Influence of Zirconium on the Microstructure, Selected Mechanical Properties, and Corrosion Resistance of Ti20Ta20Nb20(HfMo)20-xZrx High-Entropy Alloys.

The presented work considers the influence of the hafnium and molybdenum to zirconium ratio of Ti20Ta20Nb20(HfMo)20-xZrx (where x = 0, 5, 10, 15, 20 at.%) high-entropy alloys in an as-cast state for potential biomedical applications. The current research continues with our previous results of hafnium's and molybdenum's influence on a similar chemical composition. In the presented study, the microstructure, selected mechanical properties, and corrosion resistance were investigated. The phase formation thermodynamical calculations were also applied to predict solid solution formation after solidification. The calculations predicted the presence of multi-phase, body-centred cubic phases, confirmed using X-ray diffraction and scanning electron microscopy. The chemical composition analysis showed the segregation of alloying elements. Microhardness measurements revealed a decrease in microhardness with increased zirconium content in the studied alloys. The corrosion resistance was determined in Ringer's solution to be higher than that of commercially applied biomaterials. The comparison of the obtained results with previously reported data is also presented and discussed in the presented study.

White light and near-infrared emissions of Pr3+ ions in SiO2-LaF3 sol-gel nano-glass-ceramics.

In this work, we report the results of our investigations on the structural and luminescence properties of SiO2-LaF3:Pr3+ nano-glass-ceramics synthesized using the sol-gel method. Based on XRD, microscopic (TEM), and ATR-IR measurements, the crystallization of LaF3 nanocrystals favorably occupied by Pr3+ ions and overall transformations within the silicate sol-gel hosts dependent on heat-treatment conditions of the as-prepared amorphous xerogels were characterized. The fabricated oxyfluoride nano-glass-ceramics revealed the emissions within the greenish-blue (3P0,1 → 3H4, 3P0,1 → 3H5), reddish-orange (3P0,1 → 3H6, 1D2 → 3H4, 3P0 → 3F2,3), and NIR spectral scopes (1D2 → 3F4,1G4, 1G4 → 3H5, 3F3,4 → 3H4). Based on the luminescence spectra in the VIS range, the CIE chromaticity coordinates, correlated color temperatures (CCT), and color purities (CP) were calculated. The obtained results clearly indicate that the prepared Pr3+-doped sol-gel nano-glass-ceramics exhibit warm or neutral white light emissions with CCT values in the range from 2567 K to 3962 K. The lowest CP value was estimated at 12.8%, indicating that the fabricated samples are able to emit bright white light. Additionally, the NIR emissions cover E, S, C, and L bands, which are important for devices applicable in telecommunication technologies. For further characterization, the τ(3P0) and τ(1D2) decay times were estimated. It was established that the emissions from the 3P0 and the 1D2 excited states of Pr3+ ions, as well as the participation of cross-relaxation (CR) processes, are dependent on the size of crystallized LaF3 phase, distribution of optically active Pr3+ ions between amorphous and crystalline phase (determining the Pr3+-Pr3+ inter-ionic distances), and relative content of OH groups in the prepared sol-gel hosts.

Biological Activity and Thrombogenic Properties of Oxide Nanotubes on the Ti-13Nb-13Zr Biomedical Alloy.

The success of implant treatment is dependent on the osseointegration of the implant. The main goal of this work was to improve the biofunctionality of the Ti-13Nb-13Zr implant alloy by the production of oxide nanotubes (ONTs) layers for better anchoring in the bone and use as an intelligent carrier in drug delivery systems. Anodization of the Ti-13Nb-13Zr alloy was carried out in 0.5% HF, 1 M (NH4)2SO4 + 2% NH4F, and 1 M ethylene glycol + 4 wt.% NH4F electrolytes. Physicochemical characteristics of ONTs were performed by high-resolution electron microscopy (HREM), X-ray photoelectron spectroscopy (XPS), and scanning Kelvin probe (SKP). Water contact angle studies were conducted using the sitting airdrop method. In vitro biological properties and release kinetics of ibuprofen were investigated. The results of TEM and XPS studies confirmed the formation of the single-walled ONTs of three generations on the bi-phase (α + ß) Ti-13Nb-13Zr alloy. The ONTs were composed of oxides of the alloying elements. The proposed surface modification method ensured good hemolytic properties, no cytotoxity for L-929 mouse cells, good adhesion, increased surface wettability, and improved athrombogenic properties of the Ti-13Nb-13Zr alloy. Nanotubular surfaces allowed ibuprofen to be released from the polymer matrix according to the Gallagher-Corrigan model.

Synthesis and photoluminescent characterization of ceramic phosphors Li2MgGeO4:Ln3+ (Ln3+ = Pr3+ or Tm3+) under different excitation wavelengths.

In the current work, germanate phosphors Li2MgGeO4:Ln3+ (Ln = Pr, Tm) have been synthesized and then investigated using luminescence spectroscopy. The X-ray diffraction analysis demonstrate that ceramic compounds Li2MgGeO4 containing Pr3+ and Tm3+ ions crystallize in a monoclinic crystal lattice. Luminescence properties of Pr3+ and Tm3+ ions have been examined under different excitation wavelengths. The most intense blue emission band related to the 1D2 → 3F4 transition of Tm3+ is overlaps well with broad band located near 500 nm, which is assigned to F-type centers. These effects are not evident for Pr3+ ions. Ceramic phosphors Li2MgGeO4:Ln3+ (Ln = Pr, Tm) are characterized based on measurements of the excitation/emission spectra and their decays. The experimental results indicate that germanate ceramics Li2MgGeO4 doped with trivalent rare earth ions can be applied as inorganic phosphors emitting orange (Pr3+) or blue (Tm3+) light.

Influence of Hafnium Addition on the Microstructure, Microhardness and Corrosion Resistance of Ti20Ta20Nb20(ZrMo)20-xHfx (where x = 0, 5, 10, 15 and 20 at.%) High Entropy Alloys.

The presented work aimed to investigate the influence of the hafnium/(zirconium and molybdenum) ratio on the microstructure, microhardness and corrosion resistance of Ti20Ta20Nb20(ZrMo)20-xHfx (where x = 0, 5, 10, 15 and 20 at.%) high entropy alloys in an as-cast state produced from elemental powder and obtained via the vacuum arc melting technique. All studied alloys contained only biocompatible elements and were chosen based on the thermodynamical calculations of phase formation predictions after solidification. Thermodynamical calculations predicted the presence of multi-phase, body-centered cubic phases, which were confirmed using X-ray diffraction and scanning electron microscopy. Segregation of alloying elements was recorded using elemental distribution maps. A decrease in microhardness with an increase in hafnium content in the studied alloys was revealed (512-482 HV1). The electrochemical measurements showed that the studied alloys exhibited a high corrosion resistance in a simulated body fluid environment (breakdown potential 4.60-5.50 V vs. SCE).

Influence of Nd Substitution on the Phase Constitution in (Zr,Ce)Fe10Si2 Alloys with the ThMn12 Structure.

Iron-based compounds with a ThMn12-type structure have the potential to bridge the gap between ferrites and high performance Nd2Fe14B magnets. From the point of view of possible applications, the main advantage is their composition, with about 10 wt.% less rare earth elements in comparison with the 2:14:1 phase. On the other hand, the main issue delaying the development of Fe-rich alloys with a ThMn12-type structure is their structural stability. Therefore, various synthesis methods and stabilizing elements have been proposed to stabilize the structure. In this work, the influence of increasing Nd substitution on the phase constitution of Zr0.4-xNdxCe0.6Fe10Si2 (0 ≤ x ≤ 0.3) alloys was analyzed. X-ray diffraction and 57Fe Mössbauer spectrometry were used as the main methods to derive the stability range and destabilization routes of the 1:12 structure. For the arc-melted samples, an increase in the lattice parameters of the ThMn12-type structure was observed with the simultaneous growth of bcc-(Fe,Si) content with increasing Nd substitution. After isothermal annealing, the ThMn12-type structure (and the coexisting bcc-(Fe,Si)) were stable over the whole composition range. While the formation of a 1:12 phase was totally suppressed in the as-cast state for x = 0.3, further heat treatment resulted in the growth of about 45% of the ThMn12-type phase. The results confirmed that the stability range of ThMn12-type structure in the Nd-containing alloys was well improved by other substitutions and the heat treatment, which in turn, is also needed to homogenize the ThMn12-type phase. After further characterization of the magnetic properties and optimization of microstructure, such hard/soft magnetic composites can show their potential by exploiting the exchange spring mechanism.

SbI3·3S8: A Novel Promising Inorganic Adducts Crystal for Second Harmonic Generation.

In the past twenty years, the basic investigation of innovative Non-Linear Optical (NLO) crystals has received significant attention, which has built the crucial heritage for the use of NLO materials. Fundamental research is essential given the scarcity of materials for NLO compounds, especially in the deep ultraviolet (DUV) and middle- and far-infrared (MFIR) regions. In the present work, we synthesized high-quality MFIR SbI3·3S8 NLO crystals having a length in the range of 1-5 mm through rapid facile liquid phase ultrasonic reaction followed by the assistance of instantaneous natural evaporation phenomenon of the solvent at room temperature. X-ray diffraction (XRD) results ratify the hexagonal R3m structure of SbI3·3S8 crystal, and energy-dispersive X-ray spectroscopy (EDX) demonstrates that the elemental composition of SbI3·3S8 crystal is similar to that of its theoretical composition. The direct and indirect forbidden energy gaps of SbI3·3S8 were measured from the optical transmittance spectra and they were shown to be 2.893 eV and 1.986 eV, respectively. The green sparkling signal has been observed from the crystal during the second harmonic generation (SHG) experiment. Therefore, as inorganic adducts are often explored as NLO crystals, this work on the MFIR SbI3·3S8 NLO crystal can bring about additional investigations on this hot topic in the near future.

Crystallization Kinetics and Structure Evolution during Annealing of Ni-Co-Mn-In Powders Obtained by Mechanical Alloying.

The crystallization kinetics and structure evolution during annealing of the Ni45.5Co4.5Mn36.6In13.4 (at. %) powders produced by mechanical alloying (MA) was investigated. After 70 h and 100 h of MA, the powder consisted of a mixture of amorphous and nanocrystalline body-centered cubic (bcc) phases. We observed the relaxation in the as-received powder. The relaxation temperature (Tre) increases logarithmically with the annealing time. Annealing above 440 °C results in (1) ordering of L21, (2) dissolution of the residual Ni and Mn, (3) tetragonal MnNi phase formation and (4) γ phases precipitation. The activation energies of the B2 → L21 and Mn (α-Mn) → MnNi (P4/mmm) transformations were calculated.

The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin.

In this paper, thermal properties, atomic-scale structure, and molecular dynamics (at ambient and high pressure) of native melatonin (MLT) and its partially-deuterated derivative (MLT-d2) have been investigated. Based on infrared spectroscopy, it was shown that treating MLT with D2O causes the replacement of hydrogen atoms attached to the nitrogen by deuterium. The degree of such substitution was very high (> 99%) and the deuterated sample remained stable after exposure to the air as well as during the melting and vitrification processes. Further calorimetric studies revealed the appearance of a peculiar thermal event before the melting of crystalline MLT-d2, which was assigned by the X-ray diffraction to a local negative thermal expansion of the unit cell. Finally, the high-pressure dielectric experiments indicated a few interesting findings, including the variation in the shape of the structural relaxation peak during compression, the difference in the pressure evolution of the glass transition temperature, and the temperature dependence of activation volume for both MLT species. The variations in these parameters manifest a different impact of the compression/densification on the dynamics of hydrogen and deuterium bonds in the native and partially-deuterated MLT, respectively.

In Situ Cellular Localization of Nonfluorescent [60]Fullerene Nanomaterial in MCF-7 Breast Cancer Cells.

Cellular localization of carbon nanomaterials in cancer cells is essential information for better understanding their interaction with biological targets and a crucial factor for further evaluating their biological properties as nanovehicles or nanotherapeutics. Recently, increasing efforts to develop promising fullerene nanotherapeutics for cancer nanotechnology have been made. However, the main challenge regarding studying their cellular effects is the lack of effective methods for their visualization and determining their cellular fate due to the limited fluorescence of buckyball scaffolds. Herein, we developed a method for cellular localization of nonfluorescent and water-soluble fullerene nanomaterials using the in vitro click chemistry approach. First, we synthesized a triple-bonded fullerene probe (TBC60ser), which was further used as a starting material for 1,3-dipolar cycloaddition using 3-azido-7-hydroxycoumarin and sulfo-cyanine5 azide fluorophores to create fluorescent fullerene triazoles. In this work, we characterized the structurally triple-bonded [60]fullerene derivative and confirmed its high symmetry (Th) and the successful formation of fullerene triazoles by spectroscopic techniques (i.e., ultraviolet-visible, fluorescence, and Fourier transform infrared spectroscopies) and mass spectrometry. The created fluorescent fullerene triazoles were successfully localized in the MCF-7 breast cancer cell line using fluorescent microscopy. Overall, our findings demonstrate that TBC60ser localizes in the lysosomes of MCF-7 cells, with only a small affinity to mitochondria.

Synthesis and applications of [60]fullerene nanoconjugate with 5-aminolevulinic acid and its glycoconjugate as drug delivery vehicles.

The 5-aminolevulinic acid (5-ALA) prodrug is widely used in clinical applications, primarily for skin cancer treatments and to visualize brain tumors in neurosurgery. Unfortunately, its applications are limited by unfavorable pharmacological properties, especially low lipophilicity; therefore, efficient nanovehicles are needed. For this purpose, we synthesized and characterized two novel water-soluble fullerene nanomaterials containing 5-ALA and d-glucuronic acid components. Their physicochemical properties were investigated using NMR, XPS, ESI mass spectrometry, as well as TEM and SEM techniques. In addition, HPLC and fluorescence measurements were performed to evaluate the biological activity of the fullerene nanomaterials in 5-ALA delivery and photodynamic therapy (PDT); additional detection of selected mRNA targets was carried out using the qRT-PCR methodology. The cellular response to the [60]fullerene conjugates resulted in increased levels of ABCG2 and PEPT-1 genes, as determined by qRT-PCR analysis. Therefore, we designed a combination PDT approach based on two fullerene materials, C60-ALA and C60-ALA-GA, along with the ABCG2 inhibitor Ko143.

Interfacial Polarization Phenomena in Compressed Nanowires of SbSI.

The systematic studies of the extrinsic Maxwell-Wagner-Sillars polarization process in compressed antimony sulfoiodide (SbSI) nanowires are carried out by dielectric spectroscopy. The dielectric response is studied in temperature (100≤T≤350) K and frequency (10-3≤f≤106) Hz ranges. Dielectric functions commonly used for the analysis of dielectric spectra related to intrinsic polarization processes were applied in the elaboration of experimental data. It was found that the respective "semi-circles" in the Cole-Cole-type plots display a characteristic pear-like shape for the ferroelectric phase. On the other hand, the data for the paraelectric phase form symmetrical arcs. This response is effectively parametrized using the experimental Cole-Davidson and Cole-Cole functions fitted to the data obtained for the ferroelectric and paraelectric phases, respectively. It is deduced that the particular shape of spectra in the ferroelectric phase is due to spontaneous polarization, which is responsible for an asymmetric broadening of relaxation functions related to the interfacial polarization.

Influence of Molybdenum on the Microstructure, Mechanical Properties and Corrosion Resistance of Ti20Ta20Nb20(ZrHf)20-xMox (Where: x = 0, 5, 10, 15, 20) High Entropy Alloys.

The presented work was focused on investigating the influence of the (hafnium and zirconium)/molybdenum ratio on the microstructure and properties of Ti20Ta20Nb20(ZrHf)20-xMox (where: x = 0, 5, 10, 15, 20 at.%) high entropy alloys in an as-cast state. The designed chemical composition was chosen due to possible future biomedical applications. Materials were obtained from elemental powders by vacuum arc melting technique. Phase analysis revealed the presence of dual body-centered cubic phases. X-ray diffraction showed the decrease of lattice parameters of both phases with increasing molybdenum concentration up to 10% of molybdenum and further increase of lattice parameters. The presence of two-phase matrix microstructure and hafnium and zirconium precipitates was proved by scanning and transmission electron microscopy observation. Mechanical property measurements revealed decreased micro- and nanohardness and reduced Young's modulus up to 10% of Mo content, and further increased up to 20% of molybdenum addition. Additionally, corrosion resistance measurements in Ringers' solution confirmed the high biomedical ability of studied alloys due to the presence of stable oxide layers.

Influence of Sandblasting Process on Tribological Properties of Titanium Grade 4 in Artificial Saliva for Dentistry Applications.

Titanium Grade 4 (Ti G4) is widely used in medicine for dental implants. The failure-free life of implants depends on their properties such as resistance to wear and friction processes. This paper presents an analysis of the influence of sandblasting on tribological wear of commercial dental implants made of TiG4 in artificial saliva. Tribological wear measurements were performed in a reciprocating motion in the ball-on-disc system. The scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) method was used to characterize the surface of the implants before and after the tribological wear test. The microhardness of Ti G4 was measured before and after sandblasting by the Vickers method. The contact angle was determined by the method of sitting drop in air. The residual stress test using the X-Ray Diffraction (XRD) single-{hkl} sin2ψ method was carried out. The compressive residual stress of 324(7) MPa and surface hardening of Ti G4 was revealed after sandblasting with Al2O3 particles of 53-75 µm in diameter. It was found that sandblasting changes the surface wettability of Ti G4. The intermediate wettability of the mechanically polished surface and the hydrophobicity of the sandblasted surface was revealed. Sandblasting reduces the tribological wear and friction coefficient of Ti G4 surface in saliva. The three-body abrasion wear mechanism was proposed to explain the tribological wear of Ti G4 in saliva.

High-Energy Ball Milling Conditions in Formation of NiTiCu Shape Memory Alloys.

The properties and the shape memory effect depend, among other things, on chemical composition, as well as the method of shape memory alloy (SMA) production. One of the manufacturing methods that leads to the amorphous/nanocrystalline SMA is high-energy ball milling combined with annealing. Using this technique, an SMA memory alloy, with the nominal chemical composition of Ni25Ti50Cu25, was produced from commercial elemental powders (purity −99.7%). The structure and morphology were characterized (at the various stages of its production) by the use of X-ray diffraction, as well as electron microscopy (both scanning and transmission). Choosing the appropriate grinding time made it possible to produce an NiTiCu alloy with a different crystallite size. Its average size changed from 6.5 nm (after 50 h) to about 2 nm (100 h). Increasing the grinding time up to 140 h resulted in the formation of areas that showed the B19 martensite and the Ti2(Ni,Cu) phase with the average crystallite size of about 6 nm (as milled). After crystallization, the average size increased to 11 nm.

Inhibition of Carotenoid Biosynthesis by CRISPR/Cas9 Triggers Cell Wall Remodelling in Carrot.

Recent data indicate that modifications to carotenoid biosynthesis pathway in plants alter the expression of genes affecting chemical composition of the cell wall. Phytoene synthase (PSY) is a rate limiting factor of carotenoid biosynthesis and it may exhibit species-specific and organ-specific roles determined by the presence of psy paralogous genes, the importance of which often remains unrevealed. Thus, the aim of this work was to elaborate the roles of two psy paralogs in a model system and to reveal biochemical changes in the cell wall of psy knockout mutants. For this purpose, Clustered Regularly Interspaced Short Palindromic Repeats (CRISPR) and CRISPR associated (Cas9) proteins (CRISPR/Cas9) vectors were introduced to carotenoid-rich carrot (Daucus carota) callus cells in order to induce mutations in the psy1 and psy2 genes. Gene sequencing, expression analysis, and carotenoid content analysis revealed that the psy2 gene is critical for carotenoid biosynthesis in this model and its knockout blocks carotenogenesis. The psy2 knockout also decreased the expression of the psy1 paralog. Immunohistochemical staining of the psy2 mutant cells showed altered composition of arabinogalactan proteins, pectins, and extensins in the mutant cell walls. In particular, low-methylesterified pectins were abundantly present in the cell walls of carotenoid-rich callus in contrast to the carotenoid-free psy2 mutant. Transmission electron microscopy revealed altered plastid transition to amyloplasts instead of chromoplasts. The results demonstrate for the first time that the inhibited biosynthesis of carotenoids triggers the cell wall remodelling.

Towards water-soluble [60]fullerenes for the delivery of siRNA in a prostate cancer model.

This paper presents two water-soluble fullerene nanomaterials (HexakisaminoC60 and monoglucosamineC60, which is called here JK39) that were developed and synthesized as non-viral siRNA transfection nanosystems. The developed two-step Bingel-Hirsch reaction enables the chemical modification of the fullerene scaffold with the desired bioactive fragments such as D-glucosamine while keeping the crucial positive charged ethylenediamine based malonate. The ESI-MS and 13C-NMR analyses of JK39 confirmed its high Th symmetry, while X-ray photoelectron spectroscopy revealed the presence of nitrogen and oxygen-containing C-O or C-N bonds. The efficiency of both fullerenes as siRNA vehicles was tested in vitro using the prostate cancer cell line DU145 expressing the GFP protein. The HexakisaminoC60 fullerene was an efficient siRNA transfection agent, and decreased the GFP fluorescence signal significantly in the DU145 cells. Surprisingly, the glycofullerene JK39 was inactive in the transfection experiments, probably due to its high zeta potential and the formation of an extremely stable complex with siRNA.

Correlation between Microstructure and Magnetism in Ball-Milled SmCo5/α-Fe (5%wt. α-Fe) Nanocomposite Magnets.

Magnetic nanocomposites SmCo5/α-Fe were synthesized mechanically by high-energy ball milling (HEBM) from SmCo5 and 5%wt. of α-Fe powders. The X-ray diffraction analysis reveals the hexagonal 1:5 phase as the main one accompanied by the cubic α-Fe phase and 2:17 rhombohedral as the secondary phase. The content of each detected phase is modified throughout the synthesis duration. A significant decrease in crystallite size with a simultaneous increase in lattice straining is observed. A simultaneous gradual reduction in particle size is noted from the microstructural analysis. Magnetic properties reveal non-linear modification of magnetic parameters associated with the strength of the exchange coupling induced by various duration times of mechanical synthesis. The highest value of the maximum energy product (BH)max at room temperature is estimated for samples milled for 1 and 6 h. The intermediate mixed-valence state of Sm ions is confirmed by electronic structure analysis. An increase in the Co magnetic moment versus the milling time is evidenced based on the performed fitting of the Co3s core level lines.

Evaluation of mechanical properties, in vitro corrosion resistance and biocompatibility of Gum Metal in the context of implant applications.

In recent decades, several novel Ti alloys have been developed in order to produce improved alternatives to the conventional alloys used in the biomedical industry such as commercially pure titanium or dual phase (alpha and beta) Ti alloys. Gum Metal with the non-toxic composition Ti-36Nb-2Ta-3Zr-0.3O (wt. %) is a relatively new alloy which belongs to the group of metastable beta Ti alloys. In this work, Gum Metal has been assessed in terms of its mechanical properties, corrosion resistance and cell culture response. The performance of Gum Metal was contrasted with that of Ti-6Al-4V ELI (extra-low interstitial) which is commonly used as a material for implants. The advantageous mechanical characteristics of Gum Metal, e.g. a relatively low Young's modulus (below 70 GPa), high strength (over 1000 MPa) and a large range of reversible deformation, that are important in the context of potential implant applications, were confirmed. Moreover, the results of short- and long-term electrochemical characterization of Gum Metal showed high corrosion resistance in Ringer's solution with varied pH. The corrosion resistance of Gum Metal was best in a weak acid environment. Potentiodynamic polarization studies revealed that Gum Metal is significantly less susceptible to pitting corrosion compared to Ti-6Al-4V ELI. The oxide layer on the Gum Metal surface was stable up to 8.5 V. Prior to cell culture, the surface conditions of the samples, such as nanohardness, roughness and chemical composition, were analyzed. Evaluation of the in vitro biocompatibility of the alloys was performed by cell attachment and spreading analysis after incubation for 48 h. Increased in vitro MC3T3-E1 osteoblast viability and proliferation on the Gum Metal samples was observed. Gum Metal presented excellent properties making it a suitable candidate for biomedical applications.