Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate RuII-aqua complex,fac-[RuII(H2O)(dpp)(tppm)]2+

fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.     

On routing in large WDM networks

An important problem in WDM network design is to construct a logical topology and determine an optimal routing over that topology. Mixed Integer Linear Program (MILP) formulations to generate optimal solutions for this problem have been presented. Such formulations are computationally intractable, even for moderate sized networks. A standard approach is to decouple the problem of logical topology design and the problem of routing the traffic on this logical topology. Heuristics for finding the logical topology exist and a straight-forward linear program (LP), based on the node-arc formulation can be used to solve the routing problem over a given logical topology. We have found that such LP formulations become computationally infeasible for large networks. In this paper, we present a new formulation, based on the arc-chain representation, for optimally routing the specified traffic over a given logical topology to minimize the congestion of the network. We have used the revised simplex method incorporating an implicit column generation technique, and exploited the special Generalized Upper Bounding structure as well as the possibility of eta-factorization for efficiently updating the dual variables and finding the solution. Experimental results on a number of networks demonstrate the suitability of this approach.     

Beyond Biological Chelation: Coordination of f-Block Elements by Polyhydroxamate Ligands

The promise of polyhydroxamic acid ligands for the selective chelation of the f-block elements is becoming increasingly more apparent. The initial studies of polyhydroxamic acid siderophores showed the formation of highly stable complexes with Pu^IV, but a higher preference for Fe^III hindered effective applications. The development of synthetic routes toward highly pure and customizable ligands containing multiple hydroxamic acids allowed for the growth of new classes of compounds. Although the first round of these ligands focused on the incorporation of siderophore-like frameworks, the new synthetic strategies led to small molecules of various frameworks and even resins for applications in the field of f-block element separations and biological desorption. Unfortunately, a lack of consistent stability-constant data makes direct comparisons across this body of work difficult. More studies into the stability constants and separations of the f-block elements in a variety of pH ranges is necessary to truly realize the potential for polyhydroxamic acid ligands.     

Dynamics of an array formed by three neutrally buoyant cylindrical cantilevers subjected to tensile follower forces

The flexural-rotational coupled motion of three identical flexible cylindrical cantilevers joined symmetrically to a central head is investigated. Effects of the tensile follower forces and inertia parameters on the natural frequencies of the system are studied. The analysis suggests two types of inplane motion: one corresponding to the oscillation of the cantilevers without any rotation of the central body, while the other involves coupled motion of the array. The former corresponds to the repeated eigenvalues which are identical to those of a single cantilever having the same axial tension parameter, P. Three sets of eigenvalues govern the out-of-plane motion: (a) the central head remaining stationary with no rolling motion of the array; (b) vertical motion of the central body without any rolling motion of the array; and (c) rigid body rolling motion without any vertical motion of the central head. There is a possibility of dynamic instability for small inertia parameters and large axial tension.     

Towards aflatoxins: a formal synthesis of aflatoxin B2

The development of a formal synthesis of aflatoxin B2 is described, which utilizes a Dötz benzannulation reaction as a key step.     

Novel Mn(III) heterochelates: synthesis,thermal, spectroscopic,and coordination aspects

This article describes the synthesis, structural features, and thermal studies of novel Mn(III) heterochelates of the type [Mn(SB _n )(L)(H₂O)]·xH₂O [H₂SB _n  = Nicotinic acid [1-(3-methyl-5-oxo-1-phenyl-4,5 dihydro-1H-pyrazol-4yl)-acylidene]-hydrazide where acyl = acetyl (H₂SB₁); benzoyl (H₂SB₂); propionyl (H₂SB₃); buteryl (H₂SB₄); phenyl acetyl (H₂SB₅); and HL = 5-Chloro-7-iodo-8-hydroxyquinoline (clioquinol)]. The heterochelates have been characterized on the basis of elemental analyses, magnetic susceptibility measurements, cyclic voltammetric studies, (FTIR and electronic) spectra, and thermal studies. The FAB mass spectrum of [Mn(SB₁)(L)H₂O]·3H₂O has been carried out. The cyclic voltammetric studies reveal that quasi-reversible reduction process of Mn(III)/Mn(II) coupled system suggesting that the ligands readily destabilize higher oxidation states of metal ion. Kinetic parameters such as order of reaction (n) and the energy of activation (Ea) were calculated using Freeman–Carroll method. The pre-exponential factor (A), the activation entropy (S*), the activation enthalpy (H*), and the free energy of activation (G*) were calculated using Horowitz–Metzger equations.     

Al3+-modified elastic properties of copper ferrite

Ultrasonic pulse echo-overlap technique at 300 K (9 MHz) has been employed to study the elastic properties of Al³⁺-substituted CuFe₂O₄ spinel ferrite system. The longitudinal and transverse wave velocities are used to compute elastic moduli and these are corrected to the zero porosity by employing different models. Contrary to expectation, the magnitude of elastic moduli is found to decrease by 75% with only 30% of Al³⁺-substitution for Fe³⁺ in the system. The lowering of elastic stiffness is mainly due to residual stress-induced spontaneous cracking and presence of oxygen vacant sites in the material. The lower value of lattice energy for polycrystalline specimens as compared to their single crystalline counterparts have been explained in the light of an increase degree of disorientation at the grain boundary with Al³⁺-substitution.     

On the nonlinear dynamics and control of flexible orbiting manipulators

The paper studies nonlinear dynamics and control of a class of space station based mobile flexible two-link manipulators, normally referred to as the Mobile Servicing System (MSS).The governing nonlinear, nonautonomous and coupled equations of motion are described first followed by the modal discretizations procedure. A parametric response study suggests situations with unacceptable levels of deflections and accelerations for certain proposed missions, as well as station libration and payload positioning errors.An inverse control technique is proposed to achieve high tracking accuracy of the MSS in presence of maneuver induced disturbances. The control strategy is so designed as to regulate the libration of the Space Station as well as to insure joints tracking of prescribed trajectories, while limiting the effect of the structural vibration during large slewing maneuvres of the MSS. Two different control schemes, both based on the feedback linearization technique, are developed and their relative merit assessed.This investigation was supported by the Centers of Excellence Program, Grant No. IRIS/C-8, 5-55380, and Natural Sciences and Engineering Research Council of Canada, Grant No. A-2181.     

Bounds tightening based on optimality conditions for nonconvex box-constrained optimization

First-order optimality conditions have been extensively studied for the development of algorithms for identifying locally optimal solutions. In this work, we propose two novel methods that directly exploit these conditions to expedite the solution of box-constrained global optimization problems. These methods carry out domain reduction by application of bounds tightening methods on optimality conditions. This scheme is implicit and avoids explicit generation of optimality conditions through symbolic differentation, which can be memory and time intensive. The proposed bounds tightening methods are implemented in the global solver BARON. Computational results on a test library of 327 problems demonstrate the value of our proposed approach in reducing the computational time and number of nodes required to solve these problems to global optimality.