Membranes Based on Aminated Graphene Oxide with High Selectivity Toward Organic Substances.

In this work, membranes based on graphene oxide, modified with oleylamine, have been prepared by a simple wet chemistry protocol without the use of complex equipment, elevated temperature, and additional reagents. The membrane material was characterized by a set of physicochemical methods: thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffractometry, and X-ray photoelectron spectroscopy. The prepared membranes are stable in both aqueous and organic media. The membranes have a high flux for organic substances and do not permeate water at room temperature and atmospheric pressure. The selectivity of the membranes toward organic substances increases with their thickness. The highest flux among the tested organic liquids is registered for methanol. The membranes have high selectivity toward ethanol/1-butanol and acetone/1-butanol pairs, which opens up the possibility of separating actual industrial mixtures. The membrane retains 90% of methylene blue from the alcohol solution. Our work expands the possibilities of using modified GO-based membranes in purification and filtration technologies.

A Hyperbranched Polyol Process for Designing and Manufacturing Nontoxic Cobalt Nanocomposite.

A method for the design and synthesis of a metallopolymer composite (CoNP) based on cobalt nanoparticles using the hyperbranched polyol process was developed. It was shown that hyperbranched polyester polyols in a melted state can be both a reducing agent and a stabilizer of metal nanoparticles at the same time. The mechanism of oxidation of hyperbranched polyol was studied using diffuse reflectance IR spectroscopy. The process of oxidation of OH groups in G4-OH started from 90 °C and finished with the oxidation of aldehyde groups. The composition and properties of nanomaterials were determined with FT-IR and UV-Vis spectroscopy, Nanoparticle Tracking Analysis (NTA), thermogravimetric analysis (TG), powder X-ray diffraction (XRD), NMR relaxation, and in vitro biological tests. The cobalt-containing nanocomposite (CoNP) had a high colloidal stability and contained spheroid polymer aggregates with a diameter of 35-50 nm with immobilized cobalt nanoparticles of 5-7 nm. The values of R2 and R1 according to the NMR relaxation method for CoNPs were 6.77 mM·ms-1 × 10-5 and 4.14 mM·ms-1 × 10-5 for, respectively. The ratio R2/R1 = 0.61 defines the cobalt-containing nanocomposite as a T1 contrast agent. The synthesized CoNPs were nonhemotoxic (HC50 > 8 g/mL) multifunctional reagents and exhibited the properties of synthetic modulators of the enzymatic activity of chymosin aspartic proteinase and exhibited antimycotic activity against Aspergillus fumigatus. The results of the study show the unique prospects of the developed two-component method of the hyperbranched polyol process for the creation of colloidal multifunctional metal-polymer nanocomposites for theranostics.

Effect of the Synthetic Approach on the Formation and Magnetic Properties of Iron-Based Nanophase in Branched Polyester Polyol Matrix.

This article shows the success of using the chemical reduction method, the polyol thermolytic process, the sonochemistry method, and the hybrid sonochemistry/polyol process method to design iron-based magnetically active composite nanomaterials in a hyperbranched polyester polyol matrix. Four samples were obtained and characterized by transmission and scanning electron microscopy, infrared spectroscopy and thermogravimetry. In all cases, the hyperbranched polymer is an excellent stabilizer of the iron and iron oxides nanophase. In addition, during the thermolytic process and hybrid method, the branched polyol exhibits the properties of a good reducing agent. The use of various approaches to the synthesis of iron nanoparticles in a branched polyester polyol matrix makes it possible to control the composition, geometry, dispersity, and size of the iron-based nanophase and to create new promising materials with colloidal stability, low hemolytic activity, and good magnetic properties. The NMR relaxation method proved the possibility of using the obtained composites as tomographic probes.

Density Functional Theory Approach to the Vibrational Properties and Magnetic Specific Heat of the Covalent Chain Antiferromagnet KFeS2.

Ternary potassium-iron sulfide, KFeS2, belongs to the family of highly anisotropic quasi-one-dimensional antiferromagnets with unusual "anti-Curie-Weiss" susceptibility, quasi-linearly growing with a rising temperature up to 700 K, an almost vanishing magnetic contribution to the specific heat, drastically reduced magnetic moment, etc. While some of the measurements can be satisfactorily described, the deficiency of the entropy changes upon the magnetic transition and the spin state of the iron ion remains a challenge for the further understanding of magnetism. In this work, high-quality single-crystalline samples of KFeS2 were grown by the Bridgman method, and their stoichiometry, crystal structure, and absence of alien magnetic phases were checked, utilizing wave-length dispersive X-ray electron-probe microanalysis, powder X-ray diffraction, and 57Fe Mössbauer spectroscopy, respectively. An ab initio approach was developed to calculate the thermodynamic properties of KFeS2. The element-specific phonon modes and their density of states (PDOS) were calculated applying the density functional theory in the DFT + U version, which explicitly takes into account the on-site Coulomb repulsion U of electrons and their exchange interaction J. The necessary calibration of the frequency scale was carried out by comparison with the experimental iron PDOS derived from the inelastic nuclear scattering experiment. The infrared absorption measurements confirmed the presence of two high-frequency peaks consistent with the calculated PDOS. The calibrated PDOS allowed the calculation of the lattice contribution to the specific heat of KFeS2 by direct summation over the phonon modes without approximations and adjustable parameters. The temperature-dependent magnetic specific heat evaluated by subtraction of the calculated phonon contribution from the experimental specific heat provides a lower boundary for estimating the reduced spin state of the iron ion.

Nd3+, Yb3+:YF3 Optical Temperature Nanosensors Operating in the Biological Windows.

This work is devoted to the study of thermometric performances of Nd3+ (0.1 or 0.5 mol.%), Yb3+ (X%):YF3 nanoparticles. Temperature sensitivity of spectral shape is related to the phonon-assisted nature of energy transfer (PAET) between Nd3+ and Yb3+). However, in the case of single-doped Nd3+ (0.1 or 0.5 mol.%):YF3 nanoparticles, luminescence decay time (LDT) of 4F3/2 level of Nd3+ in Nd3+ (0.5 mol.%):YF3 decreases with the temperature decrease. In turn, luminescence decay time in Nd3+ (0.1 mol.%):YF3 sample remains constant. It was proposed, that at 0.5 mol.% the cross-relaxation (CR) between Nd3+ ions takes place in contradistinction from 0.1 mol.% Nd3+ concentration. The decrease of LDT with temperature is explained by the decrease of distances between Nd3+ with temperature that leads to the increase of cross-relaxation efficiency. It was suggested, that the presence of both CR and PAET processes in the studied system (Nd3+ (0.5 mol.%), Yb3+ (X%):YF3) nanoparticles provides higher temperature sensitivity compared to the systems having one process (Nd3+ (0.1 mol.%), Yb3+ (X%):YF3). The experimental results confirmed this suggestion. The maximum relative temperature sensitivity was 0.9%·K-1 at 80 K.

Advances in the Study of Gas Hydrates by Dielectric Spectroscopy.

The influence of kinetic hydrate inhibitors on the process of natural gas hydrate nucleation was studied using the method of dielectric spectroscopy. The processes of gas hydrate formation and decomposition were monitored using the temperature dependence of the real component of the dielectric constant ε'(T). Analysis of the relaxation times τ and activation energy ΔE of the dielectric relaxation process revealed the inhibitor was involved in hydrogen bonding and the disruption of the local structures of water molecules.

Epitaxial growth and superconducting properties of thin-film PdFe/VN and VN/PdFe bilayers on MgO(001) substrates.

Single-layer vanadium nitride (VN) and bilayer Pd0.96Fe0.04/VN and VN/Pd0.92Fe0.08 thin-film heterostructures for possible spintronics applications were synthesized on (001)-oriented single-crystalline magnesium oxide (MgO) substrates utilizing a four-chamber ultrahigh vacuum deposition and analysis system. The VN layers were reactively magnetron sputtered from a metallic vanadium target in Ar/N2 plasma, while the Pd1- x Fe x layers were deposited by co-evaporation of metallic Pd and Fe pellets from calibrated effusion cells in a molecular beam epitaxy chamber. The VN stoichiometry and Pd1- x Fe x composition were controlled by X-ray photoelectron spectroscopy. In situ low-energy electron diffraction and ex situ X-ray diffraction show that the 30 nm thick single-layer VN as well as the double-layer VN(30 nm)/Pd0.92Fe0.08(12 nm) and Pd0.96Fe0.04(20 nm)/VN(30 nm) structures have grown cube-on-cube epitaxially. Electric resistance measurements demonstrate a metallic-type temperature dependence for the VN film with a small residual resistivity of 9 µΩ·cm at 10 K, indicating high purity and structural quality of the film. The transition to the superconducting state was observed at 7.7 K for the VN film, at 7.2 K for the Pd0.96Fe0.04/VN structure and at 6.1 K for the VN/Pd0.92Fe0.08 structure with the critical temperature decreasing due to the proximity effect. Contrary to expectations, all transitions were very sharp with the width ranging from 25 mK for the VN film to 50 mK for the VN/Pd0.92Fe0.08 structure. We propose epitaxial single-crystalline thin films of VN and heteroepitaxial Pd1- x Fe x /VN and VN/Pd1- x Fe x (x ≤ 0.08) structures grown on MgO(001) as the materials of a choice for the improvement of superconducting magnetic random access memory characteristics.

Synthesis, Characterization, and Magnetoresistive Properties of the Epitaxial Pd0.96Fe0.04/VN/Pd0.92Fe0.08 Superconducting Spin-Valve Heterostructure.

A thin-film superconductor(S)/ferromagnet(F) F1/S/F2-type Pd0.96Fe0.04(20 nm)/VN(30 nm)/Pd0.92Fe0.08(12 nm) heteroepitaxial structure was synthesized on (001)-oriented single-crystal MgO substrate utilizing a combination of the reactive magnetron sputtering and the molecular-beam epitaxy techniques in ultrahigh vacuum conditions. The reference VN film, Pd0.96Fe0.04/VN, and VN/Pd0.92Fe0.08 bilayers were grown in one run with the target sample. In-situ low-energy electron diffraction and ex-situ X-ray diffraction investigations approved that all the Pd1-xFex and VN layers in the series grew epitaxial in a cube-on-cube mode. Electric resistance measurements demonstrated sharp transitions to the superconducting state with the critical temperature reducing gradually from 7.7 to 5.4 K in the sequence of the VN film, Pd0.96Fe0.04/VN, VN/Pd0.92Fe0.08, and Pd0.96Fe0.04/VN/Pd0.92Fe0.08 heterostructures due to the superconductor/ferromagnet proximity effect. Transition width increased in the same sequence from 21 to 40 mK. Magnetoresistance studies of the trilayer Pd0.96Fe0.04/VN/Pd0.92Fe0.08 sample revealed a superconducting spin-valve effect upon switching between the parallel and antiparallel magnetic configurations, and anomalies associated with the magnetic moment reversals of the ferromagnetic Pd0.92Fe0.08 and Pd0.96Fe0.04 alloy layers. The moderate critical temperature suppression and manifestations of superconducting spin-valve properties make this kind of material promising for superconducting spintronics applications.

γ-Iron Phase Stabilized at Room Temperature by Thermally Processed Graphene Oxide.

Stabilizing nanoparticles on surfaces, such as graphene, is a growing field of research. Thereby, iron particle stabilization on carbon materials is attractive and finds applications in charge-storage devices, catalysis, and others. In this work, we describe the discovery of iron nanoparticles with the face-centered cubic structure that was postulated not to exist at ambient conditions. In bulk, the γ-iron phase is formed only above 917 °C, and transforms back to the thermodynamically favored α-phase upon cooling. Here, with X-ray diffraction and Mössbauer spectroscopy we unambiguously demonstrate the unexpected room-temperature stability of the γ-phase of iron in the form of the austenitic nanoparticles with low carbon content from 0.60% through 0.93%. The nanoparticles have controllable diameter range from 30 nm through 200 nm. They are stabilized by a layer of Fe/C solid solution on the surface, serving as the buffer controlling carbon content in the core, and by a few-layer graphene as an outermost shell.

Revisiting the Mechanism of Oxidative Unzipping of Multiwall Carbon Nanotubes to Graphene Nanoribbons.

Unzipping multiwall carbon nanotubes (MWCNTs) attracted great interest as a method for producing graphene nanoribbons (GNRs). However, depending on the production method, the GNRs have been proposed to form by different mechanisms. Here, we demonstrate that the oxidative unzipping of MWCNTs is intercalation-driven, not oxidative chemical-bond cleavage as was formerly proposed. The unzipping mechanism involves three consecutive steps: intercalation-unzipping, oxidation, and exfoliation. The reaction can be terminated at any of these three steps. We demonstrate that even in highly oxidative media one can obtain nonoxidized GNR products. The understanding of the actual unzipping mechanism lets us produce GNRs with hybrid properties varying from nonoxidized through heavily oxidized materials. We answer several questions such as the reason for the innermost walls of the nanotubes remaining zipped. The intercalation-driven reaction mechanism provides a rationale for the difficulty in unzipping single-wall and few-wall CNTs and aids in a reevaluation of the data from the oxidative unzipping process.

Angstrom-scale probing of paramagnetic centers location in nanodiamonds by 3He NMR at low temperatures.

In this article a method to assess the location of paramagnetic centers in nanodiamonds was proposed. The nuclear magnetic relaxation of adsorbed 3He used as a probe in this method was studied at temperatures of 1.5-4.2 K and magnetic fields of 100-600 mT. A strong influence of the paramagnetic centers of the sample on the 3He nuclear spin relaxation time T1 was found. Preplating the nanodiamond surface with adsorbed nitrogen layers allowed us to vary the distance from 3He nuclei to paramagnetic centers in a controlled way and to determine their location using a simple model. The observed T1 minima in temperature dependences are well described within the frame of the suggested model and consistent with the concentration of paramagnetic centers determined by electron paramagnetic resonance. The average distance found from the paramagnetic centers to the nanodiamond surface (0.5 ± 0.1 nm) confirms the well-known statement that paramagnetic centers in this type of nanodiamond are located in the carbon shell. The proposed method can be applied to detailed studies of nano-materials at low temperatures.