Industry Viable Electrochemical DNA Detection Sensor Architecture via a Stem-Loop Methylene Blue Redox Reporter and Rapid In Situ Probe Immobilization Method for Pharmacogenetic Biomarker Testing Application

Identification of biomarkers in clinical applications for diagnostics at the point-of-care (POC) setting requires the development of industry viable biosensing platform. Herein, we report such development of biosensor architecture for the detection of pharmacogenetic biomarker HLA-B*15:02 gene. The biosensor architecture comprises of an oligonucleotide stem-loop probe modified with a methylene blue redox (MB) reporter, immobilized via a rapid 'printing' method on the commercially available disposable screen-printed electrodes (SPE). The square wave voltammetric measurements on the DNA sensor showed a clear peak difference of ~80 nA with a significant difference in peak height values of the faradaic current generated for the MB redox moiety between the positive control (biotin-modified 19 based oligonucleotides with the sequence mimicking the specific region of the HLA-B*15:02 allele and complementary to the probe sequence) and negative control samples (biotin-modified 19 based oligonucleotides with the sequence unrelated to the probe sequence and the HLA-B*15:02 allele). These initial proof of concept results provide support for the possibility of using this signal-off biosensor architecture in the intended pharmacogenetic biomarker testing.

Visible-Light-Assisted Photoelectrochemical Biosensing of Uric Acid Using Metal-Free Graphene Oxide Nanoribbons

In this study, we demonstrate the visible-light-assisted photoelectrochemical (PEC) biosensing of uric acid (UA) by using graphene oxide nanoribbons (GONRs) as PEC electrode materials. Specifically, GONRs with controlled properties were synthesized by the microwave-assisted exfoliation of multi-walled carbon nanotubes. For the detection of UA, GONRs were adopted to modify either a screen-printed carbon electrode (SPCE) or a glassy carbon electrode (GCE). Cyclic voltammetry analyses indicated that all Faradaic currents of UA oxidation on GONRs with different unzipping/exfoliating levels on SPCE increased by more than 20.0% under AM 1.5 irradiation. Among these, the GONRs synthesized under a microwave power of 200 W, namely GONR(200 W), exhibited the highest increase in Faradaic current. Notably, the GONR(200 W)/GCE electrodes revealed a remarkable elevation (~40.0%) of the Faradaic current when irradiated by light-emitting diode (LED) light sources under an intensity of illumination of 80 mW/cm2. Therefore, it is believed that our GONRs hold great potential for developing a novel platform for PEC biosensing.

Design of 3D Carbon Nanotube Monoliths for Potential-Controlled Adsorption

The design of 3D monoliths provides a promising opportunity to scale the unique properties of singular carbon nanotubes to a macroscopic level. However, the synthesis of carbon nanotube monoliths is often characterized by complex procedures and additives impairing the later macroscopic properties. Here, we present a simple and efficient synthesis protocol leading to the formation of free-standing, stable, and highly conductive 3D carbon nanotube monoliths for later application in potential-controlled adsorption in aqueous systems. We synthesized monoliths displaying high tensile strength, excellent conductivity (up to 140 S m−1), and a large specific surface area (up to 177 m2 g−1). The resulting monoliths were studied as novel electrode materials for the reversible electrosorption of maleic acid. The process principle was investigated using chronoamperometry and cyclic voltammetry in a two-electrode setup. A stable electrochemical behavior was observed, and the synthesized monoliths displayed capacitive and faradaic current responses. At moderate applied overpotentials (± 500 mV vs. open circuit potential), the monolithic electrodes showed a high loading capacity (~20 µmol g−1) and reversible potential-triggered release of the analyte. Our results demonstrate that carbon nanotube monoliths can be used as novel electrode material to control the adsorption of small organic molecules onto charged surfaces.

Recent advances on bipolar electrochemiluminescence in analytical application

Background: Bipolar electrode (BPE), as an immersed electrical conductor in the electrolyte, can be polarized into cathodic and anodic poles under a sufficient electric field without direct contact, which affords a unique way to promote asymmetrical reactions at two poles. Up to date, bipolar electrochemistry has been widely used in the preparation of Janus materials, the fabrication of sensing/screening platforms, target focusing, and microswimmers. However, the wireless feature of BPE makes the monitoring of Faradaic current difficult. Electrochemiluminescence (ECL), the light emission via an electrochemical reaction, matches the feature of bipolar electrochemistry and is widely adopted to achieve the recording of the Faradaic current flowing through the BPE. The objective of the present review aims to demonstrate the most recent advances of analytical applications (2016-2020) in combination with the high sensitive ECL as the output. Methods: Due to the difficulty in recording the Faradaic current flowing the BPE, the ECL, as a simple, sensitive and detectable signal-out, has become a popular method for analytical application based on the BPE. This review mainly summarizes the recent research on BPE/ECL based on the configuration and sensing principle of BPE designed in the ECL analysis. Results: The various sensors based on the BPE/ECL have been proposed for the electroactive targets and the bio-relevant molecules without the electroactivity by different ingenious designs. Besides, the microelectrode array and ultra-microelectrode (UME) array have also been applied in the BPE/ECL field to achieve the high temporal-spatial resolution imaging of the sample molecules based on the BPE microelectrode array. Conclusion: The combination of BPE and ECL provides a simple, portable, and versatile sensor strategy for various targets due to the unique advantages of BPE and ECL, and easily recognizes the fast, accurate, and point-of-care diagnostics of numerous diseases. Though the BPE/ECL analysis has many merits such as high-throughput, excellent sensitivity, high spatial-temporal resolution, the sensitive and commercial ECL analysis based on the BPE is still difficult to conduct and the analysis research on BPE/ECL is still in the early stage.

Novel Nanoarchitectures Based on Lignin Nanoparticles for Electrochemical Eco-Friendly Biosensing Development

Novel nanoarchitectures based on lignin nanoparticles (LNPs) were designed and realized for electrochemical eco-friendly biosensing development. Two types of lignin nanoparticles were utilized for the modification of a gold bare electrode, namely organosolv (OLNPs) and kraft lignin (KLNPs) nanoparticles, synthetized from a sulfur-free and a sulfur lignin, respectively. The electrochemical behavior of LNP-modified electrodes was studied using two electrochemical techniques, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Compared to the gold bare electrode, an evident decrease in the faradaic current and increase of the ΔEp were observed in cyclic voltammograms. In addition, larger semicircles were registered in Nyquist plots. These results suggest a strong inhibition effect of the electron transfer reaction by LNPs layer, especially in the case of KLNPs. The modified electrodes, properly assembled with concanavalin A (ConA) and glucose oxidase (GOx), were successively tested as biosensing platforms for glucose, showing a sensitivity of (4.53 ± 0.467) and (13.74 ± 1.84) μA mM−1 cm2 for Au/SAMCys/OLNPs/ConA/GOx and Au/KLNPs/ConA/GOx biosensors, respectively. Finally, different layers of the KNLPs/ConA/GOx-modified Au electrode were tested, and the three-layered Au(KNLPs/ConA/GOx)3 showed the best analytical performance.

Nanoscale redox mapping at the MoS2-liquid interface

Layered MoS2 is considered as one of the most promising two-dimensional photocatalytic materials for hydrogen evolution and water splitting; however, the electronic structure at the MoS2-liquid interface is so far insufficiently resolved. Measuring and understanding the band offset at the surfaces of MoS2 are crucial for understanding catalytic reactions and to achieve further improvements in performance. Herein, the heterogeneous charge transfer behavior of MoS2 flakes of various layer numbers and sizes is addressed with high spatial resolution in organic solutions using the ferrocene/ferrocenium (Fc/Fc+) redox pair as a probe in near-field scanning electrochemical microscopy, i.e. in close nm probe-sample proximity. Redox mapping reveals an area and layer dependent reactivity for MoS2 with a detailed insight into the local processes as band offset and confinement of the faradaic current obtained. In combination with additional characterization methods, we deduce a band alignment occurring at the liquid-solid interface.

DESENVOLVIMENTO DE SOFTWARE E INTERFACE PARA O CONTROLE POR RETROALIMENTAÇÃO ATRASADA EM SISTEMAS ELETROQUÍMICOS

DEVELOPMENT OF SOFTWARE AND INTERFACE FOR DELAYED FEEDBACK CONTROL IN ELECTROCHEMICAL SYSTEMS. In this paper, we show the development of a LabVIEW algorithm able to apply the delayed feedback control on oscillatory electrochemical reactions. The coupling of the control and the experiments was carried out by a real-time apparatus, measuring the faradaic current and, in sequence, applying a calculated circuit voltage as an analog output. The setup was used to control the oscillatory Cu/Sn electrodeposition dynamics, used as a model-system, and the results clearly demonstrate the control accuracy. Overall, the code may be a great tool for the controlled synthesis of nanomaterials in different oscillatory electrodeposition reactions, as it offers the ability to control the composition and structure of the deposit by fine tuning the dynamic properties.

A rational experimental approach to identify correctly the working voltage window of aqueous-based supercapacitors

It is common to find in the literature different values for the working voltage window (WVW) range for aqueous-based supercapacitors. In many cases, even with the best intentions of the widening the operating voltage window, the measured current using the cyclic voltammetry (CV) technique includes a significant contribution from the irreversible Faradaic reactions involved in the water-splitting process, masked by fast scan rates. Sometimes even using low scan rates is hard to determine precisely the correct WVW of the aqueous-based electrochemical capacitor. In this sense, we discuss here the best practices to determine the WVW for capacitive current in an absence of water splitting using complementary techniques such as CV, chronoamperometry (CA), and the electrochemical impedance spectroscopy (EIS). To accomplish this end, we prepare and present a model system composed of multiwalled carbon nanotubes buckypaper electrodes housed in the symmetric coin cell and soaked with an aqueous-based electrolyte. The system electrochemical characteristics are carefully evaluated during the progressive enlargement of the cell voltage window. The presence of residual Faradaic current is verified in the transients from the CA study, as well as the impedance changes revealed by EIS as a function of the applied voltage, is discussed. We verify that an apparent voltage window of 2.0 V determined using the CV technique is drastically decreased to 1.2 V after a close inspection of the CA findings used to discriminate the presence of a parasitic Faradaic process. Some orientations are presented to instigate the establishment in the literature of some good scientific practices concerned with the reliable characterization of supercapacitors.