Enantioselective phospha-Michael reaction of diethyl phosphonate with exocyclic α,β-unsaturated benzocyclic ketones catalyzed by a dinuclear zinc−AzePhenol catalyst

The dinuclear zinc complexes as high performance catalysts were used to catalyze phospha-Michael reaction of exocyclic α,β-unsaturated benzocyclic ketones under mild conditions, and the desired products possessing 1-indanones or 1-tetralones skeleton were obtained with excellent enantioselectivities of up to 99%/99% ee and yields of up to 99%. The absolute stereochemistry of the major products catalyzed by (R,R)-L1 was determined to be the (R,R)-configuration by X-ray crystallographic analysis of 3d. A positive nonlinear effect was observed and the possible mechanism was proposed.     

Existence of heteroclinic orbits in a novel three-order dynamical system

In this paper,we design a novel three-order autonomous system.Numerical simulations reveal the complex chaotic behaviors of the system.By applying the undetermined coefficient method,we find a heteroclinic orbit in the system.As a result,the Si’lnikov criterion along with some other given conditions guarantees that the system has both Smale horseshoes and chaos of horseshoe type.     

Polymer-dispersed liquid crystal composites for bio-applications: thermotropic,surface and optical properties

Polymer-dispersed liquid crystal (PDLC) systems based on polysulfone as carrying matrix and 4-cyano-4?-pentylbiphenyl (5CB) liquid crystal (LC) were obtained as thin transparent films. The PDLC films were prepared by solvent- and thermally induced phase separation methods, with various compositions in the two components. Information on the phase separation was obtained by polarised light optical microscopy, differential scanning calorimetry and scanning electron microscopy. The PDLC composites show well-defined droplets of submicrometric size, around 650 nm for a medium content of LC and around 250 nm for a low one. The droplets show a radial configuration and a homeotropic alignment of the LC molecules within. By contact angle measurement and surface free energy calculations, it was established that self-assembling of aliphatic units of the two composite components, at droplet interface, is the driving force of the homeotropic alignment. Moreover, these data indicated the potential biocompatibility of the studied composites. The photophysical behaviour shows a better light emission of the PDLCs containing bigger droplets.     

Theoretical Studies on the Mechanistic Insertions of Singlet Methylene and Halomethylene into Polar S‒H Bonds of Methanethiol,Ethanethiol, 1-Propanethiol and 2-Propanethiol

Abstract

The insertion of ¹CH₂, ¹CHF, ¹CF₂,¹CHCl, and ¹CCl₂ into primary and secondary polar S?H bonds of methanethiol, ethanethiol, 1-propanethiol, and 2-propanethiol have been investigated at HF (Hartree–Fock), MP2 (Møller–Plesset Perturbation Theory), and DFT (density functional theory) levels using 6-31G (d, p) basis set. The insertions follow a two-step mechanism. The potential energy surface exploration identifies ylide-like structures undergoing the 1,2-sigmatropic hydrogen shift concertedly giving the thioether product. But ¹CF₂ forms weak complexes involving 1,2-hydrogen shift. The barrier height in the concerted mechanism varies with the type of carbene moiety and S?H bond. The initial interaction seems to be a function of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies of thiols and carbenes, respectively. The natural bond orbital charge analysis showing a net charge flow from the substrate thiol to the reagent carbene at the transition states corroborates this fact.     

Pressure induced phase transitions in Ga1 − x In x P

We have theoretically investigated the effect of pressure on the structural stability of GaP?:?InP mixed system. The three-body-potential (TBP) model has been used. The TBP model consists of long-range as well as short-range interactions; the long-range part includes the modified Coulomb force as well as a three-body term; the short-range part in TBP defines the van der Waals and overlap repulsive interactions. We observe a pressure-induced structural phase transformation from ZnS (B3) to NaCl (B1) type phase in Ga _1?x In _x P. Our calculated transition pressures for the initial GaP and final InP compound semiconductors are in good agreement with other reported data.     

High-Density Excitons in a Diluted Magnetic Semiconductor: Cd 1 − x Mn x Te

Time-resolved magneto photoluminescence in a diluted magnetic semiconductor Cd 0.9 Mn 0.1 Te has been carried out with varying exciton density from 10 14 to 10 19 cm m 3 . The reduction of the Zeeman shift and that of the magnetic polaron energy was found under strong photoexcitation. The spectral feature is interpreted in terms of the heating of the manganese spin subsystem. Polarization dependence of the spin heating is observed for the first time, revealing the contribution of the spin flip between excitons and magnetic ions to the heating process.     

Novel Route for Preparation of 7‐Methyl‐camptothecin and Its Possible Mechanism

A novel route for preparation of 7‐methyl‐camptothecin is described. Its possible mechanism is discussed.     

One-step construction of MoO_2 uniform nanoparticles on graphene with enhanced lithium storage

Transition-metal oxides are considered to be a promising anode material for lithium-ion batteries(LIBs)due to their high capacities,low cost,and ease of synthesis.Herein,a hybrid nanosheet composed of uniform MoO_2 nanoparticles(NPs) homogeneously immobilized on the reduced graphene oxide nanosheets(MoO_2 NP@rGO) is first synthesized by a self-templating and subsequent calcination treatment.The unique two-dimensional hybridnanosheets provides several merits.rGO can be used as a favorable support for the loading of electrochemically active MoO_2 NPs.Meanwhile,MoO_2 NPs can effectively prevent the stacking of the rGO.The effective combination of MoO_2 NPs and rGO nanosheets furnish additional electrochemically interfacial active sites for extra lithium ion sto rage.Noticeably,the as-fabricated hybrid nanosheets deliver a reversible capacity of 641 mAh/g after 350 cycles at a current density of 1000 mA/g with a good rate capability.The greatly enhanced lithium storage properties of MoO_2 NP@rGO indicate the importance of elaborate construction of novel hybrid hierarchical structures.     

Dynamics of the Up-Conversion Emission in Holmium Doped Zblan Fiber

The dynamics of up-conversion, green emission under excitation at different infra-red wavelength in Ho^3? doped ZBLAN fiber is reported. Under infrared, 890 nm quasi cw pumping the complicated temporal behavior of the up-conversion signal is strongly influenced by the intermediate ⁵I₅ state cross relaxation. The mechanisms of the observed up-conversion processes are proposed and the time evolution of the ⁵S₂ population is described by the rate equation model. Parameters of the model are determined and numerical simulations of the excited state dynamics are performed.     

Overwriting information: Correlations,physical costs,and environment models

In this sequel to our previous study of the entropic and energetic costs of information erasure [N.G. Anderson, Phys. Lett. A 372 (2008) 5552], we consider direct overwriting of classical information encoded in a quantum-mechanical memory system interacting with a heat bath. Lower bounds on physical costs of overwriting – in both “single-shot” and “sequential” overwriting scenarios – are obtained from globally unitary quantum dynamics and entropic inequalities alone, all within a referential approach that grounds information content in correlations between physical system states. A heterogeneous environment model, required for consistent treatment of sequential overwriting, is introduced and used to establish and relate bounds for various cases.