Single-Entity Electrochemistry in the Agarose Hydrogel: Observation of Enhanced Signal Uniformity and Signal-to-Noise Ratio.

For the first time, single-entity electrochemistry (SEE) was demonstrated in a hydrogel matrix. SEE involves the investigation of the electrochemical characteristics of individual nanoparticles (NPs) by observing the signal generated when a single NP, suspended in an aqueous solution, collides with an electrode and triggers catalytic reactions. Challenges associated with SEE in electrolyte-containing solutions such as signal variation due to NP aggregation and noise fluctuation caused by convection phenomena can be addressed by employing a hydrogel matrix. The polymeric hydrogel matrix acts as a molecular sieve, effectively filtering out unexpected signals generated by aggregated NPs, resulting in more uniform signal observations compared to the case in a solution. Additionally, the hydrogel environment can reduce the background current fluctuations caused by natural convection and other factors such as impurities, facilitating easier signal analysis. Specifically, we performed SEE of platinum (Pt) NPs for hydrazine oxidation within the agarose hydrogel to observe the electrocatalytic reaction at a single NP level. The consistent porous structure of the agarose hydrogel leads to differential diffusion rates between individual NPs and reactants, resulting in variations in signal magnitude, shape, and frequency. The changes in the signal were analyzed in response to gel concentration variations.

Time-Resolved Electrochemical Impedance Spectroscopy of Stochastic Nanoparticle Collision: Short Time Fourier Transform versus Continuous Wavelet Transform.

This work demonstrates the utilization of short-time Fourier transform (STFT), and continuous wavelet transform (CWT) electrochemical impedance spectroscopy (EIS) for time-resolved analysis of stochastic collision events of platinum nanoparticles (NPs) onto gold ultramicroelectrode (UME). The enhanced electrocatalytic activity is observed in both chronoamperometry (CA) and EIS. CA provides the impact moment and rough estimation of the size of NPs. The quantitative information such as charge transfer resistance (Rct ) relevant to the exchange current density of a single Pt NP is estimated from EIS. The CWT analysis of the phase angle parameter is better for NP collision detection in terms of time resolution compared to the STFT method.

Special Issue: Recent Advances in Nanomaterials for Electrochemical Sensing and Nano-Biosensing.

Nanomaterials have been instrumental in the development of electrochemical nano-biosensors, offering high sensitivity and selectivity [...].

Observation and Analysis of Staircase Response of Single Palladium Nanoparticle Collision on Gold Ultramicroelectrodes.

Collision (or impact) of single palladium nanoparticles (Pd NPs) on gold (Au), copper (Cu), nickel (Ni), and platinum (Pt) ultramicroelectrodes (UMEs) were investigated via electrocatalytic amplification method. Unlike the blip responses of previous Pd NP collision studies, the staircase current response was obtained with the Au UME. The current response, including collision frequency and peak magnitude, was analyzed depending on the material of the UME and the applied potential. Adsorption factors implying the interaction between the Pd NP and the UMEs are suggested based on the experimental results.

Electrochemical Detection and Analysis of Various Current Responses of a Single Ag Nanoparticle Collision in an Alkaline Electrolyte Solution.

A single silver (Ag) nanoparticle (NP) collision was observed and analyzed in an alkaline solution using the electrocatalytic amplification (EA) method. Previously, the observation of a single Ag NP collision was only possible through limited methods based on a self-oxidation of Ag NPs or a blocking strategy. However, it is difficult to characterize the electrocatalytic activity of Ag NPs at a single NP level using a method based on the self-oxidation of Ag NPs. When using a blocking strategy, size analysis is difficult owing to the edge effect in the current signal. The fast oxidative dissolution of Ag NPs has been a problem for observing the staircase response of a single Ag NP collision signal using the EA method. In alkaline electrolyte conditions, Ag oxides are stable, and the oxidative dissolution of Ag NPs is sluggish. Therefore, in this study, the enhanced magnitude and frequency of the current response for single Ag NP collisions were obtained using the EA method in an alkaline electrolyte solution. The peak height and frequency of single Ag NP collisions were analyzed and compared with the theoretical estimation.

Electrochemical Immunosensor for Human IgE Using Ferrocene Self-Assembled Monolayers Modified ITO Electrode.

The immunoglobulin E (IgE) level in serum is an important factor in the examination of allergy. Ferrocene (Fc)-modified self-assembled monolayers (SAMs) were placed on an indium tin oxide (ITO) electrode as a sensing layer for the detection of human IgE. The Fc moiety in the SAMs facilitated the electron transfer through the organic SAMs layer and electrocatalytic signal amplification. The electrochemical measurement was accomplished after the sandwich type immobilization of the receptor antibody, target human IgE, and enzyme conjugated secondary antibody. The enzyme product, p-aminophenol, was quantitatively analyzed by redox cycling via Fc. In addition, the electrochemical impedance spectroscopy (EIS) was investigated for the detection of IgE. The limit of detection (LOD), limit of quantification (LOQ), and dynamic range of the electrochemical sensor were 3 IU/mL, 10 IU/mL, and from 10 IU/mL to 100 IU/mL, respectively.

Magneto-Biosensor for the Detection of Uric Acid Using Citric Acid-Capped Iron Oxide Nanoparticles.

In this work, a magneto-biosensor based on iron (II, III) oxide (magnetite, Fe3O4) nanoparticles for the detection of uric acid is developed and demonstrated. These Fe3O4 nanoparticles are successfully synthesized by a co-precipitation method comprising Fe2+ and Fe3+ with ammonium hydroxide, NH4OH, and using citric acid as a surfactant. Comparative studies of Fe3O4 nanoparticles with and without surfactant are also carried out to examine their characteristics. Both types of synthesized iron oxide nanoparticles are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field emission-scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometry. The images obtained by field emission-scanning electron microscopy show an average diameter of 30 nm for citric acid-Fe3O4 nanoparticles. The Fourier transform infrared spectra indicate that the carboxylate groups of citric acid are bound onto the surface of magnetite nanoparticles by chemical bonds. For sensing experiments, the synthesized nanoparticles are used to modify the glassy carbon electrode, and the resultant citric acid-Fe3O4 modified glassy carbon electrode is used for the detection of uric acid through cyclic voltammetry. In the case of the citric acid-Fe3O4 nanoparticles-modified glassy carbon electrode, uric acid is oxidized at a less positive potential compared to oxidation using the naked Fe3O4 nanoparticles and a bare glassy carbon electrode. The citric acid-Fe3O4 nanoparticles-modified glassy carbon electrode exhibit a good linear response range for the detection of uric acid of 7.5 µM-0.18 mM, with a lower detection limit of 7.5 µM uric acid. This excellent performance of the fabricated biosensor is attributed to the larger surface area availability of citric acid-Fe3O4 nanoparticles, which promotes constant electron transfer between the modified glassy carbon electrode and the biomolecules (uric acid). The improved electrocatalytic activity of this modified electrode clearly proves that the proposed method is promising for the development of other electrochemical biosensors.

Observation of Single Nanoparticle Collisions with Green Synthesized Pt, Au, and Ag Nanoparticles Using Electrocatalytic Signal Amplification Method.

This work describes the tailored design, green synthesis and characterization of noble metal (Pt, Ag and Au) nanoparticles (NPs) using Sapinduss Mukkorossi fruit extract (SMFE) and its signal NP collision signal response, based on the principle of the electrocatatlytic amplication (EA) method. Here, the SMFE can act as both the reducing and the capping agent for the fabrication of noble nanometals. The SMFE-capped NPs was available for the observation of a single NP collision signal. Two general types of current response were observed: a staircase current response for the Pt or Au NPs, and a blip/spike current response for Ag NPs. These results demonstrated that the eco-friendly synthesized SMFE-capped NPs maintained their electrocatalytic activity, therefore they can be used for the single NP experiments and place an arena for future biosensing applications.

Sustainable ecofriendly phytoextract mediated one pot green recovery of chitosan.

Chitin and chitosan are biopolymers that have diverse applications in medicine, agriculture, food, cosmetics, pharmaceuticals, wastewater treatment and textiles. With bio-origins, they easily blend with biological systems and show exemplified compatibility which is mandatory when it comes to biomedical research. Chitin and chitosan are ecofriendly, however the processes that are used to recover them aren't ecofriendly. The focus of this work is to attempt an ecofriendly, sustainable phytomediated one pot recovery of chitosan from commercial chitin and from crab and shrimp shells and squid pen solid wastes. Graviola extracts have been employed, given the fact file that their active ingredients acetogenins actively interact with chitin in insects (resulting in its application as an insecticide). With that as the core idea, the graviola extracts were chosen for orchestrating chitin recovery and a possible chitin to chitosan transformation. The results confirm that graviola extracts did succeed in recovery of chitosan nanofibers from commercial chitin flakes and recovery of chitosan particles directly from solid marine wastes of crab, shrimp and squids. This is a first time report of a phyto-extract mediated novel chitosan synthesis method.

Chronoamperometric Observation and Analysis of Electrocatalytic Ability of Single Pd Nanoparticle for Hydrogen Peroxide Reduction Reaction.

The current generated by the collision of a single nanoparticle (NP) of palladium (Pd) on a gold (Au) ultramicroelectrode (UME) surface was observed using an electrocatalytic amplification method. The hydrogen peroxide reduction reaction was used for the electrocatalytic reaction because the hydrogen peroxide reduction reaction has no gas-phase product, which would induce rapid signal decay. The electrocatalytic current resulting from a single Pd nanoparticle on the Au UME shows a staircase response with accompanying slow current decay. The applying potential and concentration of hydrogen peroxide were optimized for clear distinction of signal. The height of the current step and signal frequency were analyzed and compared with the theoretical expectation. The analysis of the electrocatalytic activity of single Pd NPs provides insight toward their future application.

Biosynthesis of Copper Oxide (CuO) Nanowires and Their Use for the Electrochemical Sensing of Dopamine.

A facile one-step, eco-friendly, and cost-effective approach for the formation of copper oxide (CuO) nanowires by a green method using saponin-rich Sapindus mukorossi fruit extract (SMFE). The physio-chemical characteristics of the synthesized CuO nanowires have been characterized by X-ray Diffractometry (XRD), X-ray Photoelectron Spectroscopy (XPS), FT-IR (Fourier Transform Infrared Spectroscopy, FE-SEM (Scanning Electron Microscopy), and High-Resolution Transmission Electron Microscopy (HR-TEM). Further, the electrocatalytic activity of the CuO nanowires synthesized with SMFE has been investigated, and they have been used as dopamine (DA) sensors. Because of their unique properties, the CuO nanowires/GCE exhibited remarkable electrochemical response for the detection of DA with enhanced current response. The anodic current demonstrated that the CuO nanowires/GCE linearly detects the concentration of DA over the range of 0.1 µM to 0.105 mM of DA with a regression co-efficient of 0.9960. The obtained results illustrated that the synthesized CuO nanowires can easily stimulate the electron transfer reaction between DA and the nanowires modified electrode with the improvement of the conductivity and stability of the electrode. This remarkable electrocatalytic property of CuO nanowires makes it a unique electrochemical sensor for the detection of DA. Furthermore, the sensor is free from the interference of ascorbic acid, uric acid, and other interfering species. Moreover, the anti-interference performance also showed that the CuO nanowires/GCE could be employed for the determination of DA in real samples with good selectivity and sensitivity.

Various Current Responses of Single Silver Nanoparticle Collisions on a Gold Ultramicroelectrode Depending on the Collision Conditions.

Collisions of silver nanoparticles (NPs) with a more electrocatalytic gold or platinum ultramicroelectrode (UME) surface have been observed by using an electrochemical method. Depending on the applied potential to the UME, the current response to the collision of Ag NPs on the UME resulted in various shape changes. A staircase decrease, a blip decrease, and a blip increase of the hydrazine oxidation current were obtained at an applied potential of 0.33, 0.80, and 1.3 V, respectively. Different collision behaviors of Ag NPs on the UME surface were suggested for each shape of current response. Ag NP attachment, which hindered the diffusion flux to the UME, caused a staircase decrease of the electrocatalytic current. Instantaneous blocking of the hydrazine oxidation by Ag NP collision and, following recovery of the current by means of oxidation of Ag NP, caused a blip decrease of the electrocatalytic current. The formation of a higher oxidation state of Ag on the Ag NP and its electrocatalytic hydrazine oxidation resulted in a blip increase of the electrocatalytic current. The analysis of the current response of a single NP collision experiment can be a useful tool to understand the various behaviors of NPs on the electrode surface.

Direct Observation of the Collision of Single Pt Nanoparticles onto Single-Crystalline Gold Nanowire Electrodes.

We observed the collision of single Pt nanoparticles (NPs) onto an Au nanowire (NW) electrode by using electrocatalytic amplification. Previously, such observations had typically been performed by using a microscale disk-type ultramicroelectrode (UME). The use of a NW electrode decreased the background noise current and provided a shielding effect, owing to adsorption of the NPs onto the insulating sheath. Therefore, the transient current signal that was caused by the collision of single NPs could be more clearly distinguished from the background current by using a NW electrode instead of a UME. Furthermore, the use of a NW electrode increased the collisional frequency and the magnitude of the transient current signal. The experimental data were analyzed by using a theoretical model and a random walk simulation model.

Observation of Single Pt Nanoparticle Collisions: Enhanced Electrocatalytic Activity on a Pd Ultramicroelectrode.

Single Pt nanoparticle (NP) collisions on an electrode surface were detected by using an electrocatalytic amplification method with a Pd ultramicroelectrode (UME). Pd is not a preferred material for UMEs for the detection of single Pt NP collisions, because Pd shows similar electrocatalytic activity compared with Pt for hydrazine oxidation, thus resulting in a high background current level. However, a Pt NP colliding on the Pd UME shows greatly enhanced activity compared with a Pt NP on an inert UME, such as a Au UME, which is usually used for the detection of single Pt NP collisions. The use of an electroactive UME material instead of an inert one facilitated the study of single-NP activity on the various solid supports, which is important in many NP applications.

Combined Blip and Staircase Response of Ascorbic Acid-Stabilized Copper Single Nanoparticle Collision by Electrocatalytic Glucose Oxidation.

The current response of the collision of ascorbic acid-stabilized copper (Cu) single nanoparticles (NPs) on a gold (Au) ultramicroelectrode (UME) surface was observed by using an electrocatalytic amplification method. Here, the glucose oxidation electrocatalyzed by oxidized Cu NPs was used as the indicating reaction. In this system, the NP collision signals were obtained simultaneously by both direct particle electrolysis and electrocatalytic amplification. For example, when the applied potential was high enough for Cu NP oxidation, a blip response combined with a staircase response was observed as a current signal. The blip part in the single Cu NP collision signal indicates the self-oxidation of a Cu NP, and the staircase part indicates the steady-state electrocatalytic reaction by oxidized Cu NP.

Skeletal octahedral nanoframe with Cartesian coordinates via geometrically precise nanoscale phase segregation in a Pt@Ni core-shell nanocrystal.

Catalytic properties of nanoparticles can be significantly enhanced by controlling nanoscale alloying and its structure. In this work, by using a facet-controlled Pt@Ni core-shell octahedron nanoparticle, we show that the nanoscale phase segregation can have directionality and be geometrically controlled to produce a Ni octahedron that is penetrated by Pt atoms along three orthogonal Cartesian axes and is coated by Pt atoms along its edges. This peculiar anisotropic diffusion of Pt core atoms along the ⟨100⟩ vertex, and then toward the ⟨110⟩ edges, is explained via the minimum strain energy for Ni-Ni pair interactions. The selective removal of the Ni-rich phase by etching then results in structurally fortified Pt-rich skeletal PtNi alloy framework nanostructures. Electrochemical evaluation of this hollow nanoframe suggests that the oxygen reduction reaction (ORR) activity is greatly improved compared to conventional Pt catalysts.

Potential-controlled current responses from staircase to blip in single Pt nanoparticle collisions on a Ni ultramicroelectrode.

Collisions of electrocatalytic platinum (Pt) single nanoparticles (NPs) with a less electrocatalytic nickel (Ni) ultramicroelectrode (UME) surface were detected by amplification of the current by electrocatalysis of NPs. Two typical types of current responses, a current staircase or blip (or spike), in single NP collision experiments were observed at a time with a new system consisting of Pt NP/Ni UME/hydrazine oxidation. The staircase current response was obtained when the collided NPs were attached to the electrode and continued to produce electrocatalytic current. On the other hand, the blip current response was believed to be obtained when the NP attached but was deactivated. The different current responses depend on the different electrocatalytic reaction mechanism, characteristics of the NP, or the electrode material. How the deactivation of the electrocatalytic process affects on the current response of NP collision was investigated using the Ni UME. The current response of a single Pt NP collision is controllable from staircase to blip by changing the applied potential. The current response of the Pt NP was observed as a staircase response with 0 V (vs Ag/AgCl) and as a blip response with 0.1 V (vs Ag/AgCl) applied to the Ni UME.

One pot synthesis of nanoscale phase-segregated PdPt nanoarchitectures via unusual Pt-doping induced structural reorganization of a Pd nanosheet into a PdPt nanotent.

Pt-doping of an ultrathin Pd nanosheet results in the unprecedented structural rearrangement of a Pd nanosheet into a PdPt nanotent structure, in which a tripod stands on a triangular nanosheet. Further growth of Pt phase on this nanotent structure is dependent on the presence of surface-stabilizing CO molecules, leading to the formation of two distinct nanoscale phase segregated structures with respective structural features of a popped out Pt facet and an overgrown Pt layer.

One-pot synthesis of ultralong coaxial Au@Pt nanocables with numerous highly catalytically active perpendicular twinning boundaries and Au@Pt core-shell bead structures.

Ultralong coaxial Au@Pt nanocables prepared by one-pot synthesis exhibit excellent electrocatalytic activity due to structural features of (1) numerous twinning boundaries and (2) lattice mismatch between the core and the shell.

Axially twinned nanodumbbell with a Pt bar and two Rh@Pt balls designed for high catalytic activity.

A fail-proof synthetic strategy has been developed for a multiply twinned dumbbell-shaped Rh@Pt nanostructure, which exhibits a superior electrocatalytic activity for methanol oxidation reaction. The unusually high electrocatalytic activity has been attributed to the synergistic effects of crystal twinning and core-shell structure.