A note on the choice of interfacial friction angle

Estimates of interfacial friction angle (delta) are necessary for the design of retaining structures and deep foundations, Recommendations in the literature regarding delta values are often contradictory and are therefore not easy to apply in geotechnical design, A critical examination of past studies in terms of data generation techniques used and conclusions drawn indicates that two distinctly different test procedures/techniques have been evolved. The interfacial situation in practice can also be categorized into two broad types, These two types of interface problems in geotechnical engineering are (a) the structure is placed on the free surface of prepared fill (type A situation) and (b) the fill is placed against the material surface which functions as a confined boundary (type B situation), The friction angle delta depends on the surface roughness of the construction material, But in the type A situation, it is independent of density and its limiting maximum value (delta(lim)) is the critical state friction angle phi(cv). In the type B situation, it is dependent on density of the fill and its limiting maximum value is the peak angle of internal friction phi(p) of the fill.

Asymptotic and finite element analyses of mode III dynamic crack growth at a ductile-brittle interface

In this work, dynamic crack growth along a ductile-brittle interface under anti-plane strain conditions is studied. The ductile solid is taken to obey the J(2) flow theory of plasticity with linear isotropic strain hardening, while the substrate is assumed to exhibit linear elastic behavior. Firstly, the asymptotic near-tip stress and velocity fields are derived. These fields are assumed to be variable-separable with a power singularity in the radial coordinate centered at the crack tip. The effects of crack speed, strain hardening of the ductile phase and mismatch in elastic moduli of the two phases on the singularity exponent and the angular functions are studied. Secondly, full-field finite element analyses of the problem under small-scale yielding conditions are performed. The validity of the asymptotic fields and their range of dominance are determined by comparing them with the results of the full-field finite element analyses. Finally, theoretical predictions are made of the variations of the dynamic fracture toughness with crack velocity. The influence of the bi-material parameters on the above variation is investigated.

Metal-Free Deprotection of Terminal Acetonides by Using tert-Butyl Hydroperoxide in Aqueous Medium

Employing aqueous tert-butyl hydroperoxide (70%) as an inexpensive reagent a useful methodology for the regioselective and chemoselective deprotection of terminal acetonide groups in aqueous medium is developed. A variety of acetonide derivatives on reaction with aqueous tert-butyl hydroperoxide in water:tert-butanol (1:1) furnish the corresponding acetonide deprotected diols in good yields. A large number of acid labile protecting functional groups and other functional moieties were found to be unaffected under the conditions employed for the present deprotection. This method has been successfully applied to sugar derivatives.

Gas-liquid nucleation at large metastability: unusual features and a new formalism

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Lectin binding to complex carbohydrate at the interface: a study by resonance energy transfer

The binding affinity of the oligosaccharide moiety of a neutral glycosphingolipid, asialoGM1, towards Ricinus communis agglutinin (RCAI) was determined for the first time by fluorescence resonance energy transfer (RET). The asialoGM1 was incorporated into a phospholipid (DMPC) vesicle doped with dansylated DPPE and then titrated with an increasing amount of the galactose specific RCAI. The efficiency of RET was determined by a saturable increase in the quenching of 'donor' fluorescence, i.e. the 'trp' residue of RCAI, due to the energy transfer from the 'acceptor' dansyl group on the surface of the vesicle. The apparent binding constant was found to be in the range of 10(5)-10(6) M-1 at 27 degrees C.

Sequential Assembly of an Active RNA Polymerase Molecule at the Air-Water Interface

At the heart of understanding cellular processes lies our ability to explore the specific nature of communication between sequential information carrying biopolymers. However, the data extracted from conventional solution phase studies may not reflect the dynamics of communication between recognized partners as they occur in the crowded cellular milieu. We use the principle of immobilization of histidine-tagged biopolymers at a Ni(II)-encoded Langmuir monolayer to study sequence-specific protein-protein interactions in an artificially crowded environment The advantage of this technique lies in increasing the surface density of one of the interacting partners that allows us to study macromolecular interactions in a controlled crowded environment, but without compromising the speed of the reactions. We have taken advantage of this technique to follow the sequential assembly process of the multiprotein complex Escherichia coil RNA polymerase at the interface and also deciphered the role of one of the proteins, omega (omega), in the assembly pathway. Our reconstitution studies indicate that in the absence of molecular chaperones or other cofactors, omega (omega) plays a decisive role in refolding the largest protein beta prime (beta') and its recruitment into the multimeric assembly to reconstitute an active RNA polymerase. It was also observed that the monolayer had the ability to distinguish between sequence-specific and -nonspecific interactions despite the immobilization of one of the biomacromolecules. The technique provides a universal two-dimensional template for studying protein-ligand interactions while mimicking molecular crowding.

Role of free valences and spin densities on the migrating atom in location of saddle points in radical-exchange reactions

The principle of the conservation of bond orders during radical-exchange reactions is examined using Mayer's definition of bond orders. This simple intuitive approximation is not valid in a quantitative sense. Ab initio results reveal that free valences (or spin densities) develop on the migrating atom during reactions. For several examples of hydrogen-transfer reactions, the sum of the reaction coordinate bond orders in the transition state was found to be 0.92 +/- 0.04 instead of the theoretical 1.00 because free valences (or spin densities) develop on the migrating atom during reactions. It is shown that free valence is almost equal to the square of the spin density on the migrating hydrogen atom and the maxima in the free valence (or spin density) profiles coincide (or nearly coincide) with the saddle points in the corresponding energy profiles.

Solubilization of n-decane into n-decyl-polyoxyethylene surfactants: A cavity forming free energy based model

The present paper reports the results of a theoretical study of the forces and factors driving the solubilization of n-alkane solubilizates into the micellar core of some non-ionic surfactants, based on a micellar model which includes the cavity forming free energy as a component of micellization. The solubilizate is n-decane and the non-ionic surfactants considered are n-decyl-polyoxyethylene surfactants. The extent of solubilization, i.e. the mole fraction of the solubilizate within the core has been calculated. The results indicate that the incorporated solubilizate has more translational and rotational degrees of freedom as compared to those of the tail parts of the surfactants present in the core. This drives the total free energy of aggregation after solubilization into a more favourable direction. The results are in fair agreement with the experimental results.

Time scales for transitions between free-energy minima of a dense hard-sphere system

Time scales associated with activated transitions between glassy metastable states of a free-energy functional appropriate for a dense hard-sphere system are calculated by using a new Monte Carlo method for the local density variables. In particular, we calculate the time the system, initially placed in a shallow glassy minimum of the free-energy, spends in the neighborhood of this minimum before making a transition to the basin of attraction of another free-energy minimum. This time scale is found to increase as the average density is increased. We find a crossover density near which this time scale increases very sharply and becomes longer than the longest times accessible in our simulation. This time scale does not show any evidence of increasing with sample size

Engineered dimer interface mutants of triosephosphate isomerase: the role of inter-subunit interactions in enzyme function and stability

The role of inter-subunit interactions in maintaining optimal catalytic activity in triosephosphate isomerase (TIM) has been probed, using the Plasmodium falciparum enzyme as a model. Examination of subunit interface contacts in the crystal structures suggests that residue 75 (Thr, conserved) and residue 13 (Cys, variable) make the largest number of inter-subunit contacts. The mutants Cys13Asp (C13D) and Cys13Glu (C13E) have been constructed and display significant reduction in catalytic activity when compared with wild-type (WT) enzyme (similar to 7.4-fold decrease in k(cat) for the C13D and similar to 3.3-fold for the C13E mutants). Analytical gel filtration demonstrates that the C13D mutant dissociates at concentrations < 1.25 mu M, whereas the WT and the C13E enzymes retain the dimeric structure. The order of stability of the mutants in the presence of chemical denaturants, like urea and guanidium chloride, is WT > Cys13Glu > Cys13Asp. Irreversible thermal precipitation temperatures follow the same order as well. Modeling studies establish that the Cys13Asp mutation is likely to cause a significantly greater structural perturbation than Cys13Glu. Analysis of sequence and structural data for TIMs from diverse sources suggests that residues 13 and 82 form a pair of proximal sites, in which a limited number of residue pairs may be accommodated.

Exact free-surface flows for shallow-water equations .2. the compressible case

Exact free surface flows with shear in a compressible barotropic medium are found, extending the authors' earlier work for the incompressible medium. The barotropic medium is of finite extent in the vertical direction, while it is infinite in the horizontal direction. The ''shallow water'' equations for a compressible barotropic medium, subject to boundary conditions at the free surface and at the bottom, are solved in terms of double psi-series, Simple wave and time-dependent solutions are found; for the former the free surface is of arbitrary shape while for the latter it is a damping traveling wave in the horizontal direction, For other types of solutions, the height of the free surface is constant either on lines of constant acceleration or on lines of constant speed. In the case of an isothermal medium, when gamma = 1, we again find simple wave and time-dependent solutions.

Free convection in power-law fluids near a three-dimensional stagnation point

Numerical results are presented for the free-convection boundary-layer equations of the Ostwald de-Waele non-Newtonian power-law type fluids near a three-dimensional (3-D) stagnation point of attachment on an isothermal surface. The existence of dual solutions that are three-dimensional in nature have been verified by means of a numerical procedure. An asymptotic solution for very large Prandtl numbers has also been derived. Solutions are presented for a range of values of the geometric curvature parameter c, the power-law index n, and the Prandtl number Pr.

Tunable Brownian vortex at the interface

A general kind of Brownian vortices is demonstrated by applying an external nonconservative force field to a colloidal particle bound by a conservative optical trapping force at a liquid-air interface. As the liquid medium is translated at a constant velocity with the bead trapped at the interface, the drag force near the surface provides enough rotational component to bias the particle's thermal fluctuations in a circulatory motion. The interplay between the thermal fluctuations and the advection of the bead in constituting the vortex motions is studied, and we infer that the angular velocity of the circulatory motion offers a comparative measure of the interface fluctuations.

Effect of Strain Rate on Ductile-to-Brittle Transition Temperature of a Free-Standing Pt-Aluminide Bond Coat

The ductile-to-brittle transition temperature (DBTT) of a free-standing Pt-aluminide (PtAl) bondcoat was determined using the microtensile testing method and the effect of strain rate variation, in the range 10(-5) to 10(-1) s(-1), on the DBTT studied. The DBTT increased appreciably with the increase in strain rate. The activation energy determined for brittle-to-ductile transition, suggested that such transition is most likely associated with vacancy diffusion. Climb of aOE (c) 100 > dislocations observed in analysis of dislocation structure using a transmission electron microscope (TEM) supported the preceding mechanism.

Some results on the reconstruction problems. p-claw-free, chordal, and p4-reducible graphs

A claw is an induced subgraph isomorphic to K-1,K-3. The claw-point is the point of degree 3 in a claw. A graph is called p-claw-free when no p-cycle has a claw-point on it. It is proved that for p greater than or equal to 4, p-claw-free graphs containing at least one chordless p-cycle are edge reconstructible. It is also proved that chordal graphs are edge reconstructible. These two results together imply the edge reconstructibility of claw-free graphs. A simple proof of vertex reconstructibility of P-4-reducible graphs is also presented. (C) 1995 John Wiley and Sons, Inc.