Temperature Evolution of Composition, Thermal, Electrical and Magnetic Properties of Ti3C2Tx-MXene.

MXenes are a family of two-dimensional nanomaterials. Titanium carbide MXene (Ti3C2Tx-MXene), reported in 2011, is the first inorganic compound reported among the MXene family. In the present work, we report on the study of the composition and various physical properties of Ti3C2Tx-MXene nanomaterial, as well as their temperature evolution, to consider MXenes for space applications. X-ray diffraction, thermal analysis and mass spectroscopy measurements confirmed the structure and terminating groups of the MXene surface, revealing a predominant single OH layer character. The temperature dependence of the specific heat shows a Debye-like character in the measured range of 2 K-300 K with a linear part below 10 K, characteristic of conduction electrons of metallic materials. The electron density of states (DOS) calculations for Ti3C2OH-MXene reveal a significant DOS value at the Fermi level, with a large slope, confirming its metallic character, which is consistent with the experimental findings. The temperature dependence of electrical resistivity of the MXene samples was tested for a wide temperature range (3 K-350 K) and shows a decrease on lowering temperature with an upturn at low temperatures, where negative magnetoresistance is observed. The magnetoresistance versus field is approximately linear and increases its magnitude with decreasing temperature. The magnetization curves are straight lines with temperature-independent positive slopes, indicating Pauli paramagnetism due to conduction electrons.

Effects of Ni/Co doping on structural and electronic properties of 122 and 112 families of Eu based iron pnictides.

Superconductivity in high-temperature superconductors such as cuprates or iron pnictides is typically achieved by hole or electron doping and it is of great interest to understand how doping affects their properties leading to superconductivity. To study it we conducted Fe and As K edge x-ray absorption spectroscopy measurements on several electron doped compounds from the 112 and 122 family of Eu-based iron pnictides. XANES and EXAFS results confirm that dopants are located at expected sites. For both families we found an electron charge redistribution between As and Fe occurring with doping. The changes it caused are stronger in the 112 family and they are bigger at As sites, which indicates that doped charges are predominantly localized on the dopant site. However, the results obtained do not provide clues why Ni doping in 122 family does not lead to occurrence of superconductivity.

Carbon Dots/Iron Oxide Nanoparticles with Tuneable Composition and Properties.

We present a simple strategy to generate a family of carbon dots/iron oxide nanoparticles (C/Fe-NPs) that relies on the thermal decomposition of iron (III) acetylacetonate in the presence of a highly fluorescent carbon-rich precursor (derived via thermal treatment of ethanolamine and citric acid at 180 °C), while polyethylene glycol serves as the passivation agent. By varying the molar ratio of the reactants, a series of C/Fe-NPs have been synthesized with tuneable elemental composition in terms of C, H, O, N and Fe. The quantum yield is enhanced from 6 to 9% as the carbon content increases from 27 to 36 wt%, while the room temperature saturation magnetization is improved from 4.1 to 17.7 emu/g as the iron content is enriched from 17 to 31 wt%. In addition, the C/Fe-NPs show excellent antimicrobial properties, minimal cytotoxicity and demonstrate promising bioimaging capabilities, thus showing great potential for the development of advanced diagnostic tools.

Selenium-Containing Exopolysaccharides Isolated from the Culture Medium of Lentinula edodes: Structure and Biological Activity.

In continuation of our research on the influence of selenium incorporation on the biosynthesis, structure, and immunomodulatory and antioxidant activities of polysaccharides of fungal origin, we have isolated from a post-culture medium of Lentinula edodes a selenium (Se)-containing exopolysaccharide fraction composed mainly of a highly branched 1-6-α-mannoprotein of molecular weight 4.5 × 106 Da, with 15% protein component. The structure of this fraction resembled mannoproteins isolated from yeast and other mushroom cultures, but it was characterized by a significantly higher molecular weight. X-ray absorption fine structure spectral analysis in the near edge region (XANES) suggested that selenium in the Se-exopolysaccharide structure was present mainly at the IV oxidation state. The simulation analysis in the EXAFS region suggested the presence of two oxygen atoms in the region surrounding the selenium. On the grounds of our previous studies, we hypothesized that selenium-enriched exopolysaccharides would possess higher biological activity than the non-Se-enriched reference fraction. To perform structure-activity studies, we conducted the same tests of biological activity as for previously obtained mycelial Se-polyglucans. The Se-enriched exopolysaccharide fraction significantly enhanced cell viability when incubated with normal (human umbilical vein endothelial cells (HUVEC)) cells (but this effect was absent for malignant human cervical HeLa cells) and this fraction also protected the cells from oxidative stress conditions. The results of tests on the proliferation of human peripheral blood mononuclear cells suggested a selective immunosuppressive activity, like previously tested Se-polyglucans isolated from L. edodes mycelium. The Se-exopolysaccharide fraction, in concentrations of 10-100 µg/mL, inhibited human T lymphocyte proliferation induced by mitogens, without significant effects on B lymphocytes. As with previously obtained Se-polyglucans, in the currently tested Se-polymannans, the selenium content increased the biological activity. However, the activity of selenium exopolysaccharides in all tests was significantly lower than that of previously tested mycelial isolates, most likely due to a different mode of selenium binding and its higher degree of oxidation.

Magnetic Properties of Collagen-Chitosan Hybrid Materials with Immobilized Superparamagnetic Iron Oxide Nanoparticles (SPIONs).

The paper presents results of our studies on hybrid materials based on polymers of natural origin containing superparamagnetic iron oxide nanoparticles (SPIONs). Such nanoparticles, coated with the chitosan derivative, were immobilized in a chitosan-collagen hydrogel matrix by crosslinking with genipin. Three types of biopolymer matrices of different collagen-to-chitosan ratios were studied. A thorough magnetic characterization was performed, including magnetic susceptibility, magnetization, and hysteresis loop measurements in a temperature range of 4 K to 300 K and a magnetic field induction up to 8 Tesla. The effect of SPION immobilization and material composition on the magnetic properties of the hybrids was investigated. The results showed that hybrid materials with covalently bounded SPIONs preserved the superparamagnetic character of SPIONs and exhibited promising magnetic properties, which are important for their potential applications.

Specific Binding of Novel SPION-Based System Bearing Anti-N-Cadherin Antibodies to Prostate Tumor Cells.

PURPOSE: Epithelial-mesenchymal (EMT) transition plays an important role in metastasis and is accompanied by an upregulation of N-cadherin expression. A new nanoparticulate system (SPION/CCh/N-cad) based on superparamagnetic iron oxide nanoparticles, stabilized with a cationic derivative of chitosan and surface-modified with anti-N-cadherin antibody, was synthetized for the effective capture of N-cadherin expressing circulating tumor cells (CTC). METHODS: The morphology, physicochemical, and magnetic properties of the system were evaluated using dynamic light scattering (DLS), fluorescence spectroscopy, Mössbauer spectroscopy, magnetometry, and fluorescence spectroscopy. Atomic force microscopy (AFM), confocal microscopy and flow cytometry were used to study the interaction of our nanoparticulate system with N-cadherin expressed in prostate cancer cell lines (PC-3 and DU 145). A purpose-built cuvette was used in the cancer cell capture experiments. RESULTS: The obtained nanoparticles were a spherical, stable colloid, and exhibited excellent magnetic properties. Biological experiments confirmed that the novel SPION/CCh/N-cad system interacts specifically with N-cadherin present on the cell surface. Preliminary studies on the magnetic capture of PC-3 cells using the obtained nanoparticles were successful. Incubation times as short as 1 minute were sufficient for the synthesized system to effectively bind to the PC-3 cells. CONCLUSION: Results obtained for our system suggest a possibility of using it to capture CTC in the flow conditions.

Structure, Morphology, Heat Capacity, and Electrical Transport Properties of Ti3(Al,Si)C2 Materials.

A study of Ti3Al1-xSixC2 (x = 0 to x = 1) MAX-phase alloys is reported. The materials were obtained from mixtures of Ti3AlC2 and Ti3SiC2 powders with hot pressing sintering technique. They were characterised with X-ray diffraction, heat capacity, electrical resistivity, and magnetoresistance measurements. The results show a good quality crystal structure and metallic properties with high residual resistivity. The resistivity weakly varies with Si doping and shows a small, positive magnetoresistance effect. The magnetoresistance exhibits a quadratic dependence on the magnetic field, which indicates a dominant contribution from open electronic orbits. The Debye temperatures and Sommerfeld coefficient values derived from specific heat data show slight variations with Si content, with decreasing tendency for the former and an increase for the latter. Experimental results were supported by band structure calculations whose results are consistent with the experiment concerning specific heat, resistivity, and magnetoresistance measurements. In particular, they reveal that of the s-electrons at the Fermi level, those of Al and Si have prevailing density of states and, thus predominantly contribute to the metallic conductivity. This also shows that the high residual resistivity of the materials studied is an intrinsic effect, not due to defects of the crystal structure.

High-Entropy Perovskites as Multifunctional Metal Oxide Semiconductors: Synthesis and Characterization of (Gd0.2Nd0.2La0.2Sm0.2Y0.2)CoO3.

Single-phase multicomponent perovskite-type cobalt oxide containing five cations in equiatomic amounts on the A-site, namely, (Gd0.2Nd0.2La0.2Sm0.2Y0.2)CoO3, has been synthesized via the modified coprecipitation hydrothermal method. Using an original approach for heat treatment, which comprises quenching utilizing liquid nitrogen as a cooling medium, a single-phase ceramic with high configuration entropy, crystallizing in an orthorhombic distorted structure was obtained. It reveals the anomalous temperature dependence of the lattice expansion with two weak transitions at approx. 80 and 240 K that are assigned to gradual crossover from the low- via intermediate- to high-spin state of Co3+. The compound exhibits weak ferromagnetism at T ≤ 10 K and signatures of antiferromagnetic correlations in the paramagnetic phase. Ab initio calculations predict a band gap Δ = 1.18 eV in the ground-state electronic structure with the dominant contribution of O_p and Co_d orbitals in the valence and conduction bands, respectively. Electronic transport measurements confirm the negative temperature coefficient of resistivity characteristic to a semiconducting material and reveal a sudden drop in activation energy at T ∼ 240 K from E a ∼ 1 eV in the low-temperature phase to E a ∼ 0.3 eV at room temperature. The possibility of fine tuning of the semiconducting band gap via a subtle change in A-site stoichiometry is discussed.

Hydrophobically Coated Superparamagnetic Iron Oxides Nanoparticles Incorporated into Polymer-Based Nanocapsules Dispersed in Water.

This paper reports the characterization of iron oxide magnetic nanoparticles obtained via the thermal decomposition of an organometallic precursor, which were then loaded into nanocapsules prepared via the emulsification process in the presence of an amphiphilic derivative of chitosan. The applied synthetic method led to the formation of a hydrophobic layer on the surface of nanoparticles that enabled their loading in the hydrophobic liquid inside of the polymer-based capsules. The average diameter of nanoparticles was determined to be equal to 15 nm, and they were thoroughly characterized using X-ray diffraction (XRD), magnetometry, and Mössbauer spectroscopy. A core-shell structure consisting of a wüstite core and maghemite-like shell was revealed, resulting in an exchange bias effect and a considerable magnetocrystalline anisotropy at low temperatures and a superparamagnetic behavior at room temperature. Importantly, superparamagnetic behavior was observed for the aqueous dispersion of the nanocapsules loaded with the superparamagnetic nanoparticles, and the dispersion was shown to be very stable (at least 48 weeks). The results were analyzed and discussed with respect to the potential future applications of these nanoparticles and nanocapsules based on biopolymers as platforms designed for the magnetically navigated transport of encapsulated hydrophobic substances.

Dynamics of Superparamagnetic Iron Oxide Nanoparticles with Various Polymeric Coatings.

In this article, the results of a study of the magnetic dynamics of superparamagnetic iron oxide nanoparticles (SPIONs) with chitosan and polyethylene glycol (PEG) coatings are reported. The materials were prepared by the co-precipitation method and characterized by X-ray diffraction, dynamic light scattering and scanning transmission electron microscopy. It was shown that the cores contain maghemite, and their hydrodynamic diameters vary from 49 nm for PEG-coated to 200 nm for chitosan-coated particles. The magnetic dynamics of the nanoparticles in terms of the function of temperature was studied with magnetic susceptometry and Mössbauer spectroscopy. Their superparamagnetic fluctuations frequencies, determined from the fits of Mössbauer spectra, range from tens to hundreds of megahertz at room temperature and mostly decrease in the applied magnetic field. For water suspensions of nanoparticles, maxima are observed in the absorption part of magnetic susceptibility and they shift to higher temperatures with increasing excitation frequency. A step-like decrease of the susceptibility occurs at freezing, and from that, the Brown's and Néel's contributions are extracted and compared for nanoparticles differing in core sizes and types of coating. The results are analyzed and discussed with respect to the tailoring of the dynamic properties of these nanoparticle materials for requirements related to the characteristic frequency ranges of MRI and electromagnetic field hyperthermia.

Magnetically Navigated Core-Shell Polymer Capsules as Nanoreactors Loadable at the Oil/Water Interface.

Polymer core-shell nanocapsules with magnetic nanoparticles embedded in their oil cores were fabricated and applied as nano(photo)reactors. Superparamagnetic iron oxide nanoparticles (SPIONs) coated with oleic acid were first synthesized and characterized structurally, and their magnetic properties were determined. The capsules with chitosan-based shells were then formed in a one-step process by sonication-assisted mixing of (1) an aqueous solution of the hydrophobically derived chitosan and (2) oleic acid containing the dispersed SPIONs. In this way, magnetic capsules with a diameter of approximately 500-600 nm containing encapsulated SPIONs with an average diameter of approximately 20-30 nm were formed as revealed by dynamic light scattering and scanning transmission electron microscopy measurements. The composition and magnetic properties of the formed capsules were also followed using dynamic light scattering, electron microscopies, and magnetic force microscopy. The water-dispersible capsules, thanks to their magnetic properties, were then navigated in a static magnetic field gradient and transferred between the water and oil phases, as evidenced by fluorescence microscopy. In this way, the capsules could be loaded in a controlled way with a hydrophobic reactant, perylene, which was later photooxidized upon transferring the capsules to the aqueous phase. The capsules were shown to serve as robust reloadable nanoreactors/nanocontainers that via magnetic navigation can be transferred between immiscible phases without disruption. These features make them promising reusable systems not only for loading and carrying lipophilic actives, conducting useful reactions in the confined environment of the capsules, but also for magnetically separating and guiding the encapsulated active molecules to the site of action.

Selenized polysaccharides - Biosynthesis and structural analysis.

The main objective of our research was to analyze the structure of the Se-containing polysaccharides and to examine how the selenium is bound to the polysaccharide molecule. During investigation of the biosynthesis of new immunomodulators, we isolated a selenium (Se)-containing polysaccharide-protein fraction containing proteoglycans of molecular weights of 3.9 × 106 Da and 2.6 × 105 Da, composed of glucose or mannose, nearly 8% of protein and 190 µg Se/g dry weight. X-ray absorption spectroscopy (XAS) data analysis in the near edge region (XANES) confirmed that selenium in the Se-polysaccharides structure is present at the -II oxidation state and that Se is organically bound. The simulation analysis in the EXAFS (extended X-ray absorption fine structure) region suggested that selenium is most likely bound by a glycosidic-link in a ß-1,3 or α-1,4-glycosidic bond or substituted for oxygen in a pyranosidic ring. Calculations performed with Gaussian 03 software predicted deformations in the polysaccharide structure caused by the incorporation of the selenium atom including change in bond lengths and torsion angles and, as a result, disappearance of hydrogen bonds in the vicinity of the selenium atoms.

T1-T2 Dual-modal MRI contrast agents based on superparamagnetic iron oxide nanoparticles with surface attached gadolinium complexes.

Dual-mode MRI contrast agents consisting of superparamagnetic iron oxide nanoparticle (SPION) cores and gadolinium ions associated with the ionic chitosan protecting layer were synthesized and studied. Gadolinium ions were introduced into the coating layer via direct complex formation on the nanoparticles surface, covalent attachment or electrostatically driven deposition of the preformed Gd complex. The modified SPIONs having hydrodynamic diameters ca. 100 nm form stable, well-defined dispersions in water and have excellent magnetic properties. Physiochemical properties of those new materials were characterized using e.g., FTIR spectroscopy, dynamic light scattering, X-ray fluorescence, TEM, and vibrating sample magnetometry. They behave as superparamagnetics and shorten both T1 and T2 proton relaxation times, thus influencing both r1 and r2 relaxivity values that reach 53.7 and 375.5 mM-1 s-1, respectively, at 15 MHz. The obtained materials can be considered as highly effective contrast agents for low-field MRI, particularly useful at permanent magnet-based scanners.