Synthesis and Properties of the Ba2PrWO6 Double Perovskite.

We report details on the synthesis and properties of barium praseodymium tungstate, Ba2PrWO6, a double perovskite that has not been synthesized before. Room-temperature (RT) powder X-ray diffraction identified the most probable space group (SG) as monoclinic I2/m, but it was only slightly distorted from the cubic structure. X-ray photoelectron spectroscopy confirmed that the initial (postsynthesis) material contained praseodymium in both 3+ and 4+ charge states. The former (Pr3+) disappeared after exposure to UV light at RT. Photoluminescence studies of Pr3+ revealed that Ba2PrWO6 is an insulator with a band gap exceeding 4.93 eV. Pressure-dependent Raman spectroscopy excluded the possibility of a phase transition up to 20 GPa; however, measurements between 8 and 873 K signified that there might be a change toward the lower symmetry SG below 200 K. Electron paramagnetic resonance spectra revealed the presence of interstitial oxygen which acts as a deep electron trap.

Alteration of zeta potential and cell viability in rat-derived L6 skeletal muscle cells and H9c2 cardiomyocytes: A study with submicron polystyrene particles.

BACKGROUND: Microand nanoplastics pollution can cause substantial damage to ecosystems. Since scientists have focused mainly on their impact on aquatic environments, less attention has been paid to the accumulation of polymer particles in terrestrial organisms. OBJECTIVES: We checked if submicron (<5 mm) polystyrene (PS) particles, which can accumulate in living organisms, lead to changes in the physicochemical properties of mammalian cell membranes. MATERIAL AND METHODS: The influence of submicron PS particles on the properties of rat-derived L6 myocytes and H9c2 cardiomyocytes was analyzed. Non-functionalized and amine-functionalized PS particles of 100 nm and 200 nm in diameter were used. The MTT assay was performed to evaluate the viability of the polymers-treated cells. The effect of short (6 h) and prolonged (48 h) incubation with different concentrations of PS particles on the cell's zeta (ζ) potential was examined with the electrophoretic light scattering technique (ELS). Polystyrene particles' physicochemical characteristics (size and stability) were performed using dynamic light scattering (DLS) and electrophoretic light scattering methods. RESULTS: The results show that submicron PS particles affect cell viability and cause changes in the physiochemical parameters of rat cell membranes. Differences were observed depending on the origin of the cells. We observed doseand time-dependent alterations in the studied parameters after submicron PS particle incubation in L6 myotubes and H9c2 cardiomyocytes. CONCLUSIONS: The size and modification of PS particle surfaces determine the extent to which they affect the analyzed properties of rat cardiomyocytes and myocytes membranes.

Structural Studies of Aluminated form of Zeolites-EXAFS and XRD Experiment, STEM Micrography, and DFT Modelling.

In this article, the results of computational structural studies on Al-containing zeolites, via periodic DFT + D modelling and FDM (Finite Difference Method) to solve the Schrödinger equation (FDMNES) for XAS simulations, corroborated by EXAFS (Extended X-ray Absorption Fine Structure) spectroscopy and PXRD (powder X-ray diffractometry), are presented. The applicability of Radial Distribution Function (RDF) to screen out the postulated zeolite structure is also discussed. The structural conclusions are further verified by HR-TEM imaging.

Monitoring of the Surface Charge Density Changes of Human Glioblastoma Cell Membranes upon Cinnamic and Ferulic Acids Treatment.

Cinnamic acid (CA) and ferulic acid (FA) are naturally occurring phenolic acids claimed to exert beneficial effects against disorders related to oxidative stress, including cancer. One such malignancy that still remains a therapeutic challenge mainly due to its heterogeneity and inaccessibility to therapeutic agents is Glioblastoma multiforme (GBM). Here, the influence of CA and FA on the surface charge density of human GBM cell line LN-229 was studied using the electrophoretic light scattering technique. Also, the cytotoxicity of both phenolic acids was determined by metabolic activity-assessing tetrazolium test (MTT) analysis after exposure to CA and FA for 24 h and 48 h. Results showed that both compounds reduced cell viability of LN-229 cells, with more pronounced effect evoked by CA as reflected in IC50 values. Further analyses demonstrated that, after treatment with both phenolic acids, the negative charge of membranes decreased at high pH values and the positive charge of the membranes increased at low pH values compared to the data obtained for untreated cells. Afterward, a four-equilibrium model was applied to estimate the total surface concentrations of both acidic and basic functional groups and their association constants with solution ions in order to calculate theoretical values of membrane surface charge densities. Then, the theoretical data were compared to the experimental data in order to verify the mathematical model. As such, our results indicate that application of electrochemical methods to determine specific drug-membrane interactions might be crucial for predicting their pharmacological activity and bioavailability.

On the Structure and Reaction Mechanism of Human Acireductone Dioxygenase.

Acireductone dioxygenase (ARD) is an intriguing enzyme from the methionine salvage pathway that is capable of catalysing two different oxidation reactions with the same substrate depending on the type of the metal ion in the active site. To date, the structural information regarding the ARD-acireductone complex is limited and possible reaction mechanisms are still under debate. The results of joint experimental and computational studies undertaken to advance knowledge about ARD are reported. The crystal structure of an ARD from Homo sapiens was determined with selenomethionine. EPR spectroscopy suggested that binding acireductone triggers one protein residue to dissociate from Fe2+ , which allows NO (and presumably O2 ) to bind directly to the metal. Mössbauer spectroscopic data (interpreted with the aid of DFT calculations) was consistent with bidentate binding of acireductone to Fe2+ and concomitant dissociation of His88 from the metal. Major features of Fe vibrational spectra obtained for the native enzyme and upon addition of acireductone were reproduced by QM/MM calculations for the proposed models. A computational (QM/MM) study of the reaction mechanisms suggests that Fe2+ promotes O-O bond homolysis, which elicits cleavage of the C1-C2 bond of the substrate. Higher M3+ /M2+ redox potentials of other divalent metals do not support this pathway, and instead the reaction proceeds similarly to the key reaction step in the quercetin 2,3-dioxygenase mechanism.

Evaluation of the correlation between Scoring Feline Allergic Dermatitis and Feline Extent and Severity Index and skin hydration in atopic cats.

BACKGROUND: Evaluation of the severity of clinical signs of cats with allergic skin diseases has used two scoring systems: Scoring Feline Allergic Dermatitis (SCORFAD) and the Feline Extent and Severity Index (FeDESI). The integrity of the cutaneous barrier can also be evaluated by measuring skin hydration. A correlation between the clinical score and skin hydration has been observed in humans and dogs with atopic dermatitis (AD). HYPOTHESIS: To demonstrate a correlation between the clinical score and skin hydration of cats affected with presumed AD. ANIMALS: European short hair cats (n = 18): 11 females and seven males with a confirmed diagnosis of AD. METHODS: SCORFAD and FeDESI scores were calculated and the measurements of skin hydration were assessed from seven body sites using corneometry. The correlation between the SCORFAD and FeDESI systems and skin hydration of each site, and the average skin hydration was calculated. RESULTS: There was a positive correlation between the SCORFAD score and skin hydration for the axilla, thorax and forelimb; for FeDESI and axilla and lumbar sites. There was a negative correlation between the FeDESI and skin hydration for the pinna (r = -0.47). CONCLUSIONS AND CLINICAL IMPORTANCE: Measurements of skin hydration could be a useful tool for the evaluation of allergic cats. There is limited evidence of any useful correlation between clinical scoring systems and measurements of hydration. The pinna may be a suitable region for the assessment of skin barrier function in normal and allergic cats.

Assessment of the relationship between transepidermal water loss (TEWL) and severity of clinical signs (CADESI-03) in atopic dogs.

BACKGROUND: Atopic dermatitis (AD) is a common allergic skin disease of dogs. Objective documentation of disease severity is important for the assessment of responses to therapeutic interventions. One common means of assessing the severity of clinical signs is the Canine Atopic Dermatitis Extent and Severity Index (CADESI)-03. In addition, studies of the biophysical parameters of the skin suggest that assessment of transepidermal water loss (TEWL) may also have value for estimation of disease severity. HYPOTHESIS/OBJECTIVES: The aim of the present study was to verify the correlation between TEWL and CADESI-03 measured at 10 different body sites. ANIMALS: Twenty-six dogs with AD (age range 1-7 years, median age 3 years). METHODS: The assessment was performed at the following 10 body sites: the lumbar, inguinal, ventral abdominal, interdigital regions, axillary fossa, lateral thorax, lateral aspect of the antebrachium, concave surface of the auricle, cheek and bridge of the nose. RESULTS: Positive correlations were found between TEWL and the total CADESI-03 for the auricle (r = 0.59), bridge of nose (r = 0.62) and interdigital skin (r = 0.47). Positive correlations were also observed between TEWL and local CADESI-03 scores for the axillary fossa (r = 0.73), inguinal region (r = 0.55) and interdigital skin (r = 0.77). CONCLUSIONS AND CLINICAL IMPORTANCE: The results indicate that it may be possible to use measurement of TEWL to assess the severity of skin lesions, but a positive correlation was found in only five of 10 body regions examined.

Impact of Synthesis Parameters upon the Electronic Structure in PVD-Deposited CdxZn1-xO Composite Thin Films: An XPS-XANES Investigation.

The impact of different synthesis parameters, such as thickness, postsynthesis annealing temperature, and oxygen gas flow rate, upon the electronic structure is discussed in detail in the present experimental investigation. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy techniques are used to evaluate the surface electronic properties along with the presence and stability of the CdO2 surface oxide in CdxZn1-xO (x = 0.4) composite thin films. The thin films were synthesized with varying thicknesses using a Cd0.4Zn0.6O (CZO) ceramic and Cd0.4Zn0.6 (CZ) metallic targets and oxygen gas flow rates during magnetron sputtering. The Zn L3,2 edge and O K edge XANES spectra are affected by the oxygen gas flow rate. For the zero rate, an increase in intensity is observed in the Zn L3,2 edge, and notable changes occur in the overall spectral features of the O K edge. In the films synthesized in the presence of oxygen, highly probable O 2p → antibonding Zn 3d electronic transitions decrease the probability of the Zn 2p1/2 → antibonding Zn 3d electronic transition by filling the vacant antibonding Zn 3d states, leading to the reduction in overall intensity in the Zn L3,2 edge. Scanning electron microscopy reveals grain growth with increasing annealing temperature. The annealing induces orbital hybridization, generating new electronic states with higher transition probabilities and intensity enhancement in both Zn L3,2 and O K edges. The presence of the CdO2 surface phase is confirmed by analyzing the Cd 3d5/2 and O 1s XPS core levels. The CdO2 surface phase is observed in the films synthesized using the CZO target for all thicknesses, while the CZ target is only observed for higher thicknesses. Further postsynthesis annealing treatment results in the disappearance of the CdO2 phase. The CdO2 surface phase can be controlled by varying the film thickness and postsynthesis annealing temperature.

Enhanced Electrochemical Performance of MnCo1.5Fe0.5O4Spinel for Oxygen Evolution Reaction through Heat Treatment.

MnCo1.5Fe0.5O4 spinel oxide was synthesized using the sol-gel technique, followed by heat treatment at various temperatures (400, 600, 800, and 1000 °C). The prepared materials were examined as anode electrocatalysts for water-splitting systems in alkaline environments. Solid-state characterization methods, such as powder X-ray diffraction and X-ray absorption spectroscopy (XAS), were used to analyze the materials' crystallographic structure and surface characteristics. The intrinsic activity of the MnCo1.5Fe0.5O4 was fine-tuned by altering the electronic structure by controlling the calcination temperature, and the highest activity was observed for the sample treated at 800 °C. A shift in the valence state of surface cations under oxidative conditions in an alkaline solution during the oxygen evolution reaction was detected through ex situ XAS measurements. Moreover, the influence of the experimental conditions on the electrocatalytic performance of the material, including the pH of the electrolyte and the temperature, was demonstrated.

Formation of Grown-In Nitrogen Vacancies and Interstitials in Highly Mg-Doped Ammonothermal GaN.

The formation of intrinsic point defects in the N-sublattice of semi-insulating Mg-doped GaN crystals grown by the ammonothermal method (SI AT GaN:Mg) was investigated for the first time. The grown-in defects produced by the displacement of nitrogen atoms were experimentally observed as deep traps revealed by the Laplace transform photoinduced transient spectroscopy in the compensated p-type crystals with the Mg concentrations of 6 × 1018 and 2 × 1019 cm-3 and resistivities of ~1011 Ωcm and ~106 Ωcm, respectively. In both kinds of materials, three closely located traps with activation energies of 430, 450, and 460 meV were revealed. The traps, whose concentrations in the stronger-doped material were found to be significantly higher, are assigned to the (3+/+) and (2+/+) transition levels of nitrogen vacancies as well as to the (2+/+) level of nitrogen split interstitials, respectively. In the material with the lower Mg concentration, a middle-gap trap with the activation energy of 1870 meV was found to be predominant. The results are confirmed and quantitatively described by temperature-dependent Hall effect measurements. The mechanism of nitrogen atom displacement due to the local strain field arising in SI AT GaN:Mg is proposed and the effect of the Mg concentration on the charge compensation is discussed.

Competing Mechanisms Determine Oxygen Redox in Doped Ni-Mn Based Layered Oxides for Na-Ion Batteries.

Cation doping is an effective strategy for improving the cyclability of layered oxide cathode materials through suppression of phase transitions in the high voltage region. In this study, Mg and Sc are chosen as dopants in P2-Na0.67Ni0.33Mn0.67O2, and both have found to positively impact the cycling stability, but influence the high voltage regime in different ways. Through a combination of synchrotron-based methods and theoretical calculations it is shown that it is more than just suppression of the P2 to O2 phase transition that is critical for promoting the favorable properties, and that the interplay between Ni and O activity is also a critical aspect that dictates the performance. With Mg doping, the Ni activity can be enhanced while simultaneously suppressing the O activity. This is surprising because it is in contrast to what has been reported in other Mn-based layered oxides where Mg is known to trigger oxygen redox. This contradiction is addressed by proposing a competing mechanism between Ni and Mg that impacts differences in O activity in Na0.67MgxNi0.33- xMn0.67O2 (x < 0 < 0.33). These findings provide a new direction in understanding the effects of cation doping on the electrochemical behavior of layered oxides.

Evaluation of electrosynthesized reduced graphene oxide-Ni/Fe/Co-based (oxy)hydroxide catalysts towards the oxygen evolution reaction.

In this work, the specific role of the addition of graphene oxide (GO) to state-of-the-art nickel-iron (NiFe) and cobalt-nickel-iron (CoNiFe) mixed oxides/hydroxides towards the oxygen evolution reaction (OER) is investigated. Morphology, structure, and OER catalytic activity of the catalysts with and without GO were studied. The catalysts were fabricated via a two-step electrodeposition. The first step included the deposition of GO flakes, which, in the second step, were reduced during the simultaneous deposition of NiFe or CoNiFe. As a result, NiFe-GO and CoNiFe-GO were fabricated without any additives directly on the nickel foam substrate. A significant improvement of the OER activity was observed after combining NiFe with GO (OER overpotential η(10 mA·cm-2): 210 mV) compared to NiFe (η: 235 mV) and GO (η: 320 mV) alone. A different OER activity was observed for CoNiFe-GO. Here, the overall catalytic activity (η: 230 mV) increased compared to GO alone. However, it was reduced in comparison to CoNiFe (η: 224 mV). The latter was associated with the change in the morphology and structure of the catalysts. Further OER studies showed that each of the catalysts specifically influenced the process. The improvement in the OER by NiFe-GO results mainly from the structure of NiFe and the electroactive surface area of GO.

Exposure to polystyrene nanoparticles leads to changes in the zeta potential of bacterial cells.

Polymer molecules, the main components of plastics, are an emerging pollutants in various environmental compartments (water, air, soil) that may induce several ecotoxicological effects on live organisms. Therefore, understanding how plastic particles interact with bacterial cell membranes is crucial in analysing their associated risks in ecosystems and human microbiota. However, relatively little is known about the interaction between nanoplastics and bacteria. The present work focuses on Staphylococcus aureus and Klebsiella pneumoniae, representing the Gram-positive and Gram-negative bacteria respectively, exposed to 100 nm diameter polystyrene nanoparticles (PS NPs). The nanoparticles attach to the cells' membranes of both bacteria, changing their electrical charge, but without the effect of killing the cells. PS NPs caused a change in zeta potential values (both species of bacterial strains), dependent on particle concentration, pH, as well as on exposure time of bacteria to them. Through the application of AFM and FTIR techniques, the presence of PS NPs on bacterial surfaces was detected, suggesting the affinity of the particles to bacterial components, but without any changes in the morphology of the tested bacteria. The zeta potential can be more widely used in the study of interactions between nanostructures and cells.

Correction to "Synthesis Attempt and Structural Studies of Novel A2CeWO6 Double Perovskites (A2+ = Ba, Ca) in and outside of Ambient Conditions".

[This corrects the article DOI: 10.1021/acsomega.2c00669.].

The Effect of Submicron Polystyrene on the Electrokinetic Potential of Cell Membranes of Red Blood Cells and Platelets.

In recent years, many scientists have studied the effects of polymer micro- and nanostructures on living organisms. As it turns out, plastic can be a component of the blood of livestock, eaten by humans around the globe. Thus, it seems important to investigate possible changes in the physicochemical parameters and morphology of the cell membranes of blood morphotic elements (red blood cells and platelets) under the influence of polymer particles. The article presents research in which cell membranes were exposed to plain polystyrene (PS) and amino-functionalized polystyrene (PS-NH2) of two different sizes. The polymers were characterized by infrared spectroscopy and dynamic light-scattering methods. To analyze possible changes caused by polymer exposure in the structure of the membranes, their zeta potentials were measured using the electrophoretic light-scattering technique. The concentration of the polymers, as well as the exposure time, were also taken into the consideration during the research. Based on the obtained results, we concluded that 100 and 200 nm PS, as well as 100 nm PS-NH2, internalize into the cells. On the contrary, 200 nm PS-NH2 particles attach to cell membranes. Our study clearly shows that particle size and surface chemistry determine the interaction with biological membranes.

Carbon and Manganese in Semi-Insulating Bulk GaN Crystals.

Co-doping with manganese and carbon was performed in gallium nitride grown by halide vapor phase epitaxy method. Native seeds of high structural quality were used. The crystallized material was examined in terms of its structural, optical, and electrical properties. For that purpose, different characterization methods: x-ray diffraction, Raman spectroscopy, low-temperature photoluminescence, and temperature-dependent Hall effect measurements, were applied. The physical properties of the co-doped samples were compared with the properties of crystals grown in the same reactor, on similar seeds, but doped only with manganese or carbon. A comparison of the electrical and optical properties allowed to determine the role of manganese and carbon in doped and co-doped gallium nitride crystals.

Negative Magnetoresistivity in Highly Doped n-Type GaN.

This paper presents low-temperature measurements of magnetoresistivity in heavily doped n-type GaN grown by basic GaN growth technologies: molecular beam epitaxy, metal-organic vapor phase epitaxy, halide vapor phase epitaxy and ammonothermal. Additionally, GaN crystallized by High Nitrogen Pressure Solution method was also examined. It was found that all the samples under study exhibited negative magnetoresistivity at a low temperature (10 K < T < 50 K) and for some samples this effect was observed up to 100 K. This negative magnetoresistivity effect is analyzed in the frame of the weak localization phenomena in the case of three-dimensional electron gas in a highly doped semiconductor. This analysis allows for determining the phasing coherence time τφ for heavily doped n-type GaN. The obtained τφ value is proportional to T−1.34, indicating that the electron−electron interaction is the main dephasing mechanism for the free carriers.

The influence of the pH on the incorporation of caffeic acid into biomimetic membranes and cancer cells.

Caffeic acid (CA) is a phenolic compound synthesized by all plant species. It constitutes the main hydroxycinnamic acid found in human diet and presents a variety of beneficial effects including anticancer activity. Current data suggests essential role of the interplay between anticancer drugs and the cell membrane. Given this, biophysical interactions between CA and cancer cells or biomimetic membranes were investigated. Glioblastoma cell line U118MG and colorectal adenocarcinoma cell line DLD-1, as well as lipid bilayers and liposomes, were used as in vitro models. Electrophoretic light scattering was used to assess the effect of CA on the surface charge of cancer cells and liposomal membranes. Electrochemical impedance spectroscopy was chosen to evaluate CA-dependent modulatory effect on the electrical capacitance and electrical resistance of the bilayers. Our results suggest that CA fulfills physicochemical criteria determining drug-like properties of chemical compounds, and may serve as a potential cytostatic agent in cancer treatment.

Antiviral Properties against SARS-CoV-2 of Nanostructured ZnO Obtained by Green Combustion Synthesis and Coated in Waterborne Acrylic Coatings.

The COVID-19 pandemic has increased the need for developing disinfectant surfaces as well as reducing the spread of infections on contaminated surfaces and the contamination risk from the fomite route. The present work reports on the antiviral activity of coatings containing ZnO particles obtained by two simple synthesis routes using Aloe vera (ZnO-aloe) or cassava starch (ZnO-starch) as reaction fuel. After detailed characterization using XRD and NEXAFS, the obtained ZnO particles were dispersed in a proportion of 10% with two different waterborne acrylic coatings (binder and commercial white paint) and brushed on the surface of polycarbonates (PC). The cured ZnO/coatings were characterized by scanning electron microscopes (SEM) and energy-dispersive X-ray spectroscopy (EDS). Wettability tests were performed. The virucidal activity of the ZnO particles dispersed in the waterborne acrylic coating was compared to a reference control sample (PC plates). According to RT-PCR results, the ZnO-aloe/coating displays the highest outcome for antiviral activity against SARS-CoV-2 using the acrylic binder, inactivating >99% of the virus after 24 h of contact relative to reference control.

Synthesis Attempt and Structural Studies of Novel A2CeWO6 Double Perovskites (A2+ = Ba, Ca) in and outside of Ambient Conditions.

This comprehensive work showcases two novel, rock-salt-type minerals in the form of amphoteric cerium-tungstate double perovskite and ilmenite powders created via a high-temperature solid-state reaction in inert gases. The presented studies have fundamental meaning and will mainly focus on a detailed synthesis description of undoped structures, researching their possible polymorphism in various conditions and hinting at some nontrivial physicochemical properties like charge transfer for upcoming optical studies after eventual doping with selectively chosen rare-earth ions. The formerly mentioned, targeted A2BB'X6 group of compounds contains mainly divalent alkali cations in the form of XIIA = Ba2+, Ca2+ sharing, here, oxygen-arranged clusters (IIX = O2-) with purposely selected central ions from f-block VIB = Ce4/3+ and d-block VIB' = W4/5/6+ since together they often possess some exotic properties that could be tuned and implemented into futuristic equipment like sensors or energy converters. Techniques like powder XRD, XPS, XAS, EPR, Raman, and FTIR spectroscopies alongside DSC and TG were involved with an intent to thoroughly describe any possible changes within these materials. Mainly, to have a full prospect of any desirable or undesirable phenomena before diving into more complicated subjects like: energy or charge transfer in low temperatures; to reveal whether or not the huge angular tilting generates large enough dislocations within the material's unit cell to change its initial properties; or if temperature and pressure stimuli are responsible for any phase transitions and eventual, irreversible decomposition.