Waste for Product-Synthesis and Electrocatalytic Properties of Palladium Nanopyramid Layer Enriched with PtNPs.

The presented research is the seed of a vision for the development of a waste-for-product strategy. Following this concept, various synthetic solutions containing low concentrations of platinum group metals were used to model their recovery and to produce catalysts. This is also the first report that shows the method for synthesis of a pyramid-like structure deposited on activated carbon composed of Pd and Pt. This unique structure was obtained from a mixture of highly diluted aqueous solutions containing both metals and chloride ions. The presence of functional groups on the carbon surface and experimental conditions allowed for: the adsorption of metal complexes, their reduction to metal atoms and enabled further hierarchical growth of the metal layer on the carbon surface. During experiments, spherical palladium and platinum nanoparticles were obtained. The addition of chloride ions to the solution promoted the hierarchical growth and formation of palladium nanopyramids, which were enriched with platinum nanoparticles. The obtained materials were characterized using UV-Vis, Raman, IR spectroscopy, TGA, SEM/EDS, and XRD techniques. Moreover, Pd@ROY, Pt@ROY, and Pd-Pt@ROY were tested as possible electrocatalysts for hydrogen evolution reactions.

Copper Oxide Electrochemical Deposition to Create Antiviral and Antibacterial Nanocoatings.

The impact of the reaction environment on the formation of the polycrystalline layer and its biomedical (antimicrobial) applications were analyzed in detail. Copper oxide layers were synthesized using an electrodeposition technique, with varying additives influencing the morphology, thickness, and chemical composition. Scanning electron microscopy (SEM) images confirmed the successful formation of polyhedral structures. Unmodified samples (CuL) crystallized as a mixture of copper oxide (I) and (II), with a thickness of approximately 1.74 µm. The inclusion of the nonconductive polymer polyvinylpyrrolidone (PVP) during synthesis led to a regular and compact CuO-rich structure (CuL-PVP). Conversely, adding glucose resulted in forming a Cu2O-rich nanostructured layer (CuL-D(+)G). Both additives significantly reduced the sample thickness to 617 nm for CuL-PVP and 560 nm for CuL-D(+)G. The effectiveness of the synthesized copper oxide layers was demonstrated in their ability to significantly reduce the T4 phage titer by approximately 2.5-3 log. Notably, CuL-PVP and CuL-D(+)G showed a more substantial reduction in the MS2 phage titer, achieving about a 5-log decrease. In terms of antibacterial activity, CuL and CuL-PVP exhibited moderate efficacy against Escherichia coli, whereas CuL-D(+)G reduced the E. coli titer to undetectable levels. All samples induced similar reductions in Staphylococcus aureus titer. The study revealed differential susceptibilities, with Gram-negative bacteria being more vulnerable to CuL-D(+)G due to its unique composition and morphology. The antimicrobial properties were attributed to the redox cycling of Cu ions, which generate ROS, and the mechanical damage caused by nanostructured surfaces. A crucial finding was the impact of surface composition rather than surface morphology on antimicrobial efficacy. Samples with a dominant Cu2O composition exhibited potent antibacterial and antiviral properties, whereas CuO-rich materials showed predominantly enhanced antiviral activity. This research highlights the significance of phase composition in determining the antimicrobial properties of copper oxide layers synthesized through electrodeposition.

Study of amorphous alumina coatings for next-generation nuclear reactors: High-temperature in-situ and post-mortem Raman spectroscopy and X-ray diffraction.

The present work focuses on the investigation of the thermal stability and structural integrity of amorphous alumina coatings intended for use as protective coatings on cladding tubes in Generation IV nuclear reactors, specifically in the Lead-cooled Fast Reactor (LFR) type. High-temperature Raman spectroscopy and high-temperature X-ray diffraction analyses were carried out up to 1050 °C on a 5 µm coating deposited by the pulsed laser deposition (PLD) technique on a 316L steel substrate. The experiments involved the in-situ examination of structural changes in the material under increasing temperature, along with ex-situ Raman imaging of the surface and cross-section of the coating after thermal treatments of different lengths. As it was expected, the presence of α-alumina was detected with the addition of other polymorphs, γ- and θ-Al2O3, found in the material after longer high-temperature exposure. The use of two structural analysis methods and two lasers excitation wavelengths with Raman spectroscopy allowed us to detect all the mentioned phases despite different mode activity. Alumina analysis was based on the emission spectra, while substrate oxidation products were identified through the structural bands. The experiments depicted a dependence of the phase composition of oxidation products and alumina's degree of crystallization on the length of the treatment. Nevertheless, the observed structural changes did not occur rapidly, and the coating's integrity remained intact. Moreover, oxidation signs occurred locally at temperatures exceeding the LFR reactor's working temperature, confirming the material's great potential as a protective coating in the operational conditions of LFR nuclear reactors.

Crystal Clear: Metal-Organic Frameworks Pioneering the Path to Future Drug Detox.

The growing number of acute drug abuse overdoses demands the development of innovative detoxification strategies for emergency purposes. In this study, an innovative approach for the application of porous Zr-based metal-organic frameworks for the treatment of acute overdoses of popular drugs of abuse including amphetamine, methamphetamine, cocaine, and MDMA is presented. A comprehensive approach determining the efficacy and the kinetics of drug removal, considering dosage, adsorption time, and adsorption mechanisms, was tested and corroborated with density functional theory (DFT) modeling. The experimental results showed high removal efficiency reaching up to 90% in the case of the application of the NU-1000 metal-organic framework. The difference Raman spectroscopy method presented in this study corroborated with DFT-based vibrational analysis allows the detection of drug adsorbed in the MOF framework even with as low a concentration as 5 mg/g. Additionally, the drug adsorption mechanisms were modeled with DFT, showing the π-π stacking in a vast majority of considered cases. The performance and influence on the living organisms were evaluated throughout the in vitro and in vivo experiments, indicating that Zr-based MOFs could serve as efficient, organic, safe drug adsorbents.

CdSe/ZnS quantum dots as a booster in the active layer of distributed ternary organic photovoltaics.

Organic solar cells are a promising candidate for practical use because of their low material cost and simple production procedures. The challenge is selecting materials with the right properties and how they interrelate in the context of manufacturing the device. This paper presents studies on CdSe/ZnS nanodots as dopants in a polymer-fullerene matrix for application in organic solar cells. An assembly of poly(3-hexylthiophene-2,5-diyl) and 6,6-phenyl-C71-butyric acid methyl ester was used as the active reference layer. Absorption and luminescence spectra as well as the dispersion relations of refractive indices and extinction coefficient were investigated. The morphologies of the thin films were studied with atomic force microscopy. The chemical boundaries of the ternary layers were determined by Raman spectroscopy. Based on UPS studies, the energy diagram of the potential devices was determined. The resistivity of the layers was determined using impedance spectroscopy. Simulations (General-Purpose Photovoltaic Device Model) showed a performance improvement in the cells with quantum dots of 0.36-1.45% compared to those without quantum dots.

Multiscale characterization of electrospun non-wovens for corneal regeneration: Impact of microstructure on mechanical, optical and biological properties.

The multiscale approach in designing substrates for regenerative medicine endows them with beneficial properties determining their performance in the body. Substrates for corneal regeneration should reveal the proper transparency, mechanical properties and microstructure to maintain the functionality of the regenerated tissue. In our study, series of non-wovens with different fibres orientation (random (R), aligned (A)), topography (shish-kebab (KK), core-shell (CS)) and thickness were fabricated via electrospinning. The samples were assessed for mechanical (static tensile test) and optical properties (spectroscopy UV-Vis). The research evaluated the impact of different microstructures on the viability and morphology of three cell lines (Hs 680, HaCaT and RAW 264.7). The results showed how the fibres arrangement influenced mechanical behaviour of the non-wovens. The randomly oriented fibres were more elongated (up to 50 mm) and had a lower maximum tensile force (up to 0.46 N). In turn, the aligned fibres were characterized by lower elongation (up to 19 mm) and higher force (up to 1.45 N). The conducted transparency tests showed the relation between thickness (of the non-woven and fibres) and morphology of the substrate and light transmission. To simulate the in vivo conditions, prior to the light transmission studies, samples were immersed in water. All the samples exhibited high transparency after immersion in water (>80%). The impact of various morphologies was observed in the in vitro studies. All the samples proved high cells viability. Moreover, the substrate morphology had a significant impact on the orientation and arrangement of the fibroblast cytoskeleton. The aligned fibres were oriented in exactly the same direction. The conducted research proved that, by altering the non-wovens microstructure, the properties can be adjusted so as to induce the desirable cellular reaction. This indicates the high potential of electrospun fibres in terms of modulating the corneal cell behaviour in response to the implanted substrate.

Exploring CVD Method for Synthesizing Carbon-Carbon Composites as Materials to Contact with Nerve Tissue.

The main purpose of these studies was to obtain carbon-carbon composites with a core built of carbon fibers and a matrix in the form of pyrolytic carbon (PyC), obtained by using the chemical vapor deposition (CVD) method with direct electrical heating of a bundle of carbon fibers as a potential electrode material for nerve tissue stimulation. The methods used for the synthesis of PyC proposed in this paper allow us, with the appropriate selection of parameters, to obtain reproducible composites in the form of rods with diameters of about 300 µm in 120 s (CF_PyC_120). To evaluate the materials, various methods such as scanning electron microscopy (SEM), scanning transmission electron microscope (STEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and tensiometer techniques were used to study their microstructural, structural, chemical composition, surface morphology, and surface wettability. Assessing their applicability for contact with nervous tissue cells, the evaluation of cytotoxicity and biocompatibility using the SH-SY5Y human neuroblastoma cell line was performed. Viability and cytotoxicity tests (WST-1 and LDH release) along with cell morphology examination demonstrated that the CF_PyC_120 composites showed high biocompatibility compared to the reference sample (Pt wire), and the best adhesion of cells to the surface among all tested materials.

Poly(sebacic acid) microparticles loaded with azithromycin as potential pulmonary drug delivery system: Physicochemical properties, antibacterial behavior, and cytocompatibility studies.

Recurrent bacterial infections are a common cause of death for patients with cystic fibrosis and chronic obstructive pulmonary disease. Herein, we present the development of the degradable poly(sebacic acid) (PSA) microparticles loaded with different concentrations of azithromycin (AZ) as a potential powder formulation to deliver AZ locally to the lungs. We characterized microparticle size, morphology, zeta potential, encapsulation efficiency, interaction PSA with AZ and degradation profile in phosphate buffered saline (PBS). The antibacterial properties were evaluated using the Kirby-Bauer method against Staphylococcus aureus. Potential cytotoxicity was evaluated in BEAS-2B and A549 lung epithelial cells by the resazurin reduction assay and live/dead staining. The results show that microparticles are spherical and their size, being in the range of 1-5 µm, should be optimal for pulmonary delivery. The AZ encapsulation efficiency is nearly 100 % for all types of microparticles. The microparticles degradation rate is relatively fast - after 24 h their mass decreased by around 50 %. The antibacterial test showed that released AZ was able to successfully inhibit bacteria growth. The cytotoxicity test showed that the safe concentration of both unloaded and AZ-loaded microparticles was equal to 50 µg/ml. Thus, appropriate physicochemical properties, controlled degradation and drug release, cytocompatibility, and antibacterial behavior showed that our microparticles may be promising for the local treatment of lung infections.

Spectroscopic characterization of calcium phosphate precipitated under human eye conditions: An in vitro study.

Calcification is a well-known process of calcium phosphate mineralization observed in intraocular lenses. Despite the many works conducted in this field, there is no strict explanation of the mechanisms of this process. In order to better understand the phenomenon, i.e., the mechanisms and structural conditions that promote calcification, any research observations should be conducted under conditions that best reflect those of the human eye. Taking into account the specific anatomy and physicochemical conditions of the human eye, the problem under discussion becomes difficult to solve in vitro. In the present study, calcium phosphates formed under conditions similar to those in the human eye were characterized using SEM/EDS and infrared spectroscopy. Conducted study showed the formation of white spherical precipitates, which are unstable when extracted from solution. Such precipitates were characteristic of solutions containing 1.5-3.0 mM2 of solutes. Elemental analysis showed a Ca/P ratio of 1.64-1.65, which is similar to the ratio for hydroxyapatite (1.67). Chemical structure analysis revealed the presence of broad bending and stretching bands at 475-830 cm-1 and 880-1250 cm-1, respectively, which are characteristic of PO43- groups in apatite calcium phosphates. In further analysis involving numerical fitting the bands corresponding to apatitic PO43- and indicating the presence of calcium phosphates hydration were found. The results allow the selection of immersion media for further studies involving the incubation of hydrogel intraocular lenses.

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties.

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal-organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

Near-infrared to visible and ultraviolet upconversion in TiO2 thin films modified with Er and Yb.

Upconversion as a modification strategy to enhance the utilization of sunlight in titanium dioxide photoanodes with an internal upconverter was investigated. TiO2 thin films containing an Er activator and Yb sensitizer were deposited in the magnetron sputtering process on conducting glass, amorphous silica, and silicon. Scanning electron microscopy, energy dispersive spectroscopy, grazing incidence X-ray diffraction, and X-ray absorption spectroscopy allowed assessment of the thin film composition, structure, and microstructure. Optical and photoluminescence properties were measured by means of spectrophotometry and spectrofluorometry. Changing the content of Er3+ (1, 2, 10 at%) and Yb3+ (1, 10 at%) ions allowed us to achieve thin film upconverters with a crystallized and amorphous host. Upon 980 nm laser excitation Er3+ exhibits upconversion with the main emission in green (2H11/2 → 4I15/2, λ em ≈ 525 nm) and weak emission in red (4F9/2 → 4I15/2, λ em ≈ 660 nm). For a thin film with a higher ytterbium content (10 at%) a significant increase in red emission and upconversion from NIR to UV was observed. The average decay times of green emission for TiO2:Er and TiO2:Er,Yb thin films were calculated based on time-resolved emission measurements.

Spectroscopic studies on phosphate-modified silicon oxycarbide-based amorphous materials.

Vibrational spectroscopy is the most effective, efficient and informative method of structural analysis of amorphous materials with silica matrix and, therefore, an indispensable tool for examining silicon oxycarbide-based amorphous materials (SiOC). The subject of this work is a description of the modification process of SiOC glasses with phosphate ions based on the structural examination including mainly Infrared and Raman Spectroscopy. They were obtained as polymer-derived ceramics based on ladder-like silsesquioxanes synthesised via the sol-gel method. With the high phosphate's volatility, it was decided to introduce the co-doping ions to create [AlPO4] and [BPO4] stable structural units. As a result, several samples from the SiPOC, SiPAlOC and SiPBOC systems were obtained with various quantities of the modifiers. All samples underwent a detailed structural evaluation of both polymer precursors and ceramics after high-temperature treatment with Fourier-transformed infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD) and magic angle spinning nuclear magnetic resonance (MAS-NMR). Obtained results proved the efficient preparation of desired materials that exhibit structural parameters similar to the unmodified one. They were X-ray-amorphous with no phase separation and crystallisation. Spectroscopic measurements confirmed the presence of the crucial Si-C bond and how modifying ions are incorporated into the SiOC network. It was also possible to characterise the turbostratic free carbon phase. The modification was aimed to improve the bioperformance of the materials in the context of their future application as bioactive coatings on metallic implants.

An Overview of Some Nonpiezoelectric Properties of BaTiO3 Ceramics Doped by Eu Ions.

Ferroelectric ceramics BaTiO3:x%Eu (x = 0, 0.1, 1, 2, 3) were synthesized by a conventional method. Structural investigation confirmed that all ceramics possessed tetragonal (P4mm) symmetries at room temperature for the undoped ceramics as well as for the doped ceramics. Furthermore, a slight downshifting of the Curie temperature (TC) with an increasing Eu3+ doping amount has been noted. The Raman spectra unveiled the existence of new modes for higher-doped BaTiO3:x%Eu (BTEx) which are related to local disorders and defects. The ferroelectric properties were found to depend on both doping and the microstructure. The electrocaloric effect was also studied for those ceramics. It was observed that ΔT decreases with doping; however, the temperature range of its occurrence widens considerably.

Cuprous Oxide Thin Films Implanted with Chromium Ions-Optical and Physical Properties Studies.

Cuprous oxide is a semiconductor with potential for use in photocatalysis, sensors, and photovoltaics. We used ion implantation to modify the properties of Cu2O oxide. Thin films of Cu2O were deposited with magnetron sputtering and implanted with low-energy Cr ions of different dosages. The X-ray diffraction method was used to determine the structure and composition of deposited and implanted films. The optical properties of the material before and after implantation were studied using spectrophotometry and spectroscopic ellipsometry. The investigation of surface topography was performed with atomic force microscopy. The implantation had little influence on the atomic lattice constant of the oxide structure, and no clear dependence of microstrain or crystalline size on the dose of implantation was found. The appearance of phase change was observed, which could have been caused by the implantation. Ellipsometry measurements showed an increase in the total thickness of the sample with an increase in the amount of implanted Cr ions, which indicates the influence of implantation on the properties of the surface and subsurface region. The refractive index n, extinction coefficient k, and absorption coefficient optical parameters show different energy dependences related to implantation dose.

Influence of Cr Ion Implantation on Physical Properties of CuO Thin Films.

Cupric oxide is a semiconductor with applications in sensors, solar cells, and solar thermal absorbers. To improve its properties, the oxide was doped with a metallic element. No studies were previously performed on Cr-doping using the ion implantation technique. The research goal of these studies is to investigate how Cr ion implantation impacts the properties of the oxide thin films. CuO thin films were deposited using magnetron sputtering, and then chromium ions with different energies and doses were implanted. Structural, optical, and vibrational properties of the samples were studied using X-ray diffraction, X-ray reflectivity, infra-red spectroscopy, Raman spectroscopy, and spectrophotometry. The surface morphology and topography were studied with ellipsometry, atomic force microscopy, and scanning electron microscopy. A simulation of the range of ions in the materials was performed. Ion implantation had an impact on the properties of thin films that could be used to tailor the optical properties of the cupric oxide and possibly also its electrical properties. A study considering the influence of ion implantation on electrical properties is proposed as further research on ion-implanted CuO thin films.

Corrosion Resistance and Electrical Conductivity of Hybrid Coatings Obtained from Polysiloxane and Carbon Nanotubes by Electrophoretic Co-Deposition.

Nanocomposites developed based on siloxanes modified with carbon nanoforms are materials with great application potential in the electronics industry, medicine and environmental protection. This follows from the fact that such nanocomposites can be endowed with biocompatibility characteristics, electric conductivity and a high mechanical durability. Moreover, their surface, depending on the type and the amount of carbon nanoparticles, may exhibit antifouling properties, as well as those that limit bacterial adhesion. The paper reports on the properties of polysiloxane (PS) and carbon nanotubes (CNT) nanocomposite coatings on metal surfaces produced by the electrophoretic deposition (EPD). A comparison with coatings made of pure PS or pure CNT on the same substrates using the same deposition method (EPD) is provided. The coatings were examined for morphology and elemental composition (SEM, EDS), structural characteristics (confocal Raman spectroscopy), electrical conductivity and were tested for corrosion (electrochemical impedance spectroscopy-EIS, potentiodynamic polarization-PDP). The results obtained in this study clearly evidenced that such hybrid coatings conduct electricity and protect the metal from corrosion. However, their corrosion resistance differs slightly from that of a pure polymeric coating.

New Ceramics Precursors Containing Si and Ge Atoms-Cubic Germasilsesquioxanes-Synthesis, Thermal Decomposition and Spectroscopic Analysis.

Compounds of the silsesquioxane type are attractive material precursors. High molecular weights and well-defined structures predestine them to create ceramics with a controlled composition at the molecular level. New molecular precursors of ceramic materials with the ratio of Si:Ge = 7:1 atoms were obtained. The influence of organic substituents on the thermal decomposition processes of germasilsesquioxanes was investigated. Some of the structures obtained are characterized by a high non-volatile residue after the thermal decomposition process. The introduction of the germanium atom to the structure of the silsesquioxane molecular cage reduces the thermal stability of the obtained structures.

Investigating the Crystallization Process of Boron-Bearing Silicate-Phosphate Glasses by Thermal and Spectroscopic Methods.

Glasses and devitrificates from the SiO2-B2O3-P2O5-K2O-CaO-MgO system with constant contents of SiO2 and P2O5 network formers, modified by the addition of B2O3, were analyzed. All materials were synthesized by the traditional melt-quenching technique. The glass stability (GS) parameters (Krg, ∆T, KW, KH) were determined. The effect of the addition of B2O3 on the GS, liquation phenomenon, crystallization process, and the type of crystallizing phases were examined using SEM-EDS, DSC, XRD, and Raman spectroscopy imaging methods. It was observed that the addition of B2O3 increased the tendency of the glass to crystallize. Both phosphates (e.g., Ca9MgK(PO4)7, Mg3Ca3(PO4)4), and silicates (e.g., K2Mg5(Si12O30), CaMg(Si2O6), MgSiO3) crystallized in the studied system. The Raman spectrum for the orthophosphate Mg3Ca3(PO4)4 stanfieldite type was obtained. Boron ions were introduced into the structures of crystalline compounds at high crystallization temperatures. The type of crystallizing phases was found to be related to the phenomenon of liquation, and the order of their occurrence was dependent on the Gibbs free enthalpy.

Investigation of Dye Dopant Influence on Electrooptical and Morphology Properties of Polymeric Acceptor Matrix Dedicated for Ternary Organic Solar Cells.

The publication presents the results of investigations of the influence of dye dopant on the electrooptical and morphology properties of a polymeric donor:acceptor mixture. Ternary thin films (polymer:dye:fullerene) were investigated for potential application as an active layer in organic solar cells. The aim of the research is to determine the effect of selected dye materials (dye D131, dye D149, dye D205, dye D358) on the three-component layer and their potential usefulness as an additional donor in ternary cells, based on P3HT donor and PC71BM acceptor. UV-vis spectroscopy studies were performed, and absorption and luminescence spectra were determined. Ellipsometry parameters for single dye and ternary layers have been measured. The analyses were performed using the Raman spectroscopy method, and the Raman spectra of the mixtures and single components have been determined. Organic layers were prepared and studied using scanning electron microscope and atomic force microscope. For dyes, ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy studies were carried out and the ternary system was presented and analyzed in terms of energy bands.

The Effect of Heat Treatment on the Structure of Zeolite A.

Knowledge about the thermal properties of zeolites is extremely important due to their potential application in the chemical industry. In this work, the thermal stability and the dehydration process of zeolite A were investigated by in situ high temperature Fourier transform infrared spectroscopy. The progress of thermal decomposition that zeolite A underwent during the controlled temperature increase in the range of 25-600 °C was determined by the DRIFT spectroscopic method. Infrared spectra are presented and discussed for this compound on the basis of the crystal structure. Based on the courses of the obtained DRIFT spectra, it was found that, during heating, water was gradually removed from the structure of the material, followed by dehydration and formation of hydrogen bonds. It was established that the process of thermal degradation began as early as 550 °C. The analysis of the obtained results of structural tests can be repeated on other materials from the zeolite group and complements the research work on the thermal analysis of these materials.