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.

Characterization of Microbial Communities in Acidified, Sulfur Containing Soils.

Over a period of three years, microbial communities in acidified soil with high sulfur content were analyzed. In soil water extracts ureolytic, proteolytic, oxidoreductive, and lipolytic activity were detected. The presented results indicate that the enzymatic activity of soil microbial communities varied considerably over time. Isolated 26 (80%) bacterial strains belonged to genus Bacillus sp. and were identified by cultivation and 16S rRNA methods. The commercially available procedures for bacterial DNA isolation from acidified soil failed, therefore a new, specific DNA isolation method was established. Ureolytic activity, detected in soil extracts as well as in isolated Bacillus sp. strains may be considered as a tool for the bioremediation of acidified soils with high sulfate content.

Implementation and validation of multisinusoidal, fast impedance measurements in atomic force microscope contact mode.

This study presents a novel approach to impedance measurements. The methodology discussed is limited to contact in the sample-probe system under ambient conditions without the presence of electrolyte. Comparison with results of direct and alternating current measurements for well-defined metallic surfaces are made. In spite of idealization related to the type of contact examined, the proposed technique provides an improvement of traditional impedance measurement related to sequential changes in system perturbation compared with the sine wave superposition type.

Dynamic nanoimpedance characterization of the atomic force microscope tip-surface contact.

Nanoimpedance measurements, using the dynamic impedance spectroscopy technique, were carried out during loading and unloading force of a probe on three kinds of materials of different resistivity. These materials were: gold, boron-doped diamond, and AISI 304 stainless steel. Changes of impedance spectra versus applied force were registered and differences in the tip-to-sample contact character on each material were revealed. To enable comparison between materials and phases, a new standardization method is proposed, which simulates conditions of initial contact.

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.

Improving AFM images with harmonic interference by spectral analysis.

Atomic force microscopy (AFM) is one of the most sensitive tools for nanoscale imaging. As such, it is very sensitive to external noise sources that can affect the quality of collected data. The intensity of the disturbance depends on the noise source and the mode of operation. In some cases, the internal noise from commercial AFM controllers can be significant and difficult to remove. Thus, a new method based on spectrum analysis of the scanned images is proposed to reduce harmonic disturbances. The proposal is a post-processing method and can be applied at any time after measurements. This article includes a few methods of harmonic cancellation (e.g., median filtering, wavelet denoising, Savitzky-Golay smoothing) and compares their effectiveness. The proposed method, based on Fourier transform of the scanned images, was more productive than the other methods mentioned before. The presented data were achieved for images of conductive layers taken in a contact AFM mode.

Tailoring of Optical Properties of Methacrylate Resins Enriched by HPHT Microdiamond Particles.

Diamond particles have great potential to enhance the mechanical, optical, and thermal properties of diamond-polymer composites. However, the improved properties of diamond-polymer composites depend on the size, dispersibility, and concentration of diamond particles. In the present study, diamond-polymer composites were prepared by adding the microdiamond particles (MDPs) with different concentrations (0.2-1 wt.%) into polymers (acrylate resins) and then subjected to a photocuring process. The surface morphology and topography of the MDPs-polymer composites demonstrated a uniform high-density distribution of MDPs for one wt.% MPDs. Thermogravimetric analysis was employed to investigate the thermal stability of the MDPs-polymer composites. The addition of MDPs has significantly influenced the polymers' thermal degradation. Absorption and emission spectra of thin layers were recorded through UV/Vis spectrophotometry and spectrofluorimetry. The obtained results revealed a significant increase in the fluorescence intensity of MDPs-polymer composites (at 1 wt.% of MDPs, a 1.5×, 2×, and 5× increase in fluorescence was observed for MDPs-green, MDPs-amber daylight, and MDPs-red resin, respectively) compared with the reference polymer resins. The obtained results of this work show the new pathways in producing effective and active 3D-printed optical elements.

Ultrasonic-assisted electrodeposition of Cu-Sn-TiO2 nanocomposite coatings with enhanced antibacterial activity.

Copper-based coatings are known for their high antibacterial activity. In this study, nanocomposite Cu-Sn-TiO2 coatings were obtained by electrodeposition from an oxalic acid bath additionally containing 4 g/dm3 TiO2 with mechanical and ultrasonic agitation. Ultrasound treatment was performed at 26 kHz frequency and 32 W/dm3 power. The influence of agitation mode and the current load on the inclusion and distribution of the TiO2 phase in the Cu-Sn metallic matrix were evaluated. Results indicated that ultrasonic agitation decreases agglomeration of TiO2 particles and allows for the deposition of dense Cu-Sn-TiO2 nanocomposites. It is shown that nanocomposite Cu-Sn-TiO2 coatings formed by ultrasonic-assisted electrodeposition exhibit excellent antimicrobial properties against E. coli bacteria.

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.

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.

Application of dynamic impedance spectroscopy to atomic force microscopy.

Atomic force microscopy (AFM) is a universal imaging technique, while impedance spectroscopy is a fundamental method of determining the electrical properties of materials. It is useful to combine those techniques to obtain the spatial distribution of an impedance vector. This paper proposes a new combining approach utilizing multifrequency scanning and simultaneous AFM scanning of an investigated surface.