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.

Discriminating macromolecular interactions based on an impedimetric fingerprint supported by multivariate data analysis for rapid and label-free Escherichia coli recognition in human urine.

This manuscript presents a novel approach to address the challenges of electrode fouling and highly complex electrode nanoarchitecture, which are primary concerns for biosensors operating in real environments. The proposed approach utilizes multiparametric impedance discriminant analysis (MIDA) to obtain a fingerprint of the macromolecular interactions on flat glassy carbon surfaces, achieved through self-organized, drop-cast, receptor-functionalized Au nanocube (AuNC) patterns. Real-time monitoring is combined with singular value decomposition and partial least squares discriminant analysis, which enables selective identification of the analyte from raw impedance data, without the use of electric equivalent circuits. As a proof-of-concept, the authors demonstrate the ability to detect Escherichia coli in real human urine using an aptamer-based biosensor that targets RNA polymerase. This is significant, as uropathogenic E. coli is a difficult-to-treat pathogen that is responsible for the majority of hospital-acquired urinary tract infection cases. The proposed approach offers a limit of detection of 11.3 CFU/mL for the uropathogenic E. coli strain No. 57, an analytical range in all studied concentrations (up to 105 CFU/mL), without the use of antifouling strategies, yet not being specific vs other E.coli strain studied (BL21(DE3)). The MIDA approach allowed to identify negative overpotentials (-0.35 to -0.10 V vs Ag/AgCl) as most suitable for the analysis, offering over 80% sensitivity and accuracy, and the measurement was carried out in just 2 min. Moreover, this approach is scalable and can be applied to other biosensor platforms.

Deciphering the Molecular Mechanism of Substrate-Induced Assembly of Gold Nanocube Arrays toward an Accelerated Electrocatalytic Effect Employing Heterogeneous Diffusion Field Confinement.

The complex electrocatalytic performance of gold nanocubes (AuNCs) is the focus of this work. The faceted shapes of AuNCs and the individual assembly processes at the electrode surfaces define the heterogeneous conditions for the purpose of electrocatalytic processes. Topographic and electron imaging demonstrated slightly rounded AuNC (average of 38 nm) assemblies with sizes of ≤1 µm, where the dominating patterns are (111) and (200) crystallographic planes. The AuNCs significantly impact the electrochemical performance of the investigated electrode [indium-tin oxide (ITO), glassy carbon (GC), and bulk gold] systems driven by surface electrons promoting the catalytic effect. Cyclic voltammetry in combination with scanning electrochemical microscopy allowed us to decipher the molecular mechanism of substrate-induced electrostatic assembly of gold nanocube arrays, revealing that the accelerated electrocatalytic effect should be attributed to the confinement of the heterogeneous diffusion fields with tremendous electrochemically active surface area variations. AuNC drop-casting at ITO, GC, and Au led to various mechanisms of heterogeneous charge transfer; only in the case of GC did the decoration significantly increase the electrochemically active surface area (EASA) and ferrocyanide redox kinetics. For ITO and Au substrates, AuNC drop-casting decreases system dimensionality rather than increasing the EASA, where Au-Au self-diffusion was also observed. Interactions of the gold, ITO, and GC surfaces with themselves and with surfactant CTAB and ferrocyanide molecules were investigated using density functional theory.