Microwave-Induced Processing of Free-Standing 3D Printouts: An Effortless Route to High-Redox Kinetics in Electroanalysis.

3D-printable composites have become an attractive option used for the design and manufacture of electrochemical sensors. However, to ensure proper charge-transfer kinetics at the electrode/electrolyte interface, activation is often required, with this step consisting of polymer removal to reveal the conductive nanofiller. In this work, we present a novel effective method for the activation of composites consisting of poly(lactic acid) filled with carbon black (CB-PLA) using microwave radiation. A microwave synthesizer used in chemical laboratories (CEM, Matthews, NC, USA) was used for this purpose, establishing that the appropriate activation time for CB-PLA electrodes is 15 min at 70 °C with a microwave power of 100 W. However, the usefulness of an 80 W kitchen microwave oven is also presented for the first time and discussed as a more sustainable approach to CB-PLA electrode activation. It has been established that 10 min in a kitchen microwave oven is adequate to activate the electrode. The electrochemical properties of the microwave-activated electrodes were determined by electrochemical techniques, and their topography was characterized using scanning electron microscopy (SEM), Raman spectroscopy, and contact-angle measurements. This study confirms that during microwave activation, PLAs decompose to uncover the conductive carbon-black filler. We deliver a proof-of-concept of the utility of kitchen microwave-oven activation of a 3D-printed, free-standing electrochemical cell (FSEC) in paracetamol electroanalysis in aqueous electrolyte solution. We established satisfactory limits of linearity for paracetamol detection using voltammetry, ranging from 1.9 µM to 1 mM, with a detection limit (LOD) of 1.31 µM.

Boron-doped diamond nanosheet volume-enriched screen-printed carbon electrodes: a platform for electroanalytical and impedimetric biosensor applications.

This paper focuses on the development of a novel electrode based on boron-doped diamond nanosheet full-volume-enriched screen-printed carbon electrodes (BDDPE) for use as an impedimetric biosensor. Impedimetric biosensors offer high sensitivity and selectivity for virus detection, but their use as point-of-care devices is limited by the complexity of nanomaterials' architecture and the receptor immobilisation procedures. The study presents a two-step modification process involving the electroreduction of diazonium salt at the BDDPE and the immobilisation of antibodies using zero-length cross-linkers for a selective impedimetric biosensor of Haemophilus influenzae (Hi). The incorporation of diamond nanosheets into BDDPE leads to enhanced charge transfer and electrochemical behaviour, demonstrating greatly improved electrochemically active surface area compared with unmodified screen-printed electrodes (by 44% and 10% on average for [Ru(NH3)6]Cl2 and K3[Fe(CN)6], respectively). The presented sensing system shows high specificity towards protein D in Hi bacteria, as confirmed by negative controls against potential interference from other pathogens, with an estimated tolerance limit for interference under 12%. The Hi limit of detection by electrochemical impedance spectroscopy was 1 CFU/mL (measured at - 0.13 V vs BDDPE pseudo-reference), which was achieved in under 10 min, including 5 min sample incubation in the presence of the analyte.

Tailoring diamondised nanocarbon-loaded poly(lactic acid) composites for highly electroactive surfaces: extrusion and characterisation of filaments for improved 3D-printed surfaces.

A new 3D-printable composite has been developed dedicated to electroanalytical applications. Two types of diamondised nanocarbons - detonation nanodiamonds (DNDs) and boron-doped carbon nanowalls (BCNWs) - were added as fillers in poly(lactic acid) (PLA)-based composites to extrude 3D filaments. Carbon black served as a primary filler to reach high composite conductivity at low diamondised nanocarbon concentrations (0.01 to 0.2 S/cm, depending on the type and amount of filler). The aim was to thoroughly describe and understand the interactions between the composite components and how they affect the rheological, mechanical and thermal properties, and electrochemical characteristics of filaments and material extrusion printouts. The electrocatalytic properties of composite-based electrodes, fabricated with a simple 3D pen, were evaluated using multiple electrochemical techniques (cyclic and differential pulse voltammetry and electrochemical impedance spectroscopy). The results showed that the addition of 5 wt% of any of the diamond-rich nanocarbons fillers significantly enhanced the redox process kinetics, leading to lower redox activation overpotentials compared with carbon black-loaded PLA. The detection of dopamine was successfully achieved through fabricated composite electrodes, exhibiting lower limits of detection (0.12 µM for DND and 0.18 µM for BCNW) compared with the reference CB-PLA electrodes (0.48 µM). The thermogravimetric results demonstrated that both DND and BCNW powders can accelerate thermal degradation. The presence of diamondised nanocarbons, regardless of their type, resulted in a decrease in the decomposition temperature of the composite. The study provides insight into the interactions between composite components and their impact on the electrochemical properties of 3D-printed surfaces, suggesting electroanalytic potential.

Multiple Reprocessing of Conductive PLA 3D-Printing Filament: Rheology, Morphology, Thermal and Electrochemical Properties Assessment.

Additive manufacturing technologies are gaining more and more attention, resulting in the development or modification of 3D printing techniques and dedicated materials. On the other hand, economic and ecological aspects force the industry to develop material recycling strategies. In this work, the multiple reprocessing of a commercially available PLA conductive composite with carbon black filler, dedicated to 3D printing, was investigated. The effects of extrusion temperature (190 °C and 200 °C) and reprocessing steps (1-5 steps) on the rheology, morphology, thermal and electrochemical properties of the conductive PLA 3D-printing filament were evaluated. The results showed deterioration of the thermal stability and material strength, as well as the influence of reprocessing on the melting point, which increases after initial melting. The electronic conduction mechanism of the composite depends on the percolation paths and it is also affected by the multiple processing. The reversibility of the [Fe(CN)6]3-/4- redox process diminishes with a higher degradation level of the conductive PLA. Importantly, the material fluidity was too high after the multiple reprocessing, which should be considered and suitably corrected during CB-PLA application as a 3D-printed electrode material.

The Synergistic Microbiological Effects of Industrial Produced Packaging Polyethylene Films Incorporated with Zinc Nanoparticles.

Zinc compounds in polyolefin films regulate the transmission of UV-VIS radiation, affect mechanical properties and antimicrobial activity. According to hypothesis, the use of zinc- containing masterbatches in polyethylene films (PE) with different chemical nature-hydrophilic zinc oxide (ZO) and hydrophobic zinc stearate (ZS)-can cause a synergistic effect, especially due to their antimicrobial properties. PE films obtained on an industrial scale containing zinc oxide and zinc stearate masterbatches were evaluated for antimicrobial activity against E. coli and S. aureus strains. The morphology of the samples (SEM), composition (EDX), UV barrier and transparency, mechanical properties and global migration level were also determined. SEM micrographs confirmed the good dispersion of zinc additives in the PE matrix. The use of both masterbatches in one material caused a synergistic effect of antimicrobial activity against both bacterial strains. The ZO masterbatch reduced the transparency of films, increased their UV-barrier ability and improved tensile strength, while the ZS masterbatch did not significantly change the tested parameters. The global migration limit was not exceeded for any of the samples. The use of ZO and ZS masterbatch mixtures enables the design of packaging with high microbiological protection with a controlled transmission for UV and VIS radiation.

High-Temperature Oxidation of Heavy Boron-Doped Diamond Electrodes: Microstructural and Electrochemical Performance Modification.

In this work, we reveal in detail the effects of high-temperature treatment in air at 600 °C on the microstructure as well as the physico-chemical and electrochemical properties of boron-doped diamond (BDD) electrodes. The thermal treatment of freshly grown BDD electrodes was applied, resulting in permanent structural modifications of surface depending on the exposure time. High temperature affects material corrosion, inducing crystal defects. The oxidized BDD surfaces were studied by means of cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM), revealing a significant decrease in the electrode activity and local heterogeneity of areas owing to various standard rate constants. This effect was correlated with a resultant increase of surface resistance heterogeneity by scanning spreading resistance microscopy (SSRM). The X-ray photoelectron spectroscopy (XPS) confirmed the rate and heterogeneity of the oxidation process, revealing hydroxyl species to be dominant on the electrode surface. Morphological tests using scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed that prolonged durations of high-temperature treatment lead not only to surface oxidation but also to irreversible structural defects in the form of etch pits. Our results show that even subsequent electrode rehydrogenation in plasma is not sufficient to reverse this surface oxidation in terms of electrochemical and physico-chemical properties, and the nature of high-temperature corrosion of BDD electrodes should be considered irreversible.

Obtaining and Characterization of the PLA/Chitosan Foams with Antimicrobial Properties Achieved by the Emulsification Combined with the Dissolution of Chitosan by CO2 Saturation.

A new method of obtaining functional foam material has been proposed. The materials were created by mixing the poly lactic acid (PLA) solution in chloroform, chitosan (CS) dissolved in water saturated with CO2 and polyethylene glycol (PEG), and freeze-dried for removal of the solvents. The composite foams were characterized for their structural (SEM, FT-IR, density, porosity), thermal (DSC), functional (hardness, elasticity, swelling capacity, solubility), and biological (antimicrobial and cytotoxic) properties. Chitosan in the composites was a component for obtaining their foamed form with 7.4 to 22.7 times lower density compared to the neat PLA and high porosity also confirmed by the SEM. The foams had a hardness in the range of 70-440 kPa. The FT-IR analysis confirmed no new chemical bonds between the sponge ingredients. Other results showed low sorption capacity (2.5-7.2 g/g) and solubility of materials (less than 0.2%). The obtained foams had the lower Tg value and improved ability of crystallization compared to neat PLA. The addition of chitosan provides the bacteriostatic and bactericidal properties against Escherichia coli and Staphylococcus aureus. Biocompatibility studies have shown that the materials obtained are not cytotoxic to the L929 cell line.

Multifrequency nanoscale impedance microscopy (m-NIM): A novel approach towards detection of selective and subtle modifications on the surface of polycrystalline boron-doped diamond electrodes.

In this paper, we describe the modification of Nanoscale Impedance Microscopy (NIM), namely, a combination of contact-mode atomic force microscopy with local impedance measurements. The postulated approach is based on the application of multifrequency voltage perturbation instead of standard frequency-by-frequency analysis, which among others offers more time-efficient and accurate determination of the resultant impedance spectra with high spatial resolution. Based on the impedance spectra analysis with an appropriate electric equivalent circuit, it was possible to map surface resistance and contact capacitance. Polycrystalline heavy boron-doped diamond (BDD) electrodes were the research object. Recent studies have shown that the exposure of such electrodes to oxidizing environment may result in the modification of termination type, and thus it is a key factor in describing the electric and electrochemical properties of BDD. We have successfully applied multifrequency NIM, which allowed us to prove that the modification of termination type is selective and occurs with different propensity on the grains having specific crystallographic orientation. Furthermore, our approach enabled the detection of even subtle submicroscopic surface heterogeneities, created as a result of various oxidation treatments and to distinguish them from the surface heterogeneity related to the local distribution of boron at the grain boundaries.