Implication of a sigma-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex Ru(Me)(dppe)(2)]OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species (dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)(2)}Ru]OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru-Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a sigma-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C-H are cis to each other. Migration of hydrogen from agostic C-H and elimination of methane proceed through the transition state TS2, which retains a weak metal-H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3.

The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

We investigated the nature of the cohesive energy between graphane sheets via multiple CH center dot center dot center dot HC interactions, using density functional theory (DFT) including dispersion correction (Grimmes D3 approach) computations of n]graphane sigma dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical pi/pi interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (Delta E-F) composed of electrostatic and Pauli repulsion interactions, polarization (Delta E-pol), charge-transfer interaction (Delta E-CT), and dispersion effects (Delta E-disp). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the sigma CH -> sigma*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 angstrom. The Delta E-CT term, which accounts for similar to 15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic glue for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the double faced adhesive tape style of charge transfer interactions was also observed among graphene sheets in which it accounts for similar to 18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH center dot center dot center dot HC interactions, or as a function of the number of C-H bonds.

Variational approach to homogenization of doubly-nonlinear flow in a periodic structure

This work deals with the homogenization of an initial- and boundary-value problem for the doubly-nonlinear system D(t)w - del.(z) over right arrow = g(x, t, x/epsilon) (0.1) w is an element of alpha(u, x/epsilon) (0.2) (z) over right arrow is an element of (gamma) over right arrow (del u, x/epsilon) (0.3) Here epsilon is a positive parameter; alpha and (gamma) over right arrow are maximal monotone with respect to the first variable and periodic with respect to the second one. The inclusions (0.2) and (0.3) are here formulated as null-minimization principles, via the theory of Fitzpatrick MR 1009594]. As epsilon -> 0, a two-scale formulation is derived via Nguetseng's notion of two-scale convergence, and a (single-scale) homogenized problem is then retrieved. (C) 2015 Elsevier Ltd. All rights reserved.

Variational approach to homogenization of doubly-nonlinear flow in a periodic structure

This work deals with the homogenization of an initial- and boundary-value problem for the doubly-nonlinear system D(t)w - del.(z) over right arrow = g(x, t, x/epsilon) (0.1) w is an element of alpha(u, x/epsilon) (0.2) (z) over right arrow is an element of (gamma) over right arrow (del u, x/epsilon) (0.3) Here epsilon is a positive parameter; alpha and (gamma) over right arrow are maximal monotone with respect to the first variable and periodic with respect to the second one. The inclusions (0.2) and (0.3) are here formulated as null-minimization principles, via the theory of Fitzpatrick MR 1009594]. As epsilon -> 0, a two-scale formulation is derived via Nguetseng's notion of two-scale convergence, and a (single-scale) homogenized problem is then retrieved. (C) 2015 Elsevier Ltd. All rights reserved.

VAM Applied to Dimensional Reduction of Nonlinear Multifunctional Film-fabric Laminates

This work aims at asymptotically accurate dimensional reduction of non-linear multi-functional film-fabric laminates having specific application in design of envelopes for High Altitude Airships (HAA). The film-fabric laminate for airship envelope consists of a woven fabric core coated with thin films on each face. These films provide UV protection and Helium leakage prevention, while the core provides required structural strength. This problem is both geometrically and materially non-linear. To incorporate the geometric non-linearity, generalized warping functions are used and finite deformations are allowed. The material non-linearity is handled by using hyper-elastic material models for each layer. The development begins with three-dimensional (3-D) nonlinear elasticity and mathematically splits the analysis into a one-dimensional through-the-thickness analysis and a two-dimensional (2-D) plate analysis. The through-the-thickness analysis provides the 2-D constitutive law which is then given as an input to the 2-D reference surface analysis. The dimensional reduction is carried out using Variational Asymptotic Method (VAM) for moderate strains and very small thickness-to-wavelength ratio. It features the identification and utilization of additional small parameters such as ratio of thicknesses and stiffness coefficients of core and films. Closed form analytical expressions for warping functions and 2-D constitutive law of the film-fabric laminate are obtained.

Robust Whisper Activity Detection Using Long-Term Log Energy Variation of Sub-Band Signal

The goal in the whisper activity detection (WAD) is to find the whispered speech segments in a given noisy recording of whispered speech. Since whispering lacks the periodic glottal excitation, it resembles an unvoiced speech. This noise-like nature of the whispered speech makes WAD a more challenging task compared to a typical voice activity detection (VAD) problem. In this paper, we propose a feature based on the long term variation of the logarithm of the short-time sub-band signal energy for WAD. We also propose an automatic sub-band selection algorithm to maximally discriminate noisy whisper from noise. Experiments with eight noise types in four different signal-to-noise ratio (SNR) conditions show that, for most of the noises, the performance of the proposed WAD scheme is significantly better than that of the existing VAD schemes and whisper detection schemes when used for WAD.

Investigations on growth, structure, optical properties and laser damage threshold of organic nonlinear optical crystals of Guanidinium L-Ascorbate

Single crystals of Guanidinium L-Ascorbate (GuLA) were grown and crystal structure was determined by direct methods. GuLA crystallizes in orthorhombic, non-centrosymmetric space group P2(1)2(1)2(1). The UV-cutoff was determined as 325 nm. The morphology was generated and the interplanar angles estimated and compared with experimental values. Second harmonic generation conversion efficiency was measured and compared with other salts of L-Ascorbic acid. Surface laser damage threshold was calculated as 11.3GW/cm(2) for a single shot of laser of 1064 nm wavelength.

Nonlinear Differential Games-Based Impact-Angle-Constrained Guidance Law

The problem of intercepting a maneuvering target at a prespecified impact angle is posed in nonlinear zero-sum differential games framework. A feedback form solution is proposed by extending state-dependent Riccati equation method to nonlinear zero-sum differential games. An analytic solution is obtained for the state-dependent Riccati equation corresponding to the impact-angle-constrained guidance problem. The impact-angle-constrained guidance law is derived using the states line-of-sight rate and projected terminal impact angle error. Local asymptotic stability conditions for the closed-loop system corresponding to these states are studied. Time-to-go estimation is not explicitly required to derive and implement the proposed guidance law. Performance of the proposed guidance law is validated using two-dimensional simulation of the relative nonlinear kinematics as well as a thrust-driven realistic interceptor model.

Comparison of a priori and a posteriori meshes for singularly perturbed nonlinear parameterized problems

This paper deals with the adaptive mesh generation for singularly perturbed nonlinear parameterized problems with a comparative research study on them. We propose an a posteriori error estimate for singularly perturbed parameterized problems by moving mesh methods with fixed number of mesh points. The well known a priori meshes are compared with the proposed one. The comparison results show that the proposed numerical method is highly effective for the generation of layer adapted a posteriori meshes. A numerical experiment of the error behavior on different meshes is carried out to highlight the comparison of the approximated solutions. (C) 2015 Elsevier B.V. All rights reserved.

Crystallographic studies of the extracytoplasmic function sigma factor sigma(J) from Mycobacterium tuberculosis

Mycobacterium tuberculosis has multiple sigma factors which enable the bacterium to reprogram its transcriptional machinery under diverse environmental conditions. sigma(J), an extracytoplasmic function sigma factor, is upregulated in late stationary phase cultures and during human macrophage infection. sigma(J) governs the cellular response to hydrogen peroxide-mediated oxidative stress. sigma(J) differs from other canonical sigma factors owing to the presence of a SnoaL_2 domain at the C-terminus. sigma(J) crystals belonged to the tetragonal space group I422, with unit-cell parameters a = b = 133.85, c = 75.08 angstrom. Diffraction data were collected to 2.16 angstrom resolution on the BM14 beamline at the European Synchrotron Radiation Facility (ESRF).

Conductivity studies on microwave synthesized glasses

Conductivity measurements have been made on x V O-2(5) - (100-x) 0.5 Na2O + 0.5 B2O3] (where 10 a parts per thousand currency sign x a parts per thousand currency sign 50) glasses prepared by using microwave method. DC conductivity (sigma) measurements exhibit temperature-and compositional-dependent trends. It has been found that conductivity in these glasses changes from the predominantly `ionic' to predominantly `electronic' depending upon the chemical composition. The dc conductivity passes through a deep minimum, which is attributed to network disruption. Also, this nonlinear variation in sigma (dc) and activation energy can be interpreted using ion-polaron correlation effect. Electron paramagnetic resonance (EPR) and impedance spectroscopic techniques have been used to elucidate the nature of conduction mechanism. The EPR spectra reveals, in least modified (25 Na2O mol%) glasses, conduction is due to the transfer of electrons via aliovalent vanadium sites, while in highly modified (45 Na2O mol%) glasses Na+ ion transport dominates the electrical conduction. For highly modified glasses, frequency-dependent conductivity has been analysed using electrical modulus formalism and the observations have been discussed.

Nonlinear control of an air-breathing engine including its validation with vehicle guidance

An implementable nonlinear control design approach is presented for a supersonic air-breathing ramjet engine. The primary objective is to ensure that the thrust generated by the engine tracks the commanded thrust without violating the operational constraints. An important constraint is to manage the shock wave location in the intake so that it neither gets detached nor gets too much inside the intake. Both the objectives are achieved by regulating the fuel flow to the combustion chamber and by varying the throat area of the nozzle simultaneously. The design approach accounts for the nonlinear cross-coupling effects and nullifies those. Also, an extended Kalman filter has been used to filter out the sensor and process noises as well as to make the states available for feedback. Furthermore, independent control design has been carried out for the actuators. To test the performance of the engine for a realistic flight trajectory, a representative trajectory is generated through a trajectory optimization process, which is augmented with a newly-developed finite-time state dependent Riccati equation technique for nullifying the perturbations online. Satisfactory overall performance has been obtained during both climb and cruise phases. (C) 2015 Elsevier Masson SAS. All rights reserved.

Bearing capacity of circular footings over rock mass by using axisymmetric quasi lower bound finite element limit analysis

The ultimate bearing capacity of a circular footing, placed over rock mass, is evaluated by using the lower bound theorem of the limit analysis in conjunction with finite elements and nonlinear optimization. The generalized Hoek-Brown (HB) failure criterion, but by keeping a constant value of the exponent, alpha = 0.5, was used. The failure criterion was smoothened both in the meridian and pi planes. The nonlinear optimization was carried out by employing an interior point method based on the logarithmic barrier function. The results for the obtained bearing capacity were presented in a non-dimensional form for different values of GSI, m(i), sigma(ci)/(gamma b) and q/sigma(ci). Failure patterns were also examined for a few cases. For validating the results, computations were also performed for a strip footing as well. The results obtained from the analysis compare well with the data reported in literature. Since the equilibrium conditions are precisely satisfied only at the centroids of the elements, not everywhere in the domain, the obtained lower bound solution will be approximate not true. (C) 2015 Elsevier Ltd. All rights reserved.

Flow Cytometry Analysis of Cytotoxicity In Vitro and Long-Term Toxicity of HA-40wt% BaTiO3 Nanoparticles In Vivo

The development of new implantable biomaterials requires bone-mimicking physical properties together with desired biocompatible property. In continuation to our earlier published research to establish compositional dependent multifunctional bone-like properties and cytocompatibility response of hydroxyapatite (HA)-BaTiO3 composites, the toxicological property evaluation, both invitro and invivo, were conducted on HA-40wt% BaTiO3 and reported in this work. In particular, this work reports invitro cytotoxicity of mouse myoblast cells as well as invivo long-term tissue and nanoparticles interaction of intra-articularly injected HA-40wt% BaTiO3 and BaTiO3 up to the concentration of 25mg/mL in physiological saline over 12weeks in mouse model. The careful analysis of flow cytometry results could not reveal any statistically significant difference in terms of early/late apoptotic cells or necrotic cells over 8d in culture. Extensive histological analysis could not record any signature of cellular level toxicity or pronounced inflammatory response in vital organs as well as at knee joints of Balb/c mice after 12weeks. Taken together, this study establishes nontoxic nature of HA-40wt% BaTiO3 and therefore, HA-40wt% BaTiO3 can be used safely for various biomedical applications.

Nonlinear mode coupling and internal resonances in MoS2 nanoelectromechanical system

Atomically thin two dimensional (2D) layered materials have emerged as a new class of material for nanoelectromechanical systems (NEMS) due to their extraordinary mechanical properties and ultralow mass density. Among them, graphene has been the material of choice for nanomechanical resonator. However, recent interest in 2D chalcogenide compounds has also spurred research in using materials such as MoS2 for the NEMS applications. As the dimensions of devices fabricated using these materials shrink down to atomically thin membrane, strain and nonlinear effects have become important. A clear understanding of the nonlinear effects and the ability to manipulate them is essential for next generation sensors. Here, we report on all electrical actuation and detection of few-layer MoS2 resonator. The ability to electrically detect multiple modes and actuate the modes deep into the nonlinear regime enables us to probe the nonlinear coupling between various vibrational modes. The modal coupling in our device is strong enough to detect three distinct internal resonances. (C) 2015 AIP Publishing LLC.