C-H functionalization of tertiary amines by cross dehydrogenative coupling reactions: solvent-free synthesis of alpha-aminonitriles and beta-nitroamines under aerobic condition

A solvent-free synthesis of alpha-aminonitriles and beta-nitroamines by oxidative cross-dehydrogenative coupling under aerobic condition is reported. A catalytic amount of molybdenum(VI) acetylacetonoate was found to catalyze cyanation of tertiary amines to form alpha-aminonitriles, whereas vanadium pentoxide was found to promote aza-Henry reaction to furnish beta-nitroamines. Both of these environmentally benign reactions are performed in the absence of solvents using molecular oxygen as an oxidant.

Griffiths phase-like behavior and spin-phonon coupling in double perovskite Tb(2)NiMnO(6)

The Griffiths phase-like features and the spin-phonon coupling effects observed in Tb(2)NiMnO(6) are reported. The double perovskite compound crystallizes in monoclinic P2(1)/n space group and exhibits a magnetic phase transition at T(c) similar to 111 K as an abrupt change in magnetization. A negative deviation from ideal Curie-Weiss law exhibited by 1/chi(T) curves and less-than-unity susceptibility exponents from the power-law analysis of inverse susceptibility are reminiscent of Griffiths phase-like features. Arrott plots derived from magnetization isotherms support the inhomogeneous nature of magnetism in this material. The observed effects originate from antiferromagnetic interactions that arise from inherent disorder in the system. Raman scattering experiments display no magnetic-order-induced phonon renormalization below Tc in Tb(2)NiMnO(6), which is different from the results observed in other double perovskites and is correlated to the smaller size of the rare earth. The temperature evolution of full-width-at-half-maximum for the stretching mode at 645 cm(-1) presents an anomaly that coincides with the magnetic transition temperature and signals a close connection between magnetism and lattice in this material. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3671674]

Isolating CP-violating gamma ZZ coupling in e(+)e(-) -> gamma Z with transverse beam polarizations

We revisit the process e(+)e(-) -> gamma Z at the ILC with transverse beam polarization in the presence of anomalous CP- violating gamma ZZ coupling lambda(1) and gamma gamma Z coupling lambda(2). We point out that if the final- state spins are resolved, then it becomes possible to fingerprint the anomalous coupling Re lambda(1). 90% confidence level limit on Re lambda(1) achievable at ILC with center- of- mass energy of 500 GeVor 800 GeV with realistic initial beam polarization and integrated luminosity is of the order of few times of 10(-2) when the helicity of Z is used and 10(-3) when the helicity of gamma is used. The resulting corrections at quadratic order to the cross section and its influence on these limits are also evaluated and are shown to be small. The benefits of such polarization programmes at the ILC are compared and contrasted for the process at hand. We also discuss possible methods by which one can isolate events with a definite helicity for one of the final- state particles.

Evaluation of physico-mechanical properties and in vitro biocompatibility of compression molded HDPE based biocomposites with HA/Al2O3 ceramic fillers and titanate coupling agents

The present article demonstrates how the stiffness, hardness as well as the cellular response of bioinert high-density polyethylene (HDPE) can be significantly improved with combined addition of both bioinert and bioactive ceramic fillers. For this purpose, different amounts of hydroxyapatite and alumina, limited to a total of 40 wt %, have been incorporated in HDPE matrix. An important step in composite fabrication was to select appropriate solvent and optimal addition of coupling agent (CA). In case of chemically coupled composites, 2% Titanium IV, 2-propanolato, tris iso-octadecanoato-O was used as a CA. All the hybrid composites, except monolithic HDPE, were fabricated under optimized compression molding condition (140 degrees C, 0.75 h, 10 MPa pressure). The compression molded composites were characterized, using X-ray diffraction, Fourier transformed infrared spectroscopy, and scanning electron microscopy. Importantly, in vitro cell culture and cell viability study (MTT) using L929 fibroblast and SaOS2 osteoblast-like cells confirmed good cytocompatibility properties of the developed hybrid composites. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Molybdenum trioxide catalyzed oxidative cross-dehydrogenative coupling of benzylic sp(3) C-H bonds: synthesis of alpha-aminophosphonates under aerobic conditions

Molybdenum trioxide (MoO3) catalyzed efficient oxidative cross-dehydrogenative-coupling (CDC) method for C-H functionalization of N-aryl tetrahydroisoquinolines has been explored. This user-friendly method of synthesizing alpha-aminophosphonates employs 1.1 equiv of dialkyl-H-phosphonate under aerobic condition. Formation of new C-P bonds from unfunctionalized starting materials under environmentally benign conditions provides an excellent avenue for the synthesis of biologically active alpha-aminophosphonates. (C) 2012 Elsevier Ltd. All rights reserved.

Quantum corrections to screening at strong coupling

We compute a certain class of corrections to (specific) screening lengths in strongly coupled non-abelian plasmas using the AdS/CFT correspondence. In this holographic framework, these corrections arise from various higher curvature interactions modifying the leading Einstein gravity action. The changes in the screening lengths are perturbative in inverse powers of the `t Hooft coupling or of the number of colors, as can be made precise in the context where the dual gauge theory is superconformal. We also compare the results of these holographic calculations to lattice results for the analogous screening lengths in QCD. In particular, we apply these results within the program of making quantitative comparisons between the strongly coupled quark-gluon plasma and holographic descriptions of conformal field theory. (c) 2012 Elsevier B.V. All rights reserved.

MODELING HETEROSTRUCTURES WITH SCHRODINGER-POISSON-NAVIER ITERATIVE SCHEMES, EFFECT OF CARRIER CHARGE, AND INFLUENCE OF ELECTROMECHANICAL COUPLING

This paper presents a detailed investigation of the erects of piezoelectricity, spontaneous polarization and charge density on the electronic states and the quasi-Fermi level energy in wurtzite-type semiconductor heterojunctions. This has required a full solution to the coupled Schrodinger-Poisson-Navier model, as a generalization of earlier work on the Schrodinger-Poisson problem. Finite-element-based simulations have been performed on a A1N/GaN quantum well by using both one-step calculation as well as the self-consistent iterative scheme. Results have been provided for field distributions corresponding to cases with zero-displacement boundary conditions and also stress-free boundary conditions. It has been further demonstrated by using four case study examples that a complete self-consistent coupling of electromechanical fields is essential to accurately capture the electromechanical fields and electronic wavefunctions. We have demonstrated that electronic energies can change up to approximately 0.5 eV when comparing partial and complete coupling of electromechanical fields. Similarly, wavefunctions are significantly altered when following a self-consistent procedure as opposed to the partial-coupling case usually considered in literature. Hence, a complete self-consistent procedure is necessary when addressing problems requiring more accurate results on optoelectronic properties of low-dimensional nanostructures compared to those obtainable with conventional methodologies.

Evolution of structural phase coexistence in a half doped manganite Pr0.5Sr0.5MnO3: An evidence for magneto-structural coupling

Temperature dependent x-ray diffraction measurements have been performed to understand the implications of magnetic phase coexistence on crystallographic structure in a half-doped manganite Pr0.5Sr0.5MnO3. The compound shows a structural phase transition from high-temperature tetragonal-I4/mcm to low-temperature orthorhombic-Fmmm symmetry around the ferromagnetic to antiferro-magnetic transition. Rietveld analysis shows the coexistence of these two structures emerges at high temperature within the ferromagnetic state, and persists down to lowest temperature. Below around 40 K, however, this structural evolution stops, and a significant fraction (similar to 22%) of untransformed high-temperature phase remains. This agrees with earlier magnetization study, thus establishing its magneto-structural coupling. (C) 2012 Elsevier B.V. All rights reserved.

Influence of growth ambience and doping on the structural properties of multiferroic DyMnO3

We report on the single crystal growth of 50% Sr and Y doped multiferroic DyMnO3 using optical floating zone technique. A comparison of the effect of growth ambience and of chemical substitution on the crystal structure of DyMnO3 is attempted. It is observed that DyMnO3 adopts Pm3m cubic structure with 50% Sr doping whereas with 50% Y doping, the crystal structure is hexagonal P6(3)cm. Orthorhombic Pnma structure is adopted by DyMnO3 when grown in air, whereas hexagonal P6(3)cm structure is obtained when grown under the ambience of argon. The structural polymorphism is discussed in terms of difference in ionic sizes of Sr, Y and Dy, comparable Gibbs free energies and coordination schemes of surrounding oxygens for hexagonal and orthorhombic structures of DyMnO3. (C) 2012 Elsevier B.V. All rights reserved.

Palladium Catalyzed Coupling of Tosylhydrazones with Aryl and Heteroaryl Halides in the Absence of External Ligands: Synthesis of Substituted Olefins

Palladium catalyzed cross-coupling reaction of hydrazones with aryl halides in the absence of external ligand is reported. The versatility of this coupling reaction is demonstrated in showcasing the selectivity of coupling reaction in the presence of hydroxyl and amine functional groups. This method allows synthesizing a variety of heterocyclic compounds, which are difficult to access from other traditional methods and are not synthesized by employing similar coupling reactions. Application of the present methodology is validated in tandem reaction of ketones to the corresponding substituted olefins in a single pot experiment.

Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Coupling of photomechanical and electromechanical actuations in carbon nanotubes

It is known that carbon nanotubes (CNTs) possess multifunctional characteristics, which are applicable for a wide variety of engineering applications. CNT is also recognized as a radiation sensitive material, for example for detecting infrared (IR) radiations. One of the direct implications of exposing CNTs to radiation is the photomechanical actuation and generation of a photovoltage/photocurrent. The present work focuses on coupling electromechanical and photomechanical characteristics to enhance the resulting induced-strain response in CNTs. We have demonstrated that after applying an electric field the induced strain in CNT sheet is enhanced to about similar to 2.18 times for the maximum applied electric field at 2 V as compared to the photo-actuation response alone. This enhancement of the strain at higher bias voltages (> 1 V) can be considered as a sum of individual contributions of the bias voltage and IR stimulus. However, at lower voltage (< 1 V) the enhancement in the resulting strain has been attributed to the associated electrostatic effects when CNTs are stimulated with IR radiation under external bias conditions. This report reveals that voltage bias or IR stimulus alone could not produce the observed strain in the CNT sheet under lower bias conditions.

High power microwave coupling with a buried twisted pair cable

This paper deals with the coupling of High Power Microwaves with a buried twisted pair cable. The electric field at a distance of 1km from the HPM antenna has been computed and is used for further computation of induced voltage and current. It is found that the peak of the induced current and voltage in a buried unshielded twisted pair cable at a distance of 1km from an HPM antenna of power level 10GW is 20A and 2kV respectively.

Interplay of structural distortions, dielectric effects and magnetic order in multiferroic GdMnO3

Multiferroic materials are characterized by simultaneous magnetic and ferroelectric ordering making them good candidates for magneto-electrical applications. We conducted thermal expansion and magnetostriction measurements in magnetic fields up to 14 T on perovskitic GdMnO3 by highresolution capacitive dilatometry in an effort to determine all longitudinal and transversal components of the magnetostriction tensor. Below the ordering temperature T (N) = 42 K, i.e., within the different complex (incommensurate or complex) antiferromagnetic phases, lattice distortions of up to 100 ppm have been found. Although no change of the lattice symmetry occurs, the measurements reveal strong magneto-structural phenomena, especially in the incommensurate sinusoidal antiferromagnetic phase. A strong anisotropy of the magnetoelastic properties was found, in good agreement with the type and propagation vector of the magnetic structure. We demonstrate that our capacitive dilatometry can detect lattice expansion effects and changes of the dielectric permittivity simultaneously because the sample is housed inside the capacitor. A separation of both effects is possible by shielding the sample. Dielectric transitions could be detected by this method and compared to the critical values of H and T in the magnetic phase diagram. Dielectric changes measured at 1 kHz excitation frequency are detected in GdMnO3 at about 180 K, and between 10 K and 25 K in the canted antiferromagnetic structure which is characterized by a complex magnetic order on both the Gd- and Mn-sites.

Highly regioselective C2-alkenylation of indoles using the N-benzoyl directing group: an efficient Ru-catalyzed coupling reaction

A highly regioselective alkenylation of indole at the C2-position has been achieved using the Ru(II) catalyst by employing a directing group strategy. This strategy offers rare selectivity for the alkenylation N-benzoylindole at the C-2 position in the presence of the more active C3- and C7-position of indole and the ortho-positions of the benzoyl protecting group. A simple deprotection of the benzoyl group has also been exemplified, and the resulting product serves as a useful synthon for natural product syntheses.