Morphology, optical, and photoelectrochemical properties of electrodeposited nanocrystalline ZnO films sensitized with Cd x Zn1−x S nanoparticles

Nanocrystalline ITO/ZnO films formed by porous zinc oxide microplatelets 1–3 μm in size and 100–200 nm in thickness, which consist of 30–50 nm ZnO crystallites, were sensitized to visible light by Cd _x Zn_1?x S nanocrystals deposited using the method of successive ionic layer adsorption and reaction (SILAR). The composition of Cd _x Zn_1?x S nanocrystals as well as the dependence between molar Cd(II) fraction in the films and the ratio of cadmium and zinc nitrate concentrations in solutions used for the SILAR procedure were determined by a combination of electron, Raman, and energy-dispersive X-ray spectroscopies. The photovoltage observed at illumination of the ITO/ZnO/Cd _x Zn_1?x S heterostructures by white light (λ >400 nm) in aqueous Na₂S solution increases with a decrease of Cd(II) content proportionally to an increment in the conduction band potential of the Cd _x Zn_1?x S nanocrystals. The photocurrent density normalized to the light absorbance of the ITO/ZnO/Cd _x Zn_1?x S films increases by a factor of around four when the conduction band potential of Cd _x Zn_1?x S nanocrystals grows by 220 mV as a result of Cd(II) fraction changing from 1.0 to 0.62–0.67. The results show that Cd _x Zn_1?x S solid solutions are more advantageous sensitizers for the short-wavelength part of the sensitivity window of the liquid-junction solar cells (400–450 nm) than conventionally used cadmium sulfide.     

Reactive,nonreactive, and flash spark plasma sintering of Al2O3/SiC composites—A comparative study

The influence of different SPS-based methods, that is, conventional spark plasma sintering (SPS), flash SPS (FSPS), and reactive SPS (RSPS) on the properties of Al₂O₃/SiC composite was investigated. It was shown that the application of preliminary high energy ball milling of the powders significantly enhances the sinterability of the ceramics. It was also demonstrated that FSPS provides unique conditions for rapid, that is, less than a minute, consolidation of refractory ceramics. The Al₂O₃-20 wt% SiC composite produced by FSPS possesses the highest relative density (~99%), fracture toughness (7.5 MPa m^1/2), hardness (20.3 GPa) and wear resistance among all ceramics produced by other SPS-based approaches with dwelling time 10 minutes. The RSPS ceramics hold the highest Young's modulus (390 GPa). Substitution of micron-sized Al₂O₃ particles by nano alumina does not lead to measurable enhancement of the mechanical properties.     

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln³⁺) and 5f-elements (actinides, An³⁺) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln³⁺ and An³⁺ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu³⁺/Am³⁺ model pair cations (SF_Am/Eu) in extraction experiments on a semi-quantitative level.

The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM]³⁺, (H₂O)_nM(NO₃)₃ (n = 3, 4), and LM(NO₃)₃ (M = Eu, Am).

Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln³⁺ and An³⁺ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An³⁺ and Ln³⁺ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation.

Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N′,N′-tetraalkyl diamides (“effect of anomalous aryl strengthening”). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An³⁺/Ln³separation selectivity in the series of dipicolinic acid diamides.     

Free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid onto molten ethylene‐vinyl acetate copolymer

Distinctive features of free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid (TEDA) onto macromolecules of molten ethylene‐vinyl acetate copolymer (EVA) in the course of reactive extrusion have been investigated along with structure, mechanical characteristics, and high‐elastic properties of molten functionalized products (EVA‐g‐TEDA). It is shown that EVA‐g‐TEDA yield depends on both the peroxide initiator concentration and content of vinyl acetate units in the copolymer molecular structure. At functionalization, acid grafting is accompanied by secondary reactions of macromolecular degradation and crosslinking. With a low‐peroxide initiator concentration (0.1 wt %), degradation prevails; with a higher (0.3 wt %) concentration, crosslinking of macromolecules prevails. It is reported that monomers being grafted attach mostly over secondary carbon atoms in the polymer chain. EVA‐g‐TEDA appears to have a less perfect crystal structure with a lower‐melting temperature and crystallinity as against the starting polymer. The functionalized products display enhanced rigidity and lower deformability in comparison with the initial copolymer. Variations in the swelling ratio and melt strength of EVA‐g‐TEDA depend on the course of competing secondary processes of macromolecular degradation and crosslinking. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A model for the compression of a random assembly of carbon nanotubes

A model for calculation of the compression resistance of a random assembly of carbon nanotubes (CNTs) is proposed. The model is based on the theory of geometry and compression of fibrous materials with randomly oriented fibres. It accounts for the orientation distribution and volume fraction of CNTs in the assembly, the bending rigidity of a CNT and its decrease after onset of buckling and for friction and slippage between CNTs. The model also allows for calculation the number of contacts between CNTs in the assembly and of the percolation threshold. The predicted compression resistance is compared with experimental data on compression of “buckydisks” made of CNTs.     

Application of A4F-MALS for the Characterization of Polymers Prepared by Emulsion Polymerization: Comparison of the Molecular Structure of Styrene-Acrylate and Methyl Methacrylate-Acrylate Copolymers

In this paper, organic asymmetric flow field flow fractionation coupled to a multi-angle light scattering detector is presented as a very efficient tool for the characterization of copolymers prepared by emulsion polymerization. The molar mass distribution and the extent of branching of styrene–acrylate copolymers have been compared with corresponding copolymers of methyl methacrylate. It has been found that the presence of acrylate monomer results in the increase of molar mass and formation of branched macromolecules due to intermolecular chain transfer to polymer similarly as in case of methyl methacrylate–acrylate copolymers. However, the effect is far less pronounced.     

Synthesis and Biopharmaceutical Evaluation of Imatinib Analogues Featuring Unusual Structural Motifs

A convenient synthesis of imatinib, a potent inhibitor of ABL1 kinase and widely prescribed drug for the treatment of a variety of leukemias, was devised and applied to the construction of a series of novel imatinib analogues featuring a number of non‐aromatic structural motifs in place of the parent molecule's phenyl moiety. These analogues were subsequently evaluated for their biopharmaceutical properties (e.g., ABL1 kinase inhibitory activity, cytotoxicity). The bicyclo[1.1.1]pentane‐ and cubane‐containing analogues were found to possess higher themodynamic solubility, whereas cubane‐ and cyclohexyl‐containing analogues exhibited the highest inhibitory activity against ABL1 kinase and the most potent cytotoxicity values against cancer cell lines K562 and SUP‐B15. Molecular modeling was employed to rationalize the weak activity of the compounds against ABL1 kinase, and it is likely that the observed cytotoxicity of these agents arises through off‐target effects.     

Autonomous navigation system of near-Earth spacecraft

An autonomous navigation system for near-Earth spacecraft is described; this system allows determination of the satellite orbit and prediction of its motion parameters. Radio navigation measurements of GLONASS and GPS satellite systems are used for this purpose. The autonomous navigation system is designated for operation on near-Earth orbits which do not go beyond the navigation areas of GLONASS and/or GPS and on orbits with large eccentricity whose apocenter is at a distance of 50–70 thousand km from the Earth’s surface. The developed methods and algorithms for orbit determination are based on the application of laws of motion dynamics of a spacecraft directly at processing primary phase measurements of the carrier frequency and code pseudo-range using an extended measurement base. Algorithms for determination of motion parameters of the spacecraft and results of simulation and operation of a model system are presented. The possibility of creation of an onboard autonomous navigation system with precision and reliability higher than those of the ground measuring complex is demonstrated.