Are Redox-active Centers Bridged by Saturated Flexible Linkers Systematically Electrochemically Independent?

The extent to which electrophores covalently bridged by a saturated linker are electrochemically independent was investigated considering the charge/spin duality of the electron and functionality of the electrophore as a spin carrier upon reduction. By combining computational modeling with electrochemical experiments, we investigated the mechanism by which tethered electrophores react together within 4,4'-oligo[n]methylene-bipyridinium assemblies (with n = 2 to 5). We show that native dicationic electrophores (redox state Z = +2) are folded prior to electron injection into the system, allowing the emergence of supra-molecular orbitals (supra-MOs) likely to support the process of the reductive s bond formation giving cyclomers. Indeed, for Z = +2, London Dispersion (LD) forces contribute to flatten the potential energy surface such that all-trans and folded conformers are approximately isoenergetic. Then, upon one-electron injection, for radical cations (Z = +1), LD forces significantly stabilize the folded conformers, except for the ethylene derivative deprived of supra-MOs. For radical cations equipped with supra-MOs, the unpaired electron is delocalized over both heterocycles through space. Cyclomer completion (Z = 0) upon the second electron transfer occurs according to the inversion of redox potentials. This mechanism explains why intramolecular reactivity is favored and why pyridinium electrophores are not independent.

Pencil graphite electrodes for in-situ spectroelectrochemical sensing of reaction intermediates and products in organic solvents.

BACKGROUND: Spectroelectrochemistry (SEC) is a valuable analytical tool providing insights to reaction mechanisms and the structure of species involved in charge transfer reactions. Most of commercial SEC setups are based on platinum working electrodes where the adsorption of species involved in reactions often complicates their analysis. RESULTS: In this work, we employ an array of pencil graphite rods as an optically transparent working electrode in a custom-made air-tight thin-layer cell suitable for the SEC analysis performed here in acetonitrile as a representative non-aqueous solvent. The functionality of the device was demonstrated by UV-Vis SEC sensing of charge transfer reactions of ruthenium acetylacetonate, ferrocene and ethylviologen dibromide redox probes performed employing the cyclic voltammetry. The SEC response obtained for all three probes confirmed no adsorption and the absence of oxygen in the cell. Furthermore, we have developed and utilized finite element method numerical simulations considering charge transfer reactions coupled with the diffusional mass transport to model the cyclic voltammetric response and the reaction conversion in the thin-layer SEC cell. SIGNIFICANCE: Our work paves the way for easy-to-assemble customized air-tight adsorption-free SEC devices with the manufacturing costs well below those of commercially available platforms. Developed computational approaches have the predictive power for optimizing reaction conditions and the geometry of the SEC cell.

Probing charge transfer through antifouling polymer brushes by electrochemical methods: The impact of supporting self-assembled monolayer chain length.

Ultrathin surface-tethered polymer brushes represent attractive platforms for a wide range of sensing applications in strategically vital areas such as medicine, forensics, or security. The recent trends in such developments towards "real world conditions" highlighted the role of zwitterionic poly(carboxybetaine) (pCB) brushes which provide excellent antifouling properties combined with bio-functionalization capacity. Highly dense pCB brushes are usually prepared by the "grafting from" polymerization triggered by initiators on self-assembled monolayers (SAMs). Here, multi-methodological experimental studies are pursued to elucidate the impact of the alkanethiolate SAM chain length (C6, C8 and C11) on structural and functional properties of antifouling poly(carboxybetaine methacrylamide) (pCBMAA) brush. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a custom-made 3D printed cell employing [Ru(NH3)6]3+/2+ redox probe were used to investigate penetrability of SAM/pCBMAA bilayers for small molecules and interfacial charge transfer characteristics. The biofouling resistance of pCBMAA brushes was characterized by surface plasmon resonance; ellipsometry and FT-IRRAS spectroscopy were used to determine swelling and relative density of the brushes synthesized from initiator-bearing SAMs with varied carbon chain length. The SAM length was found to have a substantial impact on all studied characteristics; the highest value of charge transfer resistance (Rct) was observed for denser pCBMAA on longer-chain (C11) SAM when compared to shorter (C8/C6) SAMs. The observed high value of Rct for C11 implies a limitation for the analytical performance of electrochemical sensing methods. At the same time, the pCBMAA brushes on C11 SAM exhibited the best bio-fouling resistance among inspected systems. This demonstrates that proper selection of supporting structures for brushes is critical in the design of these assemblies for biosensing applications.

Spectroelectrochemical sensing of reaction intermediates and products in an affordable fully 3D printed device.

Recent advances in fused deposition modelling 3D printing (FDM 3DP) and synthesis of printable electrically conductive materials enabled the manufacture of customized electrodes and electrochemical devices by this technique. The past couple of years have seen a boom in applying approaches of FDM 3DP in the realm of spectroelectrochemistry (SEC). Despite significant progress, reported designs of SEC devices still rely on conventionally manufactured optical components such as quartz windows and cuvettes. To bridge this technological gap, in this work we apply bi-material FDM 3DP combining electrically conductive and optically translucent filaments to manufacture working electrodes and cells, constituting a fully integrated microfluidic platform for transmission absorption UV-Vis SEC measurements. The cell design enables de-aeration of samples and their convenient handling and analysis. Employing cyclic voltammetric measurements with ruthenium(III) acetylacetonate, ethylviologen dibromide and ferrocenemethanol redox-active probes as model analytes, we demonstrate that the presented platform allows SEC sensing of reactants, intermediates and products of charge transfer reactions, including the inspection of their long-term stability. Approaches developed and presented in this work pave the way for manufacturing customized SEC devices with dramatically reduced costs compared to currently available commercial platforms.

Direct electrochemical determination of environmentally harmful pharmaceutical ciprofloxacin in 3D printed flow-through cell.

Rising amounts of antibiotic residues in wastewater cause serious problems including increased bacterial resistance. Wastewater treatment plants (WWTPs) do not, in the case of new, modern pharmaceuticals, ensure their complete removal. Ciprofloxacin (CIP) is one of many micropollutants that partially pass through WWTPs, implying that its monitoring is essential for the assessment of the water quality. In real sewage systems, the determination of CIP needs to be performed under flowing conditions, which calls for the deployment of inexpensive, robust, and easily integrable approaches such as electrochemical techniques. However, to the best of our knowledge, there is no report on the electrochemical determination of CIP in a flowing matrix. To bridge this gap, we perform here cyclic and square-wave voltammetric sensing study of CIP employing boron-doped diamond screen printed electrodes in a custom-made 3D printed flow-through cell to mimic conditions in real sewage systems. An irreversible two-step oxidation of CIP is demonstrated, with the first step providing clear Faradaic response as analytically relevant signal. This response was found to scale with the sample flow rate according to the prediction given by Levich equation. Our work provides an in-depth inspection of the electrochemical response of CIP under controlled-convection conditions, which is an essential prerequisite for monitoring this antibiotic in real flowing sewage systems.

3D Printed Platform for Impedimetric Sensing of Liquids and Microfluidic Channels.

Fused deposition modeling 3D printing (FDM-3DP) employing electrically conductive filaments has recently been recognized as an exceptionally attractive tool for the manufacture of sensing devices. However, capabilities of 3DP electrodes to measure electric properties of materials have not yet been explored. To bridge this gap, we employ bimaterial FDM-3DP combining electrically conductive and insulating filaments to build an integrated platform for sensing conductivity and permittivity of liquids by impedance measurements. The functionality of the device is demonstrated by measuring conductivity of aqueous potassium chloride solution and bottled water samples and permittivity of water, ethanol, and their mixtures. We further implement an original idea of applying impedance measurements to investigate dimensions of 3DP channels as base structures of microfluidic devices, complemented by their optical microscopic analysis. We demonstrate that FDM-3DP allows the manufacture of microchannels of width down to 80 µm.

Applicability of Selected 3D Printing Materials in Electrochemistry.

This manuscript investigates the chemical and structural stability of 3D printing materials (3DPMs) frequently used in electrochemistry. Four 3D printing materials were studied: Clear photopolymer, Elastic photopolymer, PET filament, and PLA filament. Their stability, solubility, structural changes, flexibility, hardness, and color changes were investigated after exposure to selected organic solvents and supporting electrolytes. Furthermore, the available potential windows and behavior of redox probes in selected supporting electrolytes were investigated before and after the exposure of the 3D-printed objects to the electrolytes at various working electrodes. Possible electrochemically active interferences with an origin from the 3DPMs were also monitored to provide a comprehensive outline for the use of 3DPMs in electrochemical platform manufacturing.

Hierarchical TiO2 Layers Prepared by Plasma Jets.

Heterogeneous photocatalysis of TiO2 is one of the most efficient advanced oxidation processes for water and air purification. Here, we prepared hierarchical TiO2 layers (Spikelets) by hollow-cathode discharge sputtering and tested their photocatalytic performance in the abatement of inorganic (NO, NO2) and organic (4-chlorophenol) pollutant dispersed in air and water, respectively. The structural-textural properties of the photocatalysts were determined via variety of physico-chemical techniques (XRD, Raman spectroscopy, SEM, FE-SEM. DF-TEM, EDAX and DC measurements). The photocatalysis was carried out under conditions similar to real environment conditions. Although the abatement of NO and NO2 was comparable with that of industrial benchmark Aeroxide® TiO2 P25, the formation of harmful nitrous acid (HONO) product on the Spikelet TiO2 layers was suppressed. Similarly, in the decontamination of water by organics, the mineralization of 4-chlorophenol on Spikelet layers was interestingly the same, although their reaction rate constant was three-times lower. The possible explanation may be the more than half-magnitude order higher external quantum efficacy (EQE) compared to that of the reference TiO2 P25 layer. Therefore, such favorable kinetics and reaction selectivity, together with feasible scale-up, make the hierarchical TiO2 layers very promising photocatalyst which can be used for environmental remediation.

The development of a fully integrated 3D printed electrochemical platform and its application to investigate the chemical reaction between carbon dioxide and hydrazine.

The combination of computer assisted design and 3D printing has recently enabled fast and inexpensive manufacture of customized 'reactionware' for broad range of electrochemical applications. In this work bi-material fused deposition modeling 3D printing is utilized to construct an integrated platform based on a polyamide electrochemical cell and electrodes manufactured from a polylactic acid-carbon nanotube conductive composite. The cell contains separated compartments for the reference and counter electrode and enables reactants to be introduced and inspected under oxygen-free conditions. The developed platform was employed in a study investigating the electrochemical oxidation of aqueous hydrazine coupled to its bulk reaction with carbon dioxide. The analysis of cyclic voltammograms obtained in reaction mixtures with systematically varied composition confirmed that the reaction between hydrazine and carbon dioxide follows 1/1 stoichiometry and the corresponding equilibrium constant amounts to (2.8 ± 0.6) × 103. Experimental characteristics were verified by results of numerical simulations based on the finite-element-method.