Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride-Boryl-Iridium-POP Complexes: Kinetic Analysis of the Elemental Steps

The saturated trihydride IrH₃{κ³-P,O,P-[xant(PiPr₂)₂]} ( 1 ; xant(PiPr₂)₂=9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) activates the B−H bond of two molecules of pinacolborane (HBpin) to give H₂, the hydride-boryl derivatives IrH₂(Bpin){κ³-P,O,P-[xant(PiPr₂)₂]} ( 2 ) and IrH(Bpin)₂{κ³-P,O,P-[xant(PiPr₂)₂]} ( 3 ) in a sequential manner. Complex 3 activates a C−H bond of two molecules of benzene to form PhBpin and regenerates 2 and 1 , also in a sequential manner. Thus, complexes 1 , 2 , and 3 define two cycles for the catalytic direct C−H borylation of arenes with HBpin, which have dihydride 2 as a common intermediate. C−H bond activation of the arenes is the rate-determining step of both cycles, as the C−H oxidative addition to 3 is faster than to 2 . The results from a kinetic study of the reactions of 1 and 2 with HBpin support a cooperative function of the hydride ligands in the B−H bond activation. The addition of the boron atom of the borane to a hydride facilitates the coordination of the B−H bond through the formation of κ¹- and κ²-dihydrideborate intermediates.     

Synthesis and applications of graphene oxide aerogels in bone tissue regeneration: a review

Development of biocompatible porous supports is a promising strategy in the field of tissue engineering for the repair and regeneration of bone tissues with severe damage. Graphene oxide aerogels (GOAs) are excellent candidates for the manufacture of these systems due to their porosity, ability to imitate bone structure, and mechanical resistance, and according to their surface chemical reactivity, they can facilitate osseointegration, osteogenesis, osteoinduction and osteoconduction. In this review, synthesis of GOAs from the most primary source is described, and recent studies on the use of these functionalized carbonaceous foams as scaffolding for bone tissue regeneration are presented.     

Application of the finite point method to high‐Reynolds number compressible flow problems

In this work, the finite point method is applied to the solution of high‐Reynolds compressible viscous flows. The aim is to explore this important field of applications focusing on two main aspects: the easiness and automation of the meshless discretization of viscous layers and the construction of a robust numerical approximation in the highly stretched clouds of points resulting in such domain areas. The flow solution scheme adopts an upwind‐biased scheme to solve the averaged Navier–Stokes equations in conjunction with an algebraic turbulence model. The numerical applications presented involve different attached boundary layer flows and are intended to show the performance of the numerical technique. The results obtained are satisfactory and indicative of the possibilities to extend the present meshless technique to more complex flow problems. Copyright © 2014 John Wiley & Sons, Ltd.     

A meshless finite point method for three‐dimensional analysis of compressible flow problems involving moving boundaries and adaptivity

A finite point method for solving compressible flow problems involving moving boundaries and adaptivity is presented. The numerical methodology is based on an upwind‐biased discretization of the Euler equations, written in arbitrary Lagrangian–Eulerian form and integrated in time by means of a dual‐time steeping technique. In order to exploit the meshless potential of the method, a domain deformation approach based on the spring network analogy is implemented, and h‐adaptivity is also employed in the computations. Typical movable boundary problems in transonic flow regime are solved to assess the performance of the proposed technique. In addition, an application to a fluid–structure interaction problem involving static aeroelasticity illustrates the capability of the method to deal with practical engineering analyses. The computational cost and multi‐core performance of the proposed technique is also discussed through the examples provided. Copyright © 2013 John Wiley & Sons, Ltd.     

Numerical simulations of negatively buoyant jets in an immiscible fluid using the Particle Finite Element Method

Negatively buoyant jets consist in a dense fluid injected vertically upward into a lighter ambient fluid. The numerical simulation of this kind of buoyancy‐driven flows is challenging as it involves multiple fluids with different physical properties. In the case of immiscible fluids, it requires, in addition, to track the motion of the interface between fluids and accurately represent the discontinuities of the flow variables. In this paper, we investigate numerically the injection of a negatively buoyant jet into a homogenous immiscible ambient fluid using the Particle Finite Element Method and compare the two‐dimensional numerical results with experiments on the injection of a jet of dyed water through a nozzle in the base of a cylindrical tank containing rapeseed oil. In both simulations and experiments, the fountain inlet flow velocity and nozzle diameter have been varied to cover a wide range of Froude Fr and Reynolds Re numbers ( 0.1 < Fr < 30, 8 < Re < 1350), reproducing both weak and strong laminar fountains. The flow behaviors observed for the different numerical simulations fit in the regime map based on the Re and Fr values of the experiments, and the maximum fountain height is in good agreement with the experimental observations, suggesting that particle finite element method is a useful tool for the study of immiscible two‐fluid systems. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and Spectroscopic Properties of Carbazole-Oxadiazoles

Four new carbazole-oxadiazole derivatives (3a-b, 6a-b) were prepared from the reaction of aromatic aldehydes and carbohydrazides which were synthesized from carbazole aldehydes namely 9-hexyl-9H-carbazole-3-carbaldehyde 1 and 4-(9H-carbazole-9-yl)benzaldehyde 4 and acid hydrazides. The structures of the new derivatives were confirmed by ¹H-NMR and FT-IR. The optical properties such as maximum absorption and emission wavelengths (λ; nm), molar extinction coefficients (ε; cm^?1 M^?1), Stoke’s shifts (ΔλST; nm) and quantum yields (?F), of the carbazole-oxadiazole derivatives were declared in dichloromethane, toluene and tetrahydrofuran solutions.     

Comparative study of different discrete element models and evaluation of equivalent micromechanical parameters

Comparative studies of different discrete element models of a rock-type material are presented. The discrete element formulation employs spherical particles with the cohesive interaction model combining linear elastic behaviour with brittle failure. Numerical studies consisted in simulation of the uniaxial compression test. Two cylindrical specimens with particle size distributions yielding different degree of heterogeneity have been used. Macroscopic response produced by different discrete element models has been compared. The main difference between the compared models consists in the evaluation of micromechanical constitutive parameters. Two approaches are compared. In the first approach, the contact stiffness and strength parameters depend on the local particle size, while in the second approach, global uniform contact parameters are assumed for all the contacting pairs in function of average geometric measures characterizing the particle assembly. The size dependent contact parameters are calculated as functions of geometric parameters characterizing each contacting particle pair. As geometric scaling parameters, the arithmetic and harmonic means, as well as the minimum of the radii of two contacting particles are considered. Two different models with size dependent contact parameters are formulated. The performance of these models is compared with that of the discrete element model with global uniform contact parameters. Equivalence between the models with size dependent and uniform contact parameters has been checked. In search of this equivalence, different methods of evaluation of global uniform parameters have been studied. The contact stiffness has been evaluated in terms of the average radius of the particle assembly or in terms of the averages of the arithmetic and harmonic means of the contact pair radii, the geometric parameters used in the evaluation of the contact stiffness in the size-dependent models. The uniform contact strengths have been determined as functions of the averages of radii squares, squares of arithmetic radii means or squares of minimum radii of the contacting pairs.For the more homogenous specimen, the models with local size dependent parameters and models with global uniform parameters give similar response. The models with uniform parameters evaluated according to the averages of the geometric parameters used in the evaluation of local parameters ensure better agreement with the respective models with size-dependent parameters than the models with uniform parameters evaluated according to the particle radii. Simulations using the more heterogenous specimen reveal differences between the considered models. There are significant differences in stress–strain curves as well as in the failure pattern. The models with local size-dependent parameters are more sensitive to the change of heterogeneity than the model with global uniform parameters.     

Nonlinear finite element analysis of orthotropic and prestressed membrane structures

A new methodology for the geometrically nonlinear analysis of orthotropic membrane structures using triangular finite elements is presented. The approach is based on writing the constitutive equations in the principal fiber orientation of the material. A direct consequence of the fiber orientation strategy is the possibility to analyze initially out-of-plane prestressed membrane structures. An algorithm to model wrinkling behavior is also described. Examples of application to a number of membrane structures are presented.     

Discretization and resolution of the (<Emphasis Type="Italic">r</Emphasis>|<Emphasis Type="Italic">X</Emphasis><Subscript><Emphasis Type="Italic">p</Emphasis></Subscript>)-medianoid problem involving quality criteria

In this paper an extension of the (r|X _p )-medianoid on networks introduced by Hakimi (1983) is studied. In this extension the customer considers not only the distance but some characteristics of the facilities such as store size, quality of service and parking space. A new firm wants to establishr new facilities which have to compete with thep facilities that already exist in the market. The entry firm wants to find their locations and characteristics to maximize profits. Three different customer choice rules (binary, partially binary and proportional preferences) are considered. Some discretization results are obtained and a resolution procedure is proposed. The problem is solved combining a global search algorithm based on a branch and bound procedure with some combinatorial heuristics (greedy, interchange, and tabu search). Some computational experiences are presented. Partially supported by Ministerio de Ciencia y Tecnología (Spain) and FEDER, grant BFM2002-04525-C02-01.     

Construction of Hexahydropyrido[3,2‐c]carbazole and Hexahydropyrrolo[3,2‐c]carbazole Skeletons for the Synthesis of Related Indole Alkaloids

Synthesis of tetracyclic hexahydropyrido[3,2‐c]carbazoles ( 9a and 9b ) and hexahydropyrrolo[3,2‐c]carbazoles ( 13a and 13b ) structures was achieved via a new synthetic approach for the synthesis of related indole alkaloids such as deethylaspidospermidine and deethylibophyllidine. Hexahydropyrrolo[3,2‐c]carbazole structure was constructed for the first time starting from ethyl 4‐oxo‐cyclohexanecarboxylate in seven steps. Some tetrahydrocarbazole derivatives ( 4 , 5 , 6 , 7 , 11 , and 12 ) were also synthesized.