Vanadium(IV)-oxo Corrole Catalyzed Selective Oxidative Cleavage of Alkenes to Aldehydes

A practical and efficient protocol for oxidative cleavage of olefinic bonds especially in arylated olefins has been demonstrated. Herein, an oxo[5,10,15-tris(4-nitrophenyl)corrolato]vanadium (IV) complex (cat.), has been successfully synthesized and the existence of two tautomeric forms of this complex in solution has been established. Oxo[5,10,15-tris(4-nitrophenyl)corrolato]vanadium (IV) (cat.) in the presence of H₂O₂ cleaves olefinic bonds to yield the corresponding aldehyde compounds. In general, a high valent, oxo-(porphyrinoid)-metal complex catalyzes the epoxide formation reactions, however, in the present case, we have observed the exclusive formation of aldehydes. The reaction offered aryl aldehydes with good yields and excellent selectivity. A mechanism was also proposed for these catalysis reactions.     

Robust tracking control of nonlinear unmatched uncertain systems via event-based adaptive dynamic programming

Nonlinear Dynamics - In this paper, a novel robust tracking control strategy for nonlinear unmatched uncertain systems is formulated using the event-based adaptive dynamic programming (ADP)...     

Almost global attitude consensus of multi-agent rigid bodies on $$mathrm{TSO}(3)^N$$ TSO ( 3 ) N in the presence of disturbances and directed topology

Nonlinear Dynamics - The article proposes a distributed attitude consensus algorithm for multi-agent rigid bodies on the tangent bundle $$mathrm{TSO}(3)^N$$ . It is assumed that a directed fixed...     

Positron annihilation spectroscopic studies of solvothermally synthesized ZnO nanobipyramids and nanoparticles

Zinc oxide (ZnO) samples in the form of hexagonal-based bipyramids and particles of nanometer dimensions were synthesized through solvothermal route and characterized by x-ray diffraction and transmission electron microscopy. Positron annihilation experiments were performed to study the structural defects such as vacancies and surfaces in these nanosystems. From coincidence Doppler broadening measurements, the positron trapping sites were identified as Zn vacancies or Zn-O-Zn trivacancy clusters. The positron lifetimes, their relative intensities, and the Doppler broadened lineshape parameter S all showed characteristic changes across the nanobipyramid size corresponding to the thermal diffusion length of positrons. In large nanobipyramids, vacancies within the crystallites also trapped positrons and the effects of agglomeration of such vacancies due to increased temperatures of synthesis were reflected in the variation of the annihilation parameters with their base diameters. The sizes of the nanoparticles used were all in the limit of thermal diffusion length of positrons and the annihilation characteristics were in accordance with the decreasing contribution from surfaces with increasing particle size.     

Recovery of plutonium and cerium from alumina crucible

Journal of Radioanalytical and Nuclear Chemistry - Plutonium recovery is inevitable from plutonium bearing alumina crucibles generated over the years as part of carbon analysis during chemical...     

Geometry of Optimal Paths around Focal Singular Surfaces in Differential Games

We investigate a special type of singularity in non-smooth solutions of first-order partial differential equations, with emphasis on Isaacs’ equation. This type, called focal manifold, is characterized by the incoming trajectory fields on the two sides and a discontinuous gradient. We provide a complete set of constructive equations under various hypotheses on the singularity, culminating with the case where no a priori hypothesis on its geometry is known, and where the extremal trajectory fields need not be collinear. We show two examples of differential games exhibiting non-collinear fields of extremal trajectories on the focal manifold, one with a transversal approach and one with a tangential approach.     

Nonlinear Dynamics of a Cantilever Beam Carrying an Attached Mass with 1:3:9 Internal Resonances

In this paper the nonlinear response of a base-excited slender beam carrying an attached mass is investigated with 1:3:9 internal resonances for principal and combinationparametric resonances. Here the method of normal forms is used to reduce the second order nonlinear temporal differential equation of motion of the system to a set offirst order nonlinear differential equations which are used to find the fixed-point, periodic, quasi-periodic and chaotic responses of the system.Stability and bifurcation analysis of the responses are carried out and bifurcation sets are plotted. Many chaotic phenomena are reported in this paper.     

On the detection of single bond ruptures in dynamic force spectroscopy by AFM

Force spectroscopy is a novel tool in physical chemistry and biophysics. This methodology is aimed at providing kinetic parameters of dissociation at a single-molecule level by rupturing molecular bonds subjected to different loading rates. One persistent problem in the implementation of this methodology is a question about the single-bond nature of the rupture events detected in experiments based on atomic force microscopy. Here we address this question by considering the probability that the nearly simultaneous rupture of two molecular bonds might appear as a single bond rupture in the experimental data, complicating the data analysis and contributing to systematic errors in the extracted kinetic parameters. An approximate analytical model predicts that such events might be common in experiments employing soft cantilever force sensors and short tethers to immobilize the interacting molecules. These findings are confirmed by a more elaborate numerical model providing valuable guidelines on performing single-molecule force spectroscopy experiments.     

Optimal control of harvest and bifurcation of a prey-predator model with stage structure

This paper describes a prey-predator model with stage structure for prey. The adult prey and predator populations are harvested in the proposed system. The dynamic behavior of the model system is discussed. It is observed that singularity induced bifurcation phenomenon is appeared when variation of the economic interest of harvesting is taken into account. State feedback controller is incorporated to stabilize the model system in case of positive economic interest. Harvesting of prey and predator population are used as controls to develop a dynamic framework to investigate the optimal utilization of the resource, sustainability properties of the stock and the resource rent earned from the resource. The Pontryagin’s maximum principle is used to characterize the optimal controls. The optimality system is derived and then solved numerically using an iterative method with Runge-Kutta fourth order scheme. Simulation results show that the optimal control scheme can achieve sustainable ecosystem.