First principles investigation of protactinium-based oxide-perovskites for flexible opto electronic devices

The structural,elastic,mechanical,electronic,and optical properties of KPaO_3 and RbPaO_3 compounds are investigated from first-principles calculations by using the WIEN2 k code in the frame of local density approximation(LDA) and generalized gradient approximation(GGA).The calculated ground state quantities,such as lattice constant(α_0),ground state energy(E),bulk modulus(S),and their pressure derivative(B_p) are in reasonable agreement with the present analytical and previous theoretical results and available experimental data.Based on several elastic and mechanical parameters,the structural stability,hardness,stiffness and the brittle and ductile behaviors are discussed,which reveal that protactiniumbased oxide series of perovskites is mechanically stable and possesses weak resistance to shear deformation compared with resistance to unidirectional compression while flexible and covalent behaviors are dominated in them.The analysis of band profile through Trans-Blaha modified Becke-Johnson(TB-mBJ) potential highlights the underestimation of bandgap with traditional density functional theory(DFT) approximation.Specific contribution of electronic states is investigated by means of total and partial density of states and it can be evaluated that both compounds are(Γ-Γ) direct bandgap semiconductors.All fundamental optical properties are analyzed while attention is paid to absorption and reflection spectra to explore extensive absorptions and reflections of these compounds in high frequency regions.The present method represents an influential approach to calculating the whole set of elastic,mechanical,and opto-electronic parameters,which would conduce to the understanding of various physical phenomena and empower the device engineers to implement these materials in flexible opto-electronic applications.     

Quantum strategies win in a defector-dominated population

Quantum strategies are introduced into evolutionary games. The agents using quantum strategies are regarded as invaders, whose fraction generally is 1% of a population, in contrast to the 50% of the population that are defectors. In this paper, the evolution of strategies on networks is investigated in a defector-dominated population, when three networks (square lattice, Newman–Watts small-world network, and scale-free network) are constructed and three games (Prisoners’ Dilemma, Snowdrift, and Stag-Hunt) are employed. As far as these three games are concerned, the results show that quantum strategies can always invade the population successfully. Comparing the three networks, we find that the square lattice is most easily invaded by agents that adopt quantum strategies. However, a scale-free network can be invaded by agents adopting quantum strategies only if a hub is occupied by an agent with a quantum strategy or if the fraction of agents with quantum strategies in the population is significant.     

Efficient aerial oxidation of different types of alcohols using ZnO nanoparticle–MnCO3-graphene oxide composites

Graphene–metal nanocomposites have been found to remarkably enhance the catalytic performance of metal nanoparticle-based catalysts. In continuation of our previous report, in which highly reduced graphene oxide (HRG)-based nanocomposites were synthesized and evaluated, we present nanocomposites of graphene oxide (GRO) and ZnO nanoparticle-doped MnCO₃ ([ZnO–MnCO₃/(1%)GRO]) synthesized via a facile, straightforward co-precipitation technique. Interestingly, it was noticed that the incorporation of GRO in the catalytic system could noticeably improve the catalytic efficiency compared to a catalyst (ZnO–MnCO₃) without GRO, for aerial oxidation of benzyl alcohol (BzOH) employing O₂ as a nature-friendly oxidant under base-free conditions. The impacts of various reaction factors were thoroughly explored to optimize reaction conditions using oxidation of BzOH to benzaldehyde (BzH) as a model substrate. The catalysts were characterized using X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, Energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and Raman spectroscopy. The (1%)ZnO–MnCO₃/(1%)GRO exhibited significant specific activity (67 mmol.g⁻¹.hr⁻¹) with full convversion of BzOH and >99% BzH selectivity within just 6 min. The catalytic efficiency of the (1%)ZnO–MnCO₃/(1%)GRO nanocomposite was significantly better than the (1%)ZnO–MnCO₃/(1%)HRG and (1%)ZnO–MnCO₃ catalysts, presumably due to the existence of oxygen-possessing groups on the GRO surface and as well as a very high surface area that could have been instrumental in uniformly dispersing the active sites of the catalyst, i.e., ZnO–MnCO₃. Under optimum circumstances, various kinds of alcohols were selectively transformed to respective carbonyls with full convertibility over the (1%)ZnO–MnCO₃/(1%)GRO catalyst. Furthermore, the highly effective (1%)ZnO–MnCO₃/(1%)GRO catalyst could be successfully reused and recycled over five consecutive runs with a marginal reduction in its performance and selectivity.     

Effect of bication (Cu-Cr) substitution on the structure and electrochemical performance of LiMn2O4 spinel cathodes at low and high current rates

This report describes the detailed structural and electrochemical characterization of a series of low content (0.01 to 0.05) Cu-Cr bi-metal doped LiMn₂O₄ cathode material synthesized by sol–gel method. The structural and morphological features were described using XRD, SEM, TEM, EDAX and FTIR techniques. The electron transfer and its feasibility were discussed through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The charge–discharge studies were performed to evaluate the capacity fading and rate capability. It was found that the electrochemical performance is very much dependent on the amount of Cu-Cr bi-metal doping and interestingly decreased the capacity fading with high cycleability. The sample with the least amount of dopants (i.e., LiCu_0.01Cr_0.01Mn_1.98O₄) demonstrated much improved capacity, cycleability and high rate capability. The LiCu_0.01Cr_0.01Mn_1.98O₄ cathode exhibited a discharge capacity of 112 mA h g^?1 at very first cycle and retained 93 mA h g^?1 after 100 cycles at a C rate of 0.3. Further, the same material at very high current density (5 C) retained 83% of the initial discharge capacity. The Cu-Cr doping stabilized the spinel structure by suppressing the Jahn-Teller distortion effect and Mn dissolution and the resultant material showed the workability of the cathodes for devices which work at substantially high C-rate of 5C.     

Synthesis and performance of a Mono (dodecafluoroheptyl) acetate surfactant

A novel fluorinated surfactant, sodium 1?H, 1?H, 7H-dodecafluoro-1-heptyloxy acetate (DFHAS), was synthesized via a facile two-step synthetic procedure. The structure of product on each step was characterized by ^1?H NMR, ^19?F NMR, ¹³C NMR, FT-IR, and mass spectrum (MS). Ultraviolet absorption (UV) and ring measurements were performed to obtain detailed information of its surface properties. The results demonstrated that the novel surfactant possessed very low critical micelle concentration (CMC, 7.94?mM) and surface tension (20.01?mN/m). Furthermore, the surfactant had preferable thermal stability compared with other perfluorocarboxylates characterized by thermal gravimetric analysis (TGA). The practical application performance of DFHAS was finally validated through the emulsion polymerization of vinylidene fluoride (VDF) by means of its excellent emulsifying activities. It is expected that this versatile synthetic strategy may help fabricate satisfying green surfactant systems for the application in fields of emulsion polymerization, drug delivery and greases.GRAPHICAL ABSTRACT     

Metal contamination in Sunairi Point sediment core along Karachi coast,Pakistan

Journal of Radioanalytical and Nuclear Chemistry - This paper describes the pollution level in sediment core collected from Sunairi Point of Karachi coastal area Pakistan. The sediment was...     

Evaluation of quantum dots applied as switchable layer in a light-controlled electrochemical sensor

Gold electrodes with switchable conductance are created by coating the gold surface with different colloidal quantum dots. For the quantum dot immobilization, a dithiol compound was used. By polarizing the electrode and applying a light pointer, local photocurrents were generated. The performance of this setup was characterized for a variety of different nanoparticle materials regarding drift and signal-to-noise ratio. We varied the following parameters: quantum dot materials and immobilization protocol. The results indicate that the performance of the sensor strongly depends on how the quantum dots are bound to the gold electrode. The best results were obtained by inclusion of an additional polyelectrolyte film, which had been fabricated using layer-by-layer assembly.      

Constructing quantum games from symmetric non-factorizable joint probabilities

We construct quantum games from a table of non-factorizable joint probabilities, coupled with a symmetry constraint, requiring symmetrical payoffs between the players. We give the general result for a Nash equilibrium and payoff relations for a game based on non-factorizable joint probabilities, which embeds the classical game. We study a quantum version of Prisoners' Dilemma, Stag Hunt, and the Chicken game constructed from a given table of non-factorizable joint probabilities to find new outcomes in these games. We show that this approach provides a general framework for both classical and quantum games without recourse to the formalism of quantum mechanics.     

A comparative study of lithium and sodium salts in PAN-based ion conducting polymer electrolytes

The conducting polymer electrolyte films consisting of polyacrylonitrile (PAN) as the host polymer, lithium triflate (LiCF₃SO₃) and sodium triflate (NaCF₃SO₃) as inorganic salts were prepared by the solution-cast technique. The pure PAN film was prepared as a reference. The ionic conductivity for the films is characterized using impedance spectroscopy. The room temperature conductivity for the PAN + 26 wt.% LiCF₃SO₃ film and the PAN + 24 wt.% NaCF₃SO₃ film is 3.04 × 10⁻⁴ S cm⁻¹ and 7.13 × 10⁻⁴ S cm⁻¹, respectively. XRD studies show that the complexation that has occurred in the PAN containing salt films and complexes formed are amorphous. The FTIR spectra results confirmed the complexation has taken place between the salt and the polymer. These results correspond with surface morphology images obtained from SEM analysis. The conductivity–temperature dependence of the highest conducting film from PAN + LiCF₃SO₃ and PAN + NaCF₃SO₃ systems follows Arrhenius equation in the temperature range of 303 to 353 K. The PAN containing 24 wt.% LiCF₃SO₃ film has a higher ionic conductivity and lower activation energy compared to the PAN containing 26 wt.%LiCF₃SO₃ film. These results can be explained based on the Lewis acidity of the alkali ions, i.e., the interaction between Li⁺ ion and the nitrogen atom of PAN is stronger than that of Na⁺ ion.     

Structural determination of prunusins A and B,new C‐alkylated flavonoids from Prunus domestica,by 1D and 2D NMR spectroscopy

Prunusins A (1) and B (2), the new C‐alkylated flavonoids, have been isolated from the seed kernels of Prunus domestica. Their structures were assigned from ¹H and ¹³C nuclear magnetic resonating spectra, DEPT and by correlation spectroscopy, HMQC and HMBC experiments. 3, 5, 7, 4′‐Tetrahydroxyflavone (3) and 3, 5, 7‐trihydroxy‐8, 4′‐dimethoxyflavone (4) have also been reported from this species. Both compounds (1) and (2) showed significant antifungal activity against pathogenic fungus Trichophyton simmi. Copyright © 2009 John Wiley & Sons, Ltd.