Chemical Stability of High-Entropy Spinel in a High-Pressure Pure Hydrogen Atmosphere.

This paper focuses on high-entropy spinels, which represent a rapidly growing group of materials with physicochemical properties that make them suitable for hydrogen energy applications. The influence of high-pressure pure hydrogen on the chemical stability of three high-entropy oxide (HEO) sinter samples with a spinel structure was investigated. Multicomponent HEO samples were obtained via mechanochemical synthesis (MS) combined with high-temperature thermal treatment. Performing the free sintering procedure on powders after MS at 1000 °C for 3 h in air enabled achieving single-phase (Cr0.2Fe0.2Mg0.2Mn0.2Ni0.2)3O4 and (Cu0.2Fe0.2Mg0.2Ni0.2Ti0.2)3O4 powders with a spinel structure, and in the case of (Cu0.2Fe0.2Mg0.2Ti0.2Zn0.2)3O4, a spinel phase in the amount of 95 wt.% was achieved. A decrease in spinel phase crystallite size and an increase in lattice strains were established in the synthesized spinel powders. The hydrogenation of the synthesized samples in a high-pressure hydrogen atmosphere was investigated using Sievert's technique. The results of XRD, SEM, and EDS investigations clearly showed that pure hydrogen at temperatures of up to 250 °C and a pressure of up to 40 bar did not significantly impact the structure and microstructure of the (Cr0.2Fe0.2Mg0.2Mn0.2Ni0.2)3O4 ceramic, which demonstrates its potential for application in hydrogen technologies.

Synthesis and Characterization of Antibacterial Chitosan Films with Ciprofloxacin in Acidic Conditions.

This work presents the results of research on obtaining chitosan (CS) films containing on their surface ciprofloxacin (CIP). A unique structure was obtained that not only gives new properties to the films, but also changes the way of coverage and structure of the surface. The spectroscopic test showed that in the process of application of CIP on the surface of CS film, CIP was converted from its crystalline form to an amorphic one, hence improving its bioavailability. This improved its scope of microbiological effect. The research was carried out on the reduction of CIP concentration during the process of CIP adhesion to the surface of chitosan films. The antibacterial activity of the CS films with and without the drug was evaluated in relation to Escherichia coli and Staphylococcus aureus, as well as Candida albicans and Penicillium expansum. Changes in the morphology and roughness of membrane surfaces after the antibacterial molecule adhesion process were tested with atomic force microscopy (AFM) and scanning electron microscopy (SEM). Structural analysis of CS and its modifications were confirmed with Fourier-transform spectroscopy in the infrared by an attenuated total reflectance of IR radiation (FTIR-ATR) and solid-state nuclear magnetic resonance (NMR).

The Study of the Influence of ZrO2 Precursor Type and the Temperature of Annealing on the Crystallization of the Tetragonal Polymorph of ZrO2 in Zirconia-Silica Gels.

Materials of the ZrO2-SiO2 system were obtained by the sol-gel method applying two different types of ZrO2 precursors: zirconium (IV) n-propoxide Zr(OC3H7)4 and zirconium (IV) acetate Zr(OOC2H3)4 (organic acetic acid salt) while commonly used tetraethoxysilane TEOS was selected as SiO2 introducing one. ZrO2 concentration in synthesized samples varied from 20% to 50% (mol.). After drying for 28 days, all gels were annealed at 500 °C, 1000 °C, and 1200 °C in air. FTIR spectroscopy together with XRD diffraction was selected as the two main structure research methods. SEM microscopy was applied to analyze the local chemical compositions of samples and to observe the morphology of gels' surfaces. The analysis of FTIR spectra and XRD diffraction patterns allowed us to recognize different ZrO2 polymorphs which appeared in the samples depending strongly as well on ZrO2 precursor type as on the temperature of annealing. Samples synthesized by using the zirconium (IV) n-propoxide contained both cubic and tetragonal zirconia phases in general but showed the tendency of the increasing t-ZrO2 content in gels richer in ZrO2 and heated up to 1200 °C. However, in materials obtained applying zirconium (IV) acetate, the first detected at 500 °C phase was t-ZrO2 which was then conversing to m-ZrO2 form with the increasing temperature in case of samples rich in ZrO2. Meanwhile, t-ZrO2 was the predominant phase in samples of the lower content of ZrO2 but annealed at higher temperatures. By the analysis of changes in band profiles and positions, one can draw conclusions that the structure of studied samples is mostly built up of an amorphous silica matrix, in which different types of zirconia polymorphs create their own crystal lattice. The presence of the particular polymorph depends strongly on the type of zirconia precursor and the temperature of annealing.

Plasmochemical Modification of Crofer 22APU for Intermediate-Temperature Solid Oxide Fuel Cell Interconnects Using RF PA CVD Method.

The results of plasmochemical modification on Crofer 22APU ferritic stainless steel with a SiCxNy:H layer, as well as the impact of these processes on the increase in usability of the steel as intermediate-temperature solid oxide fuel cell (IT-SOFC), interconnects, are presented in this work. The layer was obtained using Radio-Frequency Plasma-Activated Chemical Vapor Deposition (RF PA CVD, 13.56 MHz) with or without the N+ ion modification process of the steel surface. To determine the impact of the surface modification on the steel's resistance to high-temperature corrosion and on its mechanical properties, the chemical composition, atomic structure, and microstructure were investigated by means of IR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Microhardness, Young's modulus, wear rate, as well as electrical resistance, were also determined. Micromechanical experiments showed that the plasmochemical modification has a positive influence on the surface hardness and Young's modulus of the investigated samples. High-temperature oxidation studies performed for the samples indicate that N+ ion modification prior to the deposition of the SiCxNy:H layer improves the corrosion resistance of Crofer 22APU steel modified via CVD. The area-specific resistance of the studied samples was 0.01 Ω·cm2, which is lower than that of bare steel after 500 h of oxidation at 1073 K. It was demonstrated that the deposition of the SiCxNy:H layer preceded by N+ ion modification yields the best properties.

Physicochemical Study of the Self-Disintegration of Calcium Orthosilicate (ß→γ) in the Presence of the C12A7 Aluminate Phase.

The ß-γ polymorphic transition of calcium orthosilicate (C2S) is a key phenomenon in cement chemistry. During this transition, the compound expands due to structural changes and a significant reduction in its density is observed, leading to its disintegration into a powder with a very high specific surface area. Owing to this tendency of the C2S material to "self-disintegrate", its production is energy-efficient and thus environmentally friendly. A physicochemical study of the self-disintegration process was conducted with the aim of determining how the amount of dodecacalcium hepta-aluminate (C12A7) in calcium orthosilicate (C2S) affects the temperature at which the polymorphic transi-tions from α'L-C2S to ß-C2S and from ß-C2S to γ-C2S undergo stabilization. The applied techniques included differential thermal analysis (DTA), calorimetry and X-ray diffraction (XRD), and they made it possible to determine what C2S/C12A7 phase ratio in the samples and what cooling rate constitute the optimal conditions of the self-disintegration process. The optimal cooling rate for C2S materials with a C12A7 content of up to 60 wt% was determined to be 5 K·min-1. The optimal mass ratio of C2S/C12A7 was found to be 70/30, which ensures both efficient self-disintegration and desirable grain size distribution.

p38 but not p53 is responsible for UVA-induced MCPIP1 expression.

MCPIP1 (Monocyte Chemotactic Protein-1 Induced Protein) is an important regulator of inflammation and cell apoptosis, but its role in UVA-induced stress response in the epidermis has never been studied. We have found that moderate apoptosis-inducing dose of UVA (27J/cm2) increases the level of MCPIP1 expression in HaCaT cells and normal human keratinocytes (NHEK) within 6-9h after the treatment. MCPIP1 upregulation was dependent on the induction of p38, but not p53, as demonstrated by using p38 inhibitor SB203580 and p53 inducer RG7388, respectively. This increase was also blocked by antioxidants (α-tocopherol and ascorbic acid), suggesting the involvement of MCPIP1 in UVA-induced oxidative stress response. Si-RNA-mediated down-regulation of MCPIP1 expression in HaCaT cells resulted in increased sensitivity to UVA-induced DNA damage and apoptosis. This was accompanied by decreased phosphorylation of p53 and p38 in MCPIP1-silenced cells following UVA irradiation. The activation of p38 in response to low doses of ultraviolet radiation was postulated to be protective for p53-inactive cells. Therefore, MCPIP1 may favor the survival of p53-defective HaCaT cells by sustaining the activation of p38. This creates a loop of mutual positive regulation between p38 and MCPIP1 protein in HaCaT cells, providing the protection against the consequences of UVA irradiation.

Institution of the health care agent in Polish legislation: position of the Polish Working Group on End-of-Life Ethics.

INTRODUCTION In numerous countries legislation has been put in place allowing citizens to appoint persons authorized to make medical decisions on their behalf, should the principal lose such decision­making capacity. OBJECTIVES The paper aimed to prepare a draft proposal of legal regulations introducing into Polish legislation the institution of the health care agent. PATIENTS AND METHODS The draft proposal has been grounded in 6 expertise workshops, in conjunction with several online debates. RESULTS The right to appoint a health care agent should apply to all persons of full legal capacity, and to minors over 16 years of age. Every non-legally incapacitated adult person would be eligible to be appointed a health care agent. Appointment of substitute agents should also be legally provided for. The prerogatives of health care agents would come into effect upon the principals' loss of their decisionmaking capacity, or upon the principals' waiving their right to be provided with pertinent information on their health status. The health care agents would make decisions in all matters pertaining to medical treatment, while remaining under no obligation to perform any hands-on caring duties for their principals. The term of medical power-of-attorney should be discretionary, while its revocation or resignation should be possible at any time. In the event of health care agents' inactivity, or in the event that their actions should appear contrary to the principals' best interests, an attending physician should notify a pertinent court of law whose prerogatives would facilitate revocation of a medical power-of-attorney.  CONCLUSIONS Statutory appointment of a health care agent allows every citizen to appoint in this capacity a person who, to the best of his or her knowledge, would best represent his or her interests in the event that the principal should ultimately lose the capacity to make medical decisions on his or her own behalf.

Modulatory Effects of Curcumin and Tyrphostins (AG494 and AG1478) on Growth Regulation and Viability of LN229 Human Brain Cancer Cells.

In this study we employed curcumin as a potent adjuvant agent in the treatment of human brain cancer involving selective EGFR kinase inhibitors: tyrphostins AG494 and AG1478. Aim of this work was to evaluate the effect of tested compounds on autocrine growth, cell cycle, and viability of LN229 cells, as well as to assess their proapoptotic and genotoxic properties. Our results showed that all tested compounds significantly inhibited autocrine growth of the investigated cell line in a dose dependent manner. However they are characterized by different kinetics of cell growth inhibition. Suppression of growth by the tyrphostins was completely or partially reversible in contrast to curcumin. Curcumin increased the cytostatic and/or cytotoxic potential of AG494 and AG1478. Tyrphostins did not have genotoxic properties regardless of concentration used, whereas curcumin cytotoxic and genotoxic properties were directly proportional to the concentration. Curcumin significantly increased tyrphostins cytotoxicity. The most promising of the obtained results may be the use of curcumin and tyrphostin AG494 in the treatment of cancer cells. Anticancer effect of the mixture was confirmed by increase of cytotoxic effect, decrease of viability, stimulation of apoptotic procesess, irreversible DNA damage, and decrease of the ROS in the culture of glioblastoma cells.

Diagnosis and management of neuropathic pain: review of literature and recommendations of the Polish Association for the Study of Pain and the Polish Neurological Society - Part Two.

Neuropathic pain may be caused by a variety of lesions or diseases of both the peripheral and central nervous system. The most common and best known syndromes of peripheral neuropathic pain are painful diabetic neuropathy, trigeminal and post-herpetic neuralgia, persistent post-operative and post-traumatic pain, complex regional pain syndrome, cancer-related neuropathic pain, HIV-related neuropathic pain and pain after amputation. The less common central pain comprises primarily central post-stroke pain, pain after spinal cord injury, central pain in Parkinson disease or in other neurodegenerative diseases, pain in syringomyelia and in multiple sclerosis. A multidisciplinary team of Polish experts, commissioned by the Polish Association for the Study of Pain and the Polish Neurological Society, has reviewed the literature on various types of neuropathic pain, with special focus on the available international guidelines, and has formulated recommendations on their diagnosis and treatment, in accordance with the principles of evidence-based medicine (EBM). High quality studies on the efficacy of various medicines and medical procedures in many neuropathic pain syndromes are scarce, which makes the recommendations less robust.

Diagnosis and management of neuropathic pain: review of literature and recommendations of the Polish Association for the study of pain and the Polish Neurological Society - part one.

Neuropathic pain still present a major diagnostic and therapeutic challenge despite considerable progress in understanding of its mechanisms and publication of number of studies which assessed the efficacy and safety of drugs used in the symptomatic treatment. In practice, it is diagnosed less frequently than recognised in the epidemiological studies, and many patients do not achieve satisfactory outcomes of treatment. A multidisciplinary team of Polish experts, commissioned by the Polish Association for the Study of Pain and the Polish Neurological Society, has reviewed the literature on neuropathic pain, with special focus on the published international recommendations, and formulated recommendations on neuropathic pain diagnosis and treatment, in accordance with the principles of evidence-based medicine. The paper presents also background information on the neuropathic pain definition, epidemiology, pathomechanism and method of assessment. The diagnosis of neuropathic pain may be established based on medical history and physical examination including special assessment of the somatosensory system. First-line drugs used in pharmacological management of neuropathic pain are: tricyclic antidepressants, serotonin and norepinephrine reuptake inhibitors, gabapentin, pregabalin, opioids and lidocaine patches.

The effect of tyrphostins AG494 and AG1478 on the autocrine growth regulation of A549 and DU145 cells.

We employed two selective EGFR tyrosine kinase inhibitors: AG494 (reversible) and AG1478 (irreversible) for growth regulation of human lung (A549) and prostate (DU145) cancer cell lines, cultured in chemically defined DMEM/F12 medium. Both tested tyrphostins significantly inhibited autocrine growth of the investigated cell lines. The action of AG494 was dose dependent, and at highest concentrations led to complete inhibition of growth. AG1478 seemed to be more effective at lower concentrations, but was unable to completely inhibit growth of A549 cells. Inhibition of EGFR kinase activity by AG494 in contrast to AG1478 had no effect on the activity of ERK in both cell lines. Both EGFR's inhibitors induced apoptosis of the investigated lung and prostate cancer cell lines, but the proapoptotic effect of the investigated tyrphostins was greater in A549 than in DU145 cells. The tyrphostins arrested cell growth of DU145 and A549 cells in the G1 phase, similarly to other known inhibitors of EGFR. The influence of AG494 and AG1478 on the activity of two signaling proteins (AKT and ERK) was dependent upon the kind of investigated cells. In the case of DU145 cells, there was an evident decline in enzymatic activity of both kinases (stronger for AG1478), while in A549, only AG1478 effectively inhibited the phosphorylation of Akt. Tyrphostins AG494 and AG1478 are ATP-competitors and are supposed to have a similar mechanism of action, but our results suggest that this is not quite true.

The FTIR studies of gels and thin films of Al2O3-TiO2 and Al2O3-TiO2-SiO2 systems.

In this work, samples in form of bulk ones and thin films were obtained using the sol-gel method. The bulk samples were heated at different temperatures (500 °C, 850 °C and 1100 °C) corresponding to the annealing process of coatings, deposited on different substrates by dipping and pulling out samples from the proper sol with the stable speed. Thin films of both Al2O3-TiO2 and Al2O3-TiO2-SiO2 systems were deposited on carbon, steel and titanium substrates in two different ways: as single layers obtained from Al2O3 sol, TiO2 sol and Al2O3 sol or deposited as mixed coatings from Al2O3-TiO2 sol as well as Al2O3-TiO2-SiO2 one. All bulk samples were studied by the FTIR spectroscopy and the X-ray diffractometry while thin films were also investigated by the electron microscopy. In the IR spectra of Al2O3-TiO2 samples, as well as gels and coatings, bands due to the vibrations of AlO bonds of the octahedrally and tetrahedrally coordinated aluminum were observed. The IR spectra of samples of Al2O3-TiO2-SiO2 system differ from that of Al2O3-TiO2 ones in presence of bands assigned to the SiO bond vibrations and in positions of bands due to AlO bond vibrations. In all spectra of bulk samples and coatings, the positions of TiO bond vibrations were ascribed basing on the IR spectra of the pure anatase and rutile.

Vanadium compounds affect growth and morphology of human rhabdomyosarcoma cell line.

Rhabdomyosarcoma (RMS) cells were incubated with four vanadium compounds: cations BMOV and vanadyl sulphate, and anions ortho- and metavanadate. Growth inhibition of RMS cells in the culture was determined by two staining methods: with N-hexamethylpararosaniline (crystal violet = CV) or bromide 3-(4,5-dimethylthiazol-2)-2,5-diphenyltetrazolium (MTT). After 48 h incubation with 10-40 µM for NaVO3 or 20-40 µM for the other three vanadium salts, the results were statistically significantly lower (0.001 < p < 0.01) as compared to the controls (without vanadium in the medium). A vanadium concentration higher than 40 µM resulted in cell destruction or death in all cells. A comparison with our previously obtained results showed the greatest sensitivity of rat hepatoma H 35-19 cells in comparison to four human cancer cell lines (A549, DU145, HTB, RMS). Investigations of human cancer cells demonstrated that the highest resistance to orthovanadate was characteristic of RMS (c.40 µM) and HTB (c. 20 µM). Electron microscopic examination showed pleomorphic nuclei with visible amounts of heterochromatin and large nucleoli, characteristic of RMS cells. Cells at various stages of differentiation were observed.

2H-solid-state-NMR study of hydrogen adsorbed on catalytically active ruthenium coated mesoporous silica materials.

(2)H solid-state NMR measurements were performed on three samples of ruthenium nanoparticles synthesized inside two different kinds of mesoporous silica, namely SBA-3 silica materials and SBA-15 functionalized with -COOH groups and loaded with deuterium gas. The line-shape analyses of the spectra reveal the different deuteron species. In all samples a strong -OD signal is found, which shows the catalytic activity of the metal, which activates the D-D bond and deuterates the -SiOH groups through the gas phase, corroborating their usability as catalysts for hydrogenation reactions. At room temperature the mobility of the -Si-OD groups depends on the sample preparation. In addition to the -Si-OD deuterons, the presence of different types of deuterons bound to the metal is revealed. The singly coordinated -Ru-D species exhibit several different quadrupolar couplings, which indicate the presence of several non-equivalent binding sites with differing binding strength. In addition to the dissociated hydrogen species there is also a dihydrogen species -Ru-D(2), which is attributed to defect sites on the surface. It exhibits a fast rotational dynamics at all temperatures. Finally there are also indications of three-fold coordinated surface deuterons and octahedrally coordinated deuterons inside the metal.

2H solid-state NMR of ruthenium complexes.

The (2)H solid-state NMR spectra of the transition metal complexes Tp*RuD(THT)(2) (1a), Tp*RuD(D(2))(THT) (1b), Tp*RuD(D(2))(2) (1c), Cp*RuD(3)(PPh(3)) (2) and RuD(2)(eta(2)-D(2))(2)(PCy(3))(2) (3) have been measured in a wide temperature range. These compounds were chosen as potential model systems for hydrogen surface species in Ru-nanoparticles. The deuterium quadrupolar coupling constants Q(cc) and asymmetry parameters were extracted by (2)H NMR line-shape analysis. The Q(cc) values of the deuterons bound to the metal vary between 13 kHz and 76 kHz. In addition all spectra show that some of the deuterium is incorporated into carbon positions exhibiting quadrupolar coupling constants in the range of 134 kHz to 192 kHz. The room temperature spectra contain an additional weak very narrow line which was assigned to deuterons exhibiting a high mobility. These deuterons are attributed to crystallographic impurity and partially to D(2) molecules which lost by the complexes. The temperature where their motion is quenched and the types of these motions depend on the chemical structure. We propose to use the values of the quadrupolar coupling constants measured in order to characterize different hydrogen species on the surface of Ru-nanoparticles.

Structural and dynamical properties of guest molecules confined in mesoporous silica materials revealed by NMR.

In the last fifteen years several novel porous silica materials, which are periodically structured on the mesoscopic length scale, have been synthesized. They are of broad interest for fundamental studies of surface-substrate interactions, for studies of the dynamics of guest molecules in confinement and for studies of the effect of confinement on the structural and thermophysical properties of fluids. Examples of such confinement effects include the change of the freezing and melting points or glass transitions of the confined liquids. These effects are studied by combinations of several NMR techniques, such as (15)N- and (2)H-solid-state NMR line shape analysis, MAS NMR and NMR diffusometry with physico-chemical characterization techniques such as nitrogen adsorption and small angle diffraction of neutrons or X-rays. This combination does not require crystalline samples or special clean and well defined surfaces such as conventional surface science techniques, but can work with typical ill-defined real world systems. The review discusses, after a short introduction, the salient features of these materials and the applied NMR experiments to give the reader a basic knowledge of the systems and the experiments. The rest of the review then focuses on the structural and dynamical properties of guest molecules confined in the mesoporous silica. It is shown that the confinement into the pores leads to fascinating new features of the guests, which are often not known for their bulk phases. These features depend strongly on the interplay of the their interactions with the silica surface and their mutual interactions.

Thyroid volume and hormone response in the early kidney transplants.

BACKGROUND: Thyroid hormones could affect renal function, and conversely renal function disturbances may affect thyroid function. Disturbances of the thyroid hormone concentration are often connected with thyroid gland enlargement. The aim of study was to estimate the function and morphology of the thyroid and kidney graft after kidney transplantation. As the indicator of thyroid and renal function we have used thyroid gland volume, plasma concentration of T3, reverse rT3, creatinine concentration, and renal arteries RI. MATERIAL/METHODS: Studied group included 17 individuals after kidney transplantation, with stabile graft function. The control group included 18 individuals after various surgical procedures. The estimated parameters were: thyroid volume, renal arteries resistive index, concentrations of creatinine,T3 and rT3.The parameters were controlled before transplantation (surgery), the day after, and at 3rd, 6th and 10th day after surgery. RESULTS: All patients, before and after surgical procedure, were clinically euthyroid. Mean creatinine concentration showed tendency to diminish. Statistical analysis revealed positive correlation between Delta concentration of creatinine and Delta volume of thyroid (R Spearman=0.46, p=0.05). Till the 6th day after transplantation T3 concentration diminished, and at the 10th day presented tendency to rise. We found negative correlation between T3 concentration and renal arteries RI. The rT3 concentration during 10 days after transplantation was above the reference level. CONCLUSIONS: The FT3 level and thyroid volume correlates with kidney transplant function. The supplementary thyroid hormones administration should be considered before and after renal transplantation.