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Abstract Cyclic tetrapeptides c(Pro-Phe-Pro-Phe) obtained by the mechanosynthetic method using a ball mill were isolated in a pure stereochemical form as a homochiral system (all L-amino acids, sample A) and as a heterochiral system with D configuration at one of the stereogenic centers of Phe (sample B). The structure and stereochemistry of both samples were determined by X-ray diffraction studies of single crystals. In DMSO and acetonitrile, sample A exists as an equimolar mixture of two conformers, while only one is monitored for sample B. The conformational space and energetic preferences for possible conformers were calculated using DFT methods. The distinctly different conformational flexibility of the two samples was experimentally proven by Variable Temperature (VT) and 2D EXSY NMR measurements. Both samples were docked to histone deacetylase HDAC8. Cytotoxic studies proved that none of the tested cyclic peptide is toxic.

Ternary alloys with CuZnIn compositions based on the binary CuZn diagram and the modeled ternary system solidus projection were investigated. The as-cast alloys, hot-rolled sheets, and samples annealed at low temperature were examined. It was found that the α-CuZn solution phase, with minor indium additions (1–2% at.), was the primary phase crystallizing during casting and remained stable at low temperatures. The ternary phase with an approximate composition of Cu8(In,Zn)4.5 and a structure analogous to the high-temperature γ-Cu9In4 phase crystallized from the liquid state and remained stable at low temperatures. This behavior results from the stabilization against peritectoidal decomposition by the Zn atoms when substituting In in the structure. A new phase γ*-Cu9(In,Zn)4 with a modified structure was identified, characterized by a reduced unit cell and an altered electronic structure. The hot-rolling process preserves the phase composition and forms a composite-like structure, with the matrix composition of γ* and large ellipsoidal α-CuZn solution particles. On a microscale, the γ* matrix exhibited a specific structure resulting from segregation processes and was composed of micrometer-sized α-CuZn(In) solution particles and nano-sized β-CuZn phase precipitates. Low-temperature annealing intensifies the γ* matrix decomposition through binary phase precipitation.

We report an idea for the synthesis of oligopeptides using a solvent‐free ball milling approach. Our concept is inspired by block play, in which it is possible to construct different objects using segments (blocks) of different sizes and lengths. We prove that by having a library of short peptides and employing the ball mill mechanosynthesis (BMMS) method, peptides can be easily coupled to form different oligopeptides with the desired functional and biological properties. Optimizing the BMMS process we found that the best yields we obtained when TBTU and cesium carbonate were used as reagents. The role of Cs2CO3 in the coupling mechanism was followed on each stage of synthesis by 1H, 13C and 133Cs NMR employing Magic Angle Spinning (MAS) techniques. It was found that cesium carbonate acts not only as a base but is also responsible for the activation of substrates and intermediates. The unique information about the BMMS mechanism is based on the analysis of 2D NMR data. The power of BMMS is proved by the example of different peptide combinations, 2+2, 3+2, 4+2, 5+2 and 4+4. The tetra‐, penta‐, hexa‐, hepta‐ and octapeptides obtained under this project were fully characterized by MS and NMR techniques. [ABSTRACT FROM AUTHOR]

Ternary alloys with CuZnIn compositions based on the binary CuZn diagram and the modeled ternary system solidus projection were investigated. The as-cast alloys, hot-rolled sheets, and samples annealed at low temperature were examined. It was found that the α-CuZn solution phase, with minor indium additions (1–2% at.), was the primary phase crystallizing during casting and remained stable at low temperatures. The ternary phase with an approximate composition of Cu8(In,Zn)4.5 and a structure analogous to the high-temperature γ-Cu9In4 phase crystallized from the liquid state and remained stable at low temperatures. This behavior results from the stabilization against peritectoidal decomposition by the Zn atoms when substituting In in the structure. A new phase γ*-Cu9(In,Zn)4 with a modified structure was identified, characterized by a reduced unit cell and an altered electronic structure. The hot-rolling process preserves the phase composition and forms a composite-like structure, with the matrix composition of γ* and large ellipsoidal α-CuZn solution particles. On a microscale, the γ* matrix exhibited a specific structure resulting from segregation processes and was composed of micrometer-sized α-CuZn(In) solution particles and nano-sized β-CuZn phase precipitates. Low-temperature annealing intensifies the γ* matrix decomposition through binary phase precipitation. [ABSTRACT FROM AUTHOR]

This work aims at assessment of TiO2 as the main layer component for self-cleaning layers in photovoltaic panels. TiO2 (derived from titanium (IV) butoxide or titanium (IV) isopropoxide) without and with silver was examined to find titania suitable microstructure and optical properties. For this purpose silver amounts ranging from 0.1 to 1% were used for 3 separate chemical methods of modification. Microstructure of powders was characterized by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) with X-ray energy dispersion spectroscopy. Three techniques: spin-coating, doctor blade, and spray-coating were used to deposit TiO2 and TiO2–Ag layers on glass and silicon solar cells. The photocatalytic activity of TiO2 and TiO2–Ag were investigated in the presence of methylene blue. Concentration of dye, amount of silver, type of TiO2 with Ag modification and stability over time were analysed towards the best photocatalytic properties. Finally, TiO2 layers which were used to coat a new type of photovoltaic modules had marginal influence on photovoltaic parameters.

The high photodynamic effect of the Newman strain of the S. aureus and of clinical strains of S. aureus MRSA 12673 and E. coli 12519 are observed for new cationic light-activated phenosafranin polyhedral oligomeric silsesquioxane (POSS) conjugates in vitro. Killing of bacteria was achieved at low concentrations of silsesquioxanes (0.38 µM) after light irradiation (λem. max = 522 nm, 10.6 mW/cm2) for 5 min. Water-soluble POSS-photosensitizers are synthesized by chemically coupling a phenosafranin dye (PSF) (3,7-diamino-5-phenylphenazine chloride) to an inorganic silsesquioxane cage activated by attachment of succinic anhydride rings. The chemical structure of conjugates is confirmed by 1H, 13C NMR, HRMS, IR, fluorescence spectroscopy and UV-VIS analyzes. The APDI and daunorubicin (DAU) synergy is investigated for POSSPSFDAU conjugates. Confocal microscopy experiments indicate a site of intracellular accumulation of the POSSPSF, whereas iBuPOSSPSF and POSSPSFDAU accumulate in the cell wall or cell membrane. Results from the TEM study show ruptured S. aureus cells with leaking cytosolic mass and distorted cells of E. coli. Bacterial cells are eradicated by ROS produced upon irradiation of the covalent conjugates that can kill the bacteria by destruction of cellular membranes, intracellular proteins and DNA through the oxidative damage of bacteria.

A simple and inexpensive method for the preparation of porous SiC microspheres is presented. Polysiloxane microspheres derived from polyhydromethylsiloxane (PHMS) cross-linked with divinylbenzene (DVB) were ceramized under conditions leading to the removal of oxygen from the material. The content of free carbon (Cf) in highly crystalline silicon carbide (SiC) particles can be controlled by using various proportions of DVB in the synthesis of the pre-ceramic material. The chemical structure of the ceramic microspheres was studied by elemental analysis for carbon and oxygen, 29Si MAS NMR, 13C MAS NMR, SEM/EDS, XRD and Raman spectroscopies, and their morphology by SEM, nitrogen adsorption and mercury intrusion porosimetries. The gaseous products of the thermal reduction processes formed during ceramization created a porous structure of the microspheres. In the SiC/Cf microspheres, meso/micro pores were formed, while in carbon-free SiC, microspheres macroporosity dominated.

In this paper, the hydrogen sorption properties of casted Ag-Mg alloys were investigated. The obtained alloys were structurally analyzed by X-ray diffraction (XRD) and observed by scanning electron microscopy (SEM). The study was carried out for four alloys from the two-phase region (Mg) + γ′ (AgMg4) with nominal concentrations of 5 wt. %, 10 wt. %, 15 wt. %, and 20 wt. % Ag, four alloys with nominal compositions equivalent to intermetallic phases: AgMg4, AgMg3, AgMg, and Ag3Mg, one alloy from the two-phase region AgMg + Ag3Mg (Ag60Mg40), and one alloy from the two-phase region AgMg + AgMg3 (Ag40Mg60). The hydrogenation process was performed using a Sievert-type sorption analyzer. The hydride decomposition temperature and kinetic properties of the synthesized hydrides were investigated by differential scanning calorimetry (DSC) coupled with thermogravimetric analysis (TGA). Samples with high magnesium content were found to readily absorb significant amounts of hydrogen, while hydrogen absorption was not observed for samples with silver concentrations higher than 50 at. % (AgMg intermetallic phase).

Biodegradable magnesium alloys with Zn, Yb, Ca and Sr additions are potential materials with increased corrosion resistance in physiological fluids that ensure a controlled resorption process in the human body. This article presents the influence of the use of a high cooling rate on the corrosion behavior of Mg60Zn20Yb15.7Ca2.6Sr1.7 alloy proposed for medical applications. The microstructure of the alloy in a form of high-pressure die-casted plates was presented using scanning electron microscopy in the backscattered electrons (BSEs) mode with energy-dispersive X-ray spectrometer (EDX) qualitative analysis of chemical composition. The crystallization mechanism and thermal properties were described on the basis of differential scanning calorimetry (DSC) results. The corrosion behavior of Mg60Zn20Yb15.7Ca2.6Sr1.7 alloy was analyzed by electrochemical studies with open circuit potential (EOCP) measurements and polarization tests. Moreover, light microscopy and X-ray photoelectron spectroscopy were used to characterize the corrosion products formed on the surface of studied samples. On the basis of the results, the influence of the cooling rate on the improvement in the corrosion resistance was proved. The presented studies are novel and important from the point of view of the impact of the technology of biodegradable materials on corrosion products that come into direct contact with the tissue environment.

Conventional administration of drugs is limited by poor water solubility, low permeability, and mediocre targeting. Safe and effective delivery of drugs and therapeutic agents remains a challenge, especially for complex therapies, such as cancer treatment, pain management, heart failure medication, among several others. Thus, delivery systems designed to improve the pharmacokinetics of loaded molecules, and allowing controlled release and target specific delivery, have received considerable attention in recent years. The last two decades have seen a growing interest among scientists and the pharmaceutical industry in mesoporous silica nanoparticles (MSNs) as drug delivery systems (DDS). This interest is due to the unique physicochemical properties, including high loading capacity, excellent biocompatibility, and easy functionalization. In this review, we discuss the current state of the art related to the preparation of drug-loaded MSNs and their analysis, focusing on the newest advancements, and highlighting the advantages and disadvantages of different methods. Finally, we provide a concise outlook for the remaining challenges in the field.

The studied copper droplets suspension in the liquid slag came from the direct-to-blister technology developed in the KGHM - Polska Miedź S.A. plants. A treatment by the stimulators and reagents was performed in the conditions delivered / ensured by the BOLMET S.A., Wiechlice. These conditions were similar to those usually applied to the industrial process. Particularly, this treatment was similar, to some extent, to that known for the electric arc-furnace technology employed in the Smelter and Refinery Plant, Głogów. An effectiveness of the newly developed and patented complex chemical/reagent for the copper removal from slag was tested during the treatment. The effect of the liquid slag stirring on the copper droplets self-cleaning was also analysed. The performed test confirmed the effectiveness of the studied complex reagent in agglomeration, coagulation and sedimentation of the copper droplets.

The aim of this research is to study the role of nanocrystalline TiO2/SnO2 n–n heterojunctions for hydrogen sensing. Nanopowders of pure SnO2, 90 mol % SnO2/10 mol % TiO2, 10 mol % SnO2/90 mol % TiO2 and pure TiO2 have been obtained using flame spray synthesis (FSS). The samples have been characterized by BET, XRD, SEM, HR-TEM, Mössbauer effect and impedance spectroscopy. Gas-sensing experiments have been performed for H2 concentrations of 1–3000 ppm at 200–400 °C. The nanomaterials are well-crystallized, anatase TiO2, rutile TiO2 and cassiterite SnO2 polymorphic forms are present depending on the chemical composition of the powders. The crystallite sizes from XRD peak analysis are within the range of 3–27 nm. Tin exhibits only the oxidation state 4+. The H2 detection threshold for the studied TiO2/SnO2 heterostructures is lower than 1 ppm especially in the case of SnO2-rich samples. The recovery time of SnO2-based heterostructures, despite their large responses over the whole measuring range, is much longer than that of TiO2-rich samples at higher H2 flows. TiO2/SnO2 heterostructures can be intentionally modified for the improved H2 detection within both the small (1–50 ppm) and the large (50–3000 ppm) concentration range. The temperature Tmax at which the semiconducting behavior begins to prevail upon water desorption/oxygen adsorption depends on the TiO2/SnO2 composition. The electrical resistance of sensing materials exhibits a power-law dependence on the H2 partial pressure. This allows us to draw a conclusion about the first step in the gas sensing mechanism related to the adsorption of oxygen ions at the surface of nanomaterials.

The goal of the work was to develop materials dedicated to spine surgery that minimized the potential for infection originating from the transfer of bacteria during long surgeries. The bacteria form biofilms, causing implant loosening, pain and finally, a risk of paralysis for patients. Our strategy focused both on improvement of antibacterial properties against bacteria adhesion and on wear and corrosion resistance of tools for spine surgery. Further, a ~35% decrease in implant and tool dimensions was expected by introducing ultrahigh-strength titanium alloys for less-invasive surgeries. The tested materials, in the form of thin, multi-layered coatings, showed nanocrystalline microstructures. Performed direct-cytotoxicity studies (including lactate dehydrogenase activity measurement) showed that there was a low probability of adverse effects on surrounding SAOS-2 (Homo sapiens bone osteosarcoma) cells. The microbiological studies (e.g., ISO 22196 contact tests) showed that implanting Ag nanoparticles into Ti/TixN coatings inhibited the growth of E. coli and S. aureus cells and reduced their adhesion to the material surface. These findings suggest that Ag-nanoparticles present in implant coatings may potentially minimize infection risk and lower inherent stress.

This paper presents research on the deposition of an indium tin oxide (ITO) layer which may act as a recombination layer in a silicon/perovskite tandem solar cell. ITO was deposited by magnetron sputtering on a highly porous surface of silicon etched by the metal-assisted etching method (MAE) for texturing as nano and microwires. The homogeneity of the ITO layer and the degree of coverage of the silicon wires were assessed using electron microscopy imaging techniques. The quality of the deposited layer was specified, and problems related to both the presence of a porous substrate and the deposition method were determined. The presence of a characteristic structure of the deposited ITO layer resembling a "match" in shape was demonstrated. Due to the specificity of the porous layer of silicon wires, the ITO layer should not exceed 80 nm. Additionally, to avoid differences in ITO thickness at the top and base of the silicon wire, the layer should be no thicker than 40 nm for the given deposition parameters. [ABSTRACT FROM AUTHOR]

This work presents, for the very first time, very promising nitrogen dioxide (NO2) sensing characteristics of SnOx nanolayers obtained by the innovative and unique rheotaxial growth and vacuum oxidation (RGVO) processing technique. The NO2 gas sensing experiments were performed using the novel surface photovoltage gas sensing device. The measured detection limit at room temperature (RT) is as low as 10 ppb NO2 in synthetic air, whereas the detection limit calculated on the basis of signal to noise ratio is around 6 ppb NO2. For the complementary study of surface chemistry of RGVO SnOx nanolayers, including nonstoichiometry, presence of carbon contamination and surface bondings, the X-ray photoelectron spectroscopy (XPS) method was applied. The SnOx RGVO samples reveal nonstoichiometry because the relative concentration [O]/[Sn] equals 0.94 for the as deposited sample and increases upon subsequent air exposure and NO2 sensing. Moreover, carbon contamination has been recognized after exposing the RGVO SnOx nanolayers to the air and during the NO2 detection.

Within this work the advantages of Rheotaxial Growth and Vacuum Oxidation i.e. maximalextension of internal surfaces, small degree of nanograins [...]

The surface chemistry and the morphology of SnO2 nanowires of average length and diameter of several µm and around 100 nm, respectively, deposited by vapor phase deposition (VPD) method on Au-covered Si substrate, were studied before and after subsequent air exposure. For this purpose, surface-sensitive methods, including X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and the scanning electron microscopy (SEM), were applied. The studies presented within this paper allowed to determine their surface non-stoichiometry combined with the presence of carbon contaminations, in a good correlation with their surface morphology. The relative concentrations of the main components [O]/[Sn]; [C]/[Sn]; [Au]/[Sn], together with the O–Sn; O–Si bonds, were analyzed. The results of TDS remained in a good agreement with the observations from XPS. Moreover, conclusions obtained for SnO2 nanowires deposited with the use of Au catalyst were compared to the previous obtained for Ag-assisted tin dioxide nanowires. The information obtained within these studies is of a great importance for the potential application of SnO2 nanowires in the field of novel chemical nanosensor devices, since the results can provide an interpretation of how aging effects influence gas sensor dynamic characteristics.

In this paper, the results of detailed X-ray photoelectron spectroscopy (XPS) studies combined with atomic force microscopy (AFM) investigation concerning the local surface chemistry and morphology of nanostructured ZnO thin films are presented. They have been deposited by direct current (DC) reactive magnetron sputtering under variable absolute Ar/O2 flows (in sccm): 3:0.3; 8:0.8; 10:1; 15:1.5; 20:2, and 30:3, respectively. The XPS studies allowed us to obtain the information on: (1) the relative concentrations of main elements related to their surface nonstoichiometry; (2) the existence of undesired C surface contaminations; and (3) the various forms of surface bondings. It was found that only for the nanostructured ZnO thin films, deposited under extremely different conditions, i.e., for Ar/O2 flow ratio equal to 3:0.3 and 30:3 (in sccm), respectively, an evident and the most pronounced difference had been observed. The same was for the case of AFM experiments. What is crucial, our experiments allowed us to find the correlation mainly between the lowest level of C contaminations and the local surface morphology of nanostructured ZnO thin films obtained at the highest Ar/O2 ratio (30:3), for which the densely packaged (agglomerated) nanograins were observed, yielding a smaller surface area for undesired C adsorption. The obtained information can help in understanding the reason of still rather poor gas sensor characteristics of ZnO based nanostructures including the undesired ageing effect, being of a serious barrier for their potential application in the development of novel gas sensor devices.

High pressure die casting (HDPC) allows to produce aluminum parts for car industry of complicated shapes in long series. Dies used in this process must be robust enough to withstand long term injection cycling with liquid aluminum alloys, as otherwise their defects are imprinted on the product making them unacceptable. It is expected that nitriding followed by coating deposition (duplex treatment) should protect them in best way and increase intervals between the cleaning/repairing operations. The present experiment covered investigations of the microstructure of the as nitride and deposited with CrAlN coating as well as its shape after foundry tests. The observations were performed with the scanning and transmission electron microscopy (SEM/TEM) method. They showed that the bottom part of this bi-layer is formed by roughly equi-axed Cr2N crystallites, while the upper one with the fine columnar (CrAl)N crystallites. This bi-layers were matched with a set of 7x nano-layers of CrN/(CrAl)N, while at the coating bottom a CrN buffer layer was placed. The foundry run for up to 19 500 cycles denuded most of coated area exposed to fast liquid flow (40 m/s) but left most of bottom part of the coating in the areas exposed to slower flow (7 m/s). The acquired data indicated that the main weakness of this coating was in its porosity present both at the columnar grain boundaries (upper layer) as well as at the bottom of droplets imbedded in it (both layers). They nucleate cracks propagating perpendicularly and the latter at an angle or even parallel to the substrate. The most crack resistant part of the coating turned-out the bottom layer built of roughly equiaxed fine Cr2N crystallites. Even application of this relatively simple duplex protection in the form of CrAlN coating deposited on the nitride substrate helped to extend the die run in the foundry by more than three times. [ABSTRACT FROM AUTHOR]