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.

Infrared spectroscopy: the key to elucidating the sorption mechanism of surfactants, dyes and pharmaceuticals on mineral composite material.

There is a global problem with the effective purification of wastewater containing organic compounds, including dyes, pharmaceuticals and surfactants. Therefore, technologies for the removal of pollutants are still being explored. One of the promising methods could be the application of mineral sorbent composite based on lignite and bentonite. However, it is crucial to comprehensively recognize the mechanisms responsible for immobilizing organic compounds using mineral composite sorbents. The purpose of this work was to prepare and investigate the sorption mechanism of lignite-bentonite composite (BL) sorbents for the removal of dyes: Rhodamine B (RB), Remazol Brilliant Blue R (RBBR), pharmaceuticals: ibuprofen (IB), sulfamethoxazole (STX) and surfactant sodium dodecylbenzenesulfonate (SDBS). The quantitative sorption results have been performed using the high-performance liquid chromatography (HPLC) method. The application of infrared (IR) spectroscopy method was crucial to describe the sorption mechanism. After completing the sorption test, the spectra for the sorbents revealed bands associated with adsorbed RB, RBBR, IB, STX, and SDBS on the BL sorbent. Because lignite is predominated in BL composite, the sorption capacity and mechanism strictly correspond to its sorption properties rather than to bentonite ones. The spectra results indicate that the physical sorption process related to electrostatic forces, hydrogen bonding, and dispersion interactions are predominantly responsible for the immobilization of organic compounds tested on mineral sorbents. The X-ray diffraction (XRD) results indicate the ion exchange process involved in the case of RB adsorption on the bentonite sample. Nevertheless, the sorption mechanism was complex because of the extensive sorption properties of mineral composite and the different chemical properties of the tested organic compounds. The results of our spectroscopic studies help interpret the sorption mechanisms of organic compounds on mineral materials.

Characterization of electrochemical deposition of copper and copper(I) oxide on the carbon nanotubes coated stainless steel substrates.

The nanocomposite coatings composed of carbon nanotubes and various forms of copper were prepared in the two-step process. Firstly, carbon nanotubes were coated on stainless steel substrate using electrophoretic deposition at constant current. Then, the process of electrochemical deposition using copper(II) sulphate solutions was performed under high overpotential conditions. The modification of the copper(II) cations concentration in the solution and the deposition time provided the formation of various forms of crystals. The samples and their cross-sections were observed and examined using scanning electron microscope equipped with electron dispersive spectroscopy system. The analysis of chemical composition revealed that in addition to the pure copper crystals, the crystals characterized by the presence of copper and oxygen were formed. Therefore, Raman spectroscopy was applied to determine the unknown stoichiometry of this copper oxide. The point and in-depth analysis identified copper(I) oxide in the form of different size crystals depending on the concentration of the copper(II) sulphate solution. To confirm these findings, grazing incidence X-ray diffraction measurements were also performed. the combination of the applied methods has provided the detailed description of the preparation of the nanocomposite coatings with the proposed mechanism of copper(I) oxide formation.

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.

The Effect of Biological Corrosion on the Hydration Processes of Synthetic Tricalcium Aluminate (C3A).

This paper presents a study related to the biological degradation of a tricalcium aluminate (C3A) phase treated with reactive media from the agricultural industry. During one month of setting and hardening, synthetic C3A was subjected to corrosion in corn silage, pig slurry and chicken manure. The hardening process of the C3A phase in water was used as a reference sample. The phase composition and microstructure of the hydrating tricalcium aluminate slurries were characterised by X-ray diffraction (XRD), thermal analysis (DTA/TG/DTG/EGA), scanning microscopy (SEM, EDS) and infrared spectroscopy (FT-IR). In the samples studied, it was observed that the qualitative and quantitative phase composition of the synthetic tricalcium aluminate preparations changed depending on the corrosion exposure conditions. The main crystalline phases formed by the hydration of the examined samples in water as well as in corrosive media were the catoite (Ca3Al2(OH)12) and hydrocalumite (Ca2Al(OH)7·3H2O) phases. Detailed analysis showed the occurrence of secondary crystallisation in hydrating samples and the phases were mainly calcium carbonates (CaCO3) with different crystallite sizes. In the phase composition of the C3A pastes, varying amounts of aluminium hydroxides (Al(OH)3) were also present. The crystalline phases formed as a result of secondary crystallisation represented biological corrosion products, probably resulting from the reaction of hydrates with secondary products resulting from the metabolic processes of anaerobic bacterial respiration (from living matter) associated with the presence of bacteria in the reaction medium. The results obtained contribute towards the development of fast-acting and bio-corrosion-resistant special cements for use in bioenergetics.

Iron inactivation by Sporobolomyces ruberrimus and its potential role in plant metal stress protection. An in vitro study.

The endophytic Basidiomycete Sporobolomyces ruberrimus protects its host Arabidopsis arenosa against metal toxicity. Plants inoculated with the fungus yielded more biomass and exhibited significantly fewer stress symptoms in medium mimicking mine dump conditions (medium supplemented with excess of Fe, Zn and Cd). Aside from fine-tuning plant metal homeostasis, the fungus was capable of precipitating Fe in the medium, most likely limiting host exposure to metal toxicity. The precipitated residue was identified by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-Ray Diffraction (XRD) and electron microscopy (SEM/TEM) with energy dispersive X-Ray analysis (EDX/SAED) techniques. The performed analyses revealed that the fungus transforms iron into amorphous (oxy)hydroxides and phosphates and immobilizes them in the form of a precipitate changing Fe behaviour in the MSR medium. Moreover, the complexation of free Fe ions by fungi could be obtained by biomolecules such as lipids, proteins, or biosynthesized redox-active molecules.

Raman and Infrared Spectroscopy of Barium-Gallo Germanate Glasses Containing B2O3/TiO2.

Modified barium gallo-germanate glass hosts are still worthy of attention in studying structure-property relationships. In this work, two different series of glass systems based on (60-x)GeO2-xTiO2-30BaO-10Ga2O3 and (60-x)GeO2-xB2O3-30BaO-10Ga2O3 (x = 10, 30, 50 mol%) were synthesized, and their properties were studied using spectroscopic techniques. X-ray diffraction (XRD) patterns revealed that all fabricated glasses were fully amorphous material. The absorption edge shifted toward the longer wavelengths with a gradual substitution of GeO2. The spectroscopic assignments of titanium ions were performed with excitation and emission spectra compared to the additional sample containing an extremely low content of TiO2 (0.005 mol%). On the basis of Raman and FT-IR investigations, it was found that increasing the TiO2 content caused a destructive effect on the GeO4 and GeO6 structural units. The Raman spectra of a sample containing a predominantly TiO2 (50 mol%) proved that the band was located near 650 cm-1, which corresponded to the stretching vibration of Ti-O in TiO6 unit. The deconvoluted IR results showed that the germanate glass network consisted of the coexistence of two BO3 and BO4 structural groups. Based on the experimental investigations, we concluded that the developed materials are a promising candidate for use as novel glass host matrices for doping rare-earth and/or transition metal ions.

Tellurite Glasses from the 70TeO2-5XO-10P2O5-10ZnO-5PbF2(X= Pb, Bi, Ti) System Doped Erbium Ions-The Influence of Erbium on the Structure and Physical Properties.

In this article, we present research on the influence of erbium ions on the structure and magneto-optical properties of 70TeO2-5XO-10P2O5-10ZnO-5PbF2 (X = Pb, Bi, Ti) tellurite glass systems. Structural changes occurring in the glasses during doping with erbium ions were investigated using positron annihilation lifetime spectroscopy (PALS) and Raman spectroscopy. The X-ray diffraction (XRD) method was used to confirm the amorphous structure of the investigated samples. Based on the Faraday effect measurements and calculated values of Verdet constant, the magneto-optical properties of the glasses were determined.

Influence of the type of substrate on the properties of carbon nanotubes layer studied by Raman spectroscopy.

The development of nanomaterials technology allows to design a novel medical strategies, and could also be useful in the field of regenerative medicine. The paper presents a study on the functionalized multi-walled carbon nanotubes (MWCNTs-f) layers deposited by electrophoretic method (EPD) on the surfaces of two types of substrates: titanium (Ti) and stainless steel. SEM and EDS analyses confirm that incubation in a simulated body fluid (SBF) caused a formation of hydroxyapatite on the surface of the Ti/MWCNTs-f. Raman micro-spectroscopy was a method of choice to study presented materials. The MWCNTs-f layer on the surface of the titanium plate shows better layer order than the corresponding layer deposited on the stainless steel. The structure and ordering of the nanocarbon layer play a key role in the biological activity of the materials. This was confirmed by the incubation of the plates with deposited layer of carbon nanotubes in SBF. A titanium substrate with a MWCNTs-f layer supports the deposition of some components from the environment, while a stainless steel substrate promotes the formation of a carbon film that inhibits the deposition of certain components from the environment. A two-trace two-dimensional (2T2D) analysis confirmed a different effect of SBF on the MWCNTs-f layer depending on the type of substrate. The MWCNTs-f layer on titanium substrate seems to represent an interesting proposition for novel bioactive strategies.

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.

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.

TEMPO-oxidized cellulose for in situ synthesis of Pt nanoparticles. Study of catalytic and antimicrobial properties.

In this work, platinum nanoparticles (PtNPs) were synthesized by a modified polyol process using TEMPO-oxidized nanocellulose (TOCN) as a stabilizing and co-reducing agent. Different ratios of TOCN nanocellulose to Pt4+ ions were studied to establish the optimum stabilizing effect of PtNPs. The effect of different pH of aqueous TOCN suspensions on the morphology of PtNPs was also examined. It was proved that PtNPs can be obtained solely in the presence of TOCN without the use of an additional reducing agent or ethylene glycol. The morphology and structural properties of the nanocellulose­platinum nanoparticles composites were assessed using spectroscopic, microscopic and diffraction techniques, The catalytic performance in 4-nitrophenol reduction was evaluated. Significant differences in reaction rate constants k were found depending on the pH of the TOCN suspension applied during Pt4+ reduction. The crucial effect of reaction conditions on PtNPs performance was confirmed in tests of antibacterial efficacy against E. coli.

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.

Biochemical changes of macrophages and U87MG cells occurring as a result of the exposure to iron oxide nanoparticles detected with the Raman microspectroscopy.

The core size of iron oxide nanoparticles (IONPs) is a crucial factor defining not only their magnetic properties but also toxicological profile and biocompatibility. On the other hand, particular IONPs may induce different biological response depending on the dose, exposure time, but mainly depending on the examined system. New light on this problem may be shed by the information concerning biomolecular anomalies appearing in various cell lines in response to the action of IONPs with different core diameters and this was accomplished in the present study. Using Raman microscopy we studied the abnormalities in the accumulation of proteins, lipids and organic matter within the nucleus, cytoplasm and cellular membrane of macrophages, HEK293T and U87MG cell line occurring as a result of 24-hour long exposure to PEG-coated magnetite IONPs. The examined nanoparticles had 5, 10 and 30 nm cores and were administered in doses 5 and 25 µg Fe/ml. The obtained results showed significant anomalies in biochemical composition of macrophages and the U87MG cells, but not the HEK293T cells, occurring as a result of exposure to all of the examined nanoparticles. However, IONPs with 10 nm core diminished the accumulation of biomolecules in cells only when they were administered at a larger dose. The Raman spectra recorded for the macrophages subjected to 30 nm IONPs and for the U87MG cells exposed to 5 and 10 nm showed the presence of additional bands in the wavenumber range 1700-2400 cm-1, probably resulting from the appearance of Fe adducts within cells. Our results indicate, moreover, that smaller IONPs may be effectively internalized into the U87MG cells, which points at their diagnostic/therapeutic potential in the case of glioblastoma multiforme.

Development of Geopolymers Based on Fly Ashes from Different Combustion Processes.

The main aim of this research is to assess different fly ashes as raw materials for the manufacturing of geopolymers. Three different fly ashes have been investigated. First, a conventional fly ash from the Skawina coal power plant (Poland), obtained at a temperature of 900-1100 °C. Second, ultra-fine fly ash from a power plant in China; the side product received at 1300 °C. The third fly ash was waste was obtained after combustion in incineration plants. To predict the properties and suitability of materials in the geopolymerization process, methods based on X-ray analysis were used. The applied precursors were tested for elemental and chemical compounds. The investigations of geopolymer materials based on these three fly ashes are also presented. The materials produced on the basis of applied precursors were subjected to strength evaluation. The following research methods were applied for this study: density, X-ray fluorescence (XRF), X-ray diffraction analysis (XRD), Scanning Electron Microscopy (SEM), flexural and compressive strength. The obtained results show that materials based on fly ashes had a similar compressive strength (about 60 MPa), while significant differences were observed during the bending test from 0.1 to 5.3 MPa. Ultra-fine fly ash had a lower flexural strength compared to conventional fly ash. This study revealed the need for process optimization for materials based on a precursor from a waste incineration plant.

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.

Microstructure and Selected Properties of Advanced Biomedical n-HA/ZnS/Sulfonated PEEK Coatings Fabricated on Zirconium Alloy by Duplex Treatment.

In this work, sulfonated polyetheretherketone (S-PEEK)-based coatings, nanocrystalline ZnS and hydroxyapatite (n-HA) particles were developed on Zr-2.5Nb zirconium alloy substrates by electrophoretic deposition (EPD) combined with subsequent heat treatment. The properties of suspensions and deposition kinetics were studied. Cationic chitosan polyelectrolyte ensured the stabilization of the suspension and allowed for the co-deposition of all coating components on the cathode. The heating of the coated samples at a temperature of 450 °C and slow cooling resulted in sulfonation of the PEEK and the formation of dense coatings. The coatings were characterized by high roughness, hardness, modulus of elasticity and adhesion strength. The coatings revealed mild hydrophilicity, improved the electrochemical corrosion resistance of the alloy and induced the formation of hydroxyapatite with a cauliflower-like morphology on its surface during the Kokubo test. This work explored the great development potential of advanced sulfonated PEEK-based coatings, incorporating antibacterial and bioactive components by EPD combined with heat treatment to stimulate the surface properties of zirconium alloy for prospective dental and orthopedic applications. The antibacterial and osteoconductive properties of the obtained coatings should be further investigated.

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.