This, however, has proved to be a challenging analytical task due to the ultracompact and dynamic evolving nature of the electrochemical interface. Here, we describe the use of an electrochemical nanocell to image the dynamic collision and oxidation process of single silver nanoparticles at the surface of a platinum nanoelectrode. A nanocell is prepared by depositing a platinum nanoparticle at the tip of a quartz nanopipette forming a bipolar nanoelectrode. The compact size of the nanocell confines the motion of the silver nanoparticle in a 1-D space. The highly dynamic process of nanoparticle collision and oxidation is imaged by single-particle fluorescence microscopy. Our results demonstrate that silver nanoparticle collision and oxidation is highly dynamic and likely controlled by a strong electrostatic effect at the electrode/solution interface. We believe that the use of a platinum nanocell and single molecule/nanoparticle fluorescence microscopy can be extended to other systems to yield highly dynamic information about the electrochemical interface.

New functional materials based on conductive polymer—metal complexes modified with metallic nanoelectrodes

The results of the synthesis and investigation of new composite functional materials are presented. The new materials are conductive polymer layers of the cobalt, nickel, and palladium complexes with the Schiff bases (poly[MSchiff)]) with gold and platinum nanoelectrodes inserted into the layers using the electrochemical deposition method. The materials were studied by cyclic voltammetry, impedance spectroscopy, scanning electron microscopy with X-ray microanalysis, and a quartz crystal microbalance. The composite materials poly[Ni(Schiff)]/Pt and poly[Co(Schiff)]/Au exhibit catalytic activity in the reactions of hydrogen evolution and electroreduction of molecular oxygen, respectively.

Study of the formation and quick growth of thick oxide films using platinum nanoelectrodes as a model electrocatalyst.

We report a study of the formation and quick growth of thick films of platinum oxide on platinum nanoelectrodes at low anodic potentials. Here, structurally well-defined platinum nanoelectrodes are used as a model platform for nanoscale platinum electrocatalysts. Platinum films are formed on the surface of the nanoelectrode upon application of a constant anodic potential in an acidic environment for an extended time period. A current spike is initially observed, which is attributed to capacitance charging, the oxidation of water, and the initial oxidation of the platinum surface. A finite residual current follows the initial current spike, which is composed of both water oxidation and the oxidation of platinum metal concealed beneath the growing oxide layer. These films are observed to be structurally irreversible, grow to be relatively thick, and protrude out of the glass insulating material encasing the nanoelectrode due to the added volume of the oxygen incorporated into the growing platinum oxide film. Once reduced, the platinum metal remains protruding out of the glass, and its presence is confirmed by both SEM imaging and cyclic voltammetry. Steady-state voltammetric data shows a finite increase in the diffusion-limited faradaic current of the nanoelectrode, relative to the initial steady-state current, after the oxidation/reduction of the platinum which is due to an increased area of the protruding platinum metal. A minimum apparent rate of ∼1.2 nm/min can be calculated for the growth of the platinum oxide film. The use of platinum nanoelectrodes has shown several distinct advantages in this study, including better control of the size and morphology of the individual electrocatalysts, the ability to image using electron microscopy, and the ability to use voltammetry to evaluate the geometry of the electrode quickly.

Fabrication of Electrochemical DNA Sensors on Gold-Modified Recessed Platinum Nanoelectrodes

We report the use of gold-modified recessed platinum (Pt) nanoelectrodes in the fabrication of linear and stem-loop probe-based electrochemical DNA (E-DNA) sensors. Pt nanoelectrodes with a radius less than 10 nm were reproducibly fabricated using an optimized laser pulling technique. Prior to sensor fabrication, the nanoelectrode was electrochemically etched to create a recessed nanopore, followed by electrodeposition of gold into the nanopore using either cyclic voltammetry or constant potential amperometry. Both techniques enabled controlled deposition of gold into the nanopores, resulting in a nanostructured gold electrode with a well-defined surface area. In addition, we systematically determined the optimal experimental condition for DNA probe immobilization and target interrogation. The electron transfer rate constants of methylene blue, as determined using alternating current voltammetry, were found to be much higher than those obtained from E-DNA sensors fabricated on conventional macroscale electrodes. While this unique phenomenon requires further investigation, our results clearly show that these gold-modified nanoelectrodes can be used as substrates for this class of electrochemical biosensors.

Fabrication of glass-coated electrodes with nano- and micrometer size by means of dissolution with HF

Platinum nano-electrodes were fabricated at the success rate 76% by the six processes; (i) etching a Pt wire in ethanol–water mixture, (ii) sealing it with a glass sheath, (iii) grinding roughly the glass tip, (iv) polishing the tip while monitoring the capacitive ac current flowing through the glass thin film on the Pt, (v) dissolving the glass film in HF solution until a part of Pt was exposed, and (vi) heating the tip at 85 °C for stabilization. A key of the process was to make a thin glass film on the Pt tip (iv) and to expose the Pt surface chemically by (v). 50 electrodes thus fabricated had diameters ranging from 1 nm to 5 μm, estimated from the steady-state diffusion-controlled current of ferrocene in acetonitrile and ferrocenyl derivative in aqueous solution. They exhibited reproducible and stable voltammograms without hysteresis, withstanding 6 hours’ continuous use and 15 hours’ iterative processes of heat and voltammetry. Not only the halfwave potentials but also slopes of the log-plots were independent of radii of the electrodes. No kinetic effect was revealed in the steady-state voltammograms.

Electrochemistry through glass

In this Article we have used new approaches to investigate a well-known chemical process, the propagation of electrochemical signals through a thin glass membrane. This process, which has been extensively studied over the last century, is the basis of the response of a potentiometric glass pH sensor; however, no amperometric glass sensors have yet been reported because of its high ohmic resistance. Voltammetry at nanoelectrodes has revealed that water molecules can diffuse through nanometre-thick layers of dry glass and undergo oxidation/reduction at the buried platinum surface. After soaking for a few hours in an aqueous solution, voltammetric waves of other redox couples, such as Ru(NH(3))(6)(3+/2+), could also be obtained at the glass-covered platinum nanoelectrodes. This behaviour suggests that the nanometre-thick insulating glass sheath surrounding the platinum core can be largely converted to hydrated gel, and electrochemical processes occur at the platinum/hydrogel interface. Potential applications range from use in nanometre-sized solid-state pH probes and determination of the water content in organic solvents to glass-modified voltammetric sensors and electrocatalysts.

Electron Transfer Kinetics at the Surface of Platinum Nanoelectrodes Prepared by Through Thin Film Ablation

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A nanofluidic channel with embedded transverse nanoelectrodes

In this paper, we demonstrate fabrication and characterization of a nanofluidicchannel with embedded transverse nanoelectrodes using a combinationof conventional photolithography and focused ion beam technologies.Glass-capped silicon dioxide nanochannels having 20 nm depth, 50 nm width, and2 µm length with embedded platinum nanoelectrodes were fabricated. Channel patency wasverified through measurements of the resistivity in phosphate buffered saline andelectrostatic action on charged fluorescent nanospheres. Platinum nanoelectrodefunctionality was also tested using transverse resistance measurements in nanochannelsfilled with air, deionized water, and saline solution.