SECM for Studying the Immobilization and Repartition of a Redox Anti-tetracycline Aptamer on Screen-printed Carbon Electrodes

Scanning electrochemical microscopy (SECM) is discussed as a versatile tool to provide a unique approach of localized electrochemical information in the context of biosensing research. The step-by-step immobilization of DNA aptamer with intrinsic redox activity on screen-printed carbon electrode (SPCE) was successfully monitored using SECM imaging tool. Control experiments were performed with a non-electroactive aptamer. After immobilization of these aptamers, SECM images showed the repartition of the electroactive anti-tetracycline aptamer when comparing with images produced for control and for all modification steps of SPCE. The possibility of tetracycline detection was also proved by causing a decrease in recorded current.     

SECM and SKPFM Studies of the Local Corrosion Mechanism of Al Alloys – A Pathway to an Integrated SKP‐SECM System

Scanning Kelvin Probe Force Microscopy and Scanning Electrochemical Microscopy were applied for the investigation of localized corrosion on heterogeneous aiming on the investigation of the possible correlation between the local surface potential differences, measured by the Kelvin probe technique in ambient conditions, and corrosion during immersion in a corrosive electrolyte. A model sample mimicking the interaction of Al and Cu in Al alloys was chosen to demonstrate the complementary nature of the information received from SKPFM and SECM. The necessary prerequisites for a future integration of SKP and SECM into a single set‐up are discussed.     

Localization of proteins in paint cross-sections by scanning electrochemical microscopy as an alternative immunochemical detection technique

The qualitative identification of proteinaceous substances, as well as their location within a complex paint stratigraphy, is one of the most challenging issues in the characterization of painting materials. Nevertheless, information on paint components represent a crucial task for studies concerning both the ancient painting techniques adopted and the state of conservation, being fundamental investigations for the selection of appropriate conservation actions. The present research was aimed at developing a new detection approach for the immunochemical localization of ovalbumin in paint cross-sections based on the use of scanning electrochemical microscopy (SECM). The immunochemical analyses were performed using an anti-ovalbumin primary antibody and a secondary antibody labelled with horseradish peroxidase (HRP). SECM measurements were performed in feedback mode using benzoquinone (BQ)/hydroquinone (H₂Q) redox couple. In presence of hydrogen peroxide (H₂O₂), HRP catalyzes the re-oxidation of H₂Q to BQ and the increment of BQ concentration in correspondence of the target protein was detected by SECM through the electrochemical reduction of the regenerated BQ at the microelectrode. Indeed, the localization of ovalbumin was possible thanks to a clear discrimination of SECM currents, achieved by the comparison of the measurements recorded before and after H₂O₂ administration, based on the HRP on/off approach. The method was evaluated both on samples from standard mocks-up and on a historical sample, collected from a Renaissance wood painting. The obtained results were promising, foreseeing a wider application of SECM on cultural heritage researches.     

Determination of the Apparent Michaelis Constant of Glucose Oxidase Immobilized on a Microelectrode with Respect to Oxygen

We report determination of the apparent Michaelis constant of glucose oxidase (GOx) immobilized on a microelectrode with respect to oxygen. We used a GOx‐modified microelectrode as a probe for scanning electrochemical microscopy. We detected hydrogen peroxide generated by the enzyme reaction at the microelectrode under controlling the oxygen concentration using water electrolysis at an interdigitated array (IDA) electrode. The response depends on the oxygen concentration, which is regulated by the microelectrode position and the potential applied to the IDA electrode. We estimated the apparent Michaelis constant with respect to oxygen in this experimental condition to be about 0.28 mM.     

The Influence of Nucleophilic and Redox Pincer Character as well as Alkali Metals on the Capture of Oxygen Substrates: The Case of Chromium(II)

Dimeric [CrL]₂, where L is the conjugate base of bis-pyrazolyl pyridine, is evaluated for its ability to undergo inner sphere and outer sphere redox chemistry. It reacts with Cp₂Fe⁺ to give [Cr₄(HL)₄(μ₄-O)]²⁺, still containing divalent Cr. Reduction (KC₈) of [CrL]₂ by two electrons gives [K₂(THF)₃Cr₃L₃(μ₃-O)], and by four electrons gives [K₄(THF)₁₀Cr₂L₂(μ-O)], each of which has scavenged (hydr)oxide from glass surface because of the electrophilicity of the underligated Cr. [K₄(THF)₁₀Cr₂L₂(μ-O)], is shown by comprehensive DFT calculations and analysis of intra-ligand bond lengths to contain a pyridyl radical L³⁻ and Cr^II, illustrating that this pincer is proton-responsive, redox active, and a versatile donor to associated K⁺ ions here. The K⁺ electrophiles interact with electron-rich oxo, but do not significantly (>5 kcal mol⁻¹) alter spin state energies. Inner sphere oxidation of [CrL]₂ with a quinone gives [Cr₂L₂(semiquinone)₂], while pre-reduced [CrL]₂²⁻ reacts with quinone to give [K₃(THF)₃Cr₂L₂(catecholate)₂(μ-OH)], a product of capture of two undercoordinated LCr(catecholate)¹⁻ by hydroxide.     

The Direct Electron Transfer of Iron‐containing Metal Organic Frameworks (Mil‐100) and Its Catalysis for the Oxygen Reduction Reaction in Room‐Temperature Alkaline Media on a Glass Carbon Electrode

The most common electrocatalysts for the oxygen reduction reaction (ORR) are platinum‐based ones. This work demonstrates the performance of iron‐containing metal organic frameworks (MOFs) as non‐platinum‐based nano‐electrocatalysts for ORR in an alkaline medium. As a new non‐platinum catalyst to achieve the active sites for the ORR, Mil‐100 (Fe) nanoparticles were used in aqueous KOH by the rotating‐disk electrode method. The main objectives of this study are the investigations on the electron transfer number (n ), Tafel slope, and catalytic performance. The particles size of the obtained powders is in the nanoscale range (approximately 25 nm). The electron transfer number for the ORR on the surface of iron‐containing catalyst is approximately 4, and the Tafel slope of diffusion‐corrected kinetic current density is ~50.7 mV per decade at low overpotential. This work might extend a new non‐precious‐metal catalyst structure for ORR for use in low‐temperature fuel cells.