New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Monitoring structural damage of components using an effective modulus approach

This paper describes a novel nondestructive damage detection method that was developed to study the influence of a crack on the dynamic properties of a cantilever beam subjected to bending. Experimental measurements of transfer functions for the cracked cantilever beam revealed a change in the natural frequency with increasing crack length. A finite element model of a cracked element was created to compute the influence of severity and location of damage on the structural stiffness. The proposed model is based on the response of the cracked beam element under a static load. The change in beam deflection as a result of the crack is used to calculate the reduction in the global component stiffness. The reduction of the beam stiffness is then used to determine its dynamic response employing a modal analysis computational model. Euler–Bernoulli and Timoshenko beam theories are used to quantify the elastic stiffness matrix of a finite element. The transfer functions from both theories compare well with the experimental results. The experimental and computational natural frequencies decreased with increasing crack length. Furthermore the Euler–Bernoulli and Timoshenko beam theories resulted in approximately the same decrease in the natural frequency with increasing crack length as experimentally measured.     

Effect of viscous dissipation on the mixed convection heat transfer from an exponentially stretching surface

The mixed convection flow and heat transfer from an exponentially stretching vertical surface in a quiescent fluid is analyzed using similarity solution technique. Wall temperature and stretching velocity are assumed to have specific exponential function forms. The influence of buoyancy along with viscous dissipation on the convective transport in the boundary layer region is analyzed in both aiding and opposing flow situations. The flow is governed by the mixed convection parameter Gr/Re². The velocity and temperature inside the boundary layer are observed to be influenced by the parameters like Prandtl number Pr, Gebhart number Gb. Significant changes are observed in non-dimensional skin friction and heat transfer coefficients due to viscous dissipation in the medium. The flow and temperature distributions inside the boundary layer are analyzed and the results for non-dimensional skin friction and heat transfer coefficients are discussed through computer generated plots.     

A three-dimensional edge-crack finite element for fracture mechanics applications

A three-dimensional extension of a previously published two-dimensional cracked finite element [Potirniche, G.P., Hearndon, J., Daniewicz, S.R., Parker, D., Cuevas, P., Wang, P.T., Horstemeyer, M.F., 2008. A two-dimensional damaged finite element for fracture applications. Engineering Fracture Mechanics 17(13), 3895–3908] is presented in this paper. The new element has an embedded edge crack, and was developed to model damage in three-dimensional structures using the finite element method. The element simulates the presence of a crack without physically inserting it in the three-dimensional finite element mesh. The method involves the derivation of a modified stiffness matrix that accounts for the change in the element flexibility due to the crack presence. The cracked element was analytically formulated and implemented in the finite element code ABAQUS Standard as a User-defined Element (UEL) subroutine. Tests of various cracked beam configurations were used to estimate the accuracy of the element by comparing two models: one with a UEL and another with an embedded edge crack. Beam deflections and natural frequencies were analyzed and compared for the two models. The results indicate that the new element has a good potential in modeling cracks in three-dimensional parts. Moreover, the method using this UEL computes the global response of damaged structures, in which cracks can be placed at various locations and in an unlimited number.