1,3-Dipolar cycloaddition reaction of ?,?-unsaturated esters and lactones with diazomethane

1,3-Dipolar cycloaddition of diazomethane to the alpha,beta-unsaturated esters and lactones such as 2-4, 6-8, 10 and 13 occurs in a stereoselective manner affording conjugated Delta(2)-pyrazolines. E and Z isomers of D-mannitol lead to identical product which was cyclised to investigate the absolute stereochemistry of the product. The regiospecificities of all the reactions are consistent with FMO coefficients obtained through AM1 calculations.

Collective Effects on Single Particle Orientational Relaxation in Slow Dipolar Liquids

Theoretical and computer simulation studies of orientational relaxation in dense molecular liquids are presented. The emphasis of the study is to understand the effects of collective orientational relaxation on the single-particle orientational dynamics. The theoretical analysis is based on a recently developed molecular hydrodynamic theory which allows a self-consistent description of both the collective and the single-particle orientational relaxation. The molecular hydrodynamic theory can be used to derive a relation between the memory function for the collective orientational correlation function and the frequency-dependent dielectric function. A novel feature of the present work is the demonstration that this collective memory function is significantly different from the single-particle rotational friction. However, a microscopic expression for the single-particle rotational friction can be derived from the molecular hydrodynamic theory where the collective memory function can be used to obtain the single-particle orientational friction. This procedure allows, us to calculate the single-particle orientational correlation function near the alpha-beta transition in the supercooled liquid. The calculated correlation function shows an interesting bimodal decay below the bifurcation temperature as the glass transition is approached from above. Brownian dynamics simulations have been carried out to check the validity of the above procedure of translating the memory function from the dielectric relaxation data. We have also investigated the following two issues important in understanding the orientational relaxation in slow liquids. First, we present an analysis of the ''orientational caging'' of translational motion. The value of the translational friction is found to be altered significantly by the orientational caging. Second, we address the question of the rank dependence of the dielectric friction using both simulation and the molecular hydrodynamic theory.

Self-consistent microscopic treatment of the effects of self-motion of the probe on ionic and dipolar solvation dynamics

A simple but self-consistent microscopic theory for the time dependent solvation energy of both ions and dipoles is presented which includes, for the first time, the details of the self-motion of the probe on its own solvation dynamics. The theory leads to several interesting predictions. The most important of them is that, for dipolar solvation, both the rotational and the translational motions of the dipolar solute probe can significantly accelerate the rate of solvation. In addition, the rotational self-motion of the solute can also give rise to an additional mechanism of nonexponentiality in solvation time correlation functions in otherwise slow liquids. A comparison between the present theoretical predictions and the recent experimental studies of Maroncelli et al. on solvation dynamics of aniline in l-propanol seems to indicate that the said experiments have missed the initial solvent response up to about 45 ps. After mapping the experimental results on the redefined time scale, the theoretical results can explain the experimental results for solvation of aniline in 1-propanol very well. For ionic solvation, the translational motion is significant for light solutes only. For example, for Li+ in water, translational motion speeds up the solvation by about 20%. The present theory demonstrates that in dipolar solvation the partial quenching of the self-motion due to the presence of specific solute-solvent interactions (such as H-bonding) may lead to a much slower solvation than that when the self-motion is present. This point has been discussed. In addition, we present the theoretical results for solvation of aniline in propylene carbonate, Here, the solvation is predicted to be complete within 15-20 ps.

Orientational relaxation in dipolar systems: How much do we understand the role of correlations

Dipolar systems, both liquids and solids, constitute a class of naturally abundant systems that are important in all branches of natural science. The study of orientational relaxation provides a powerful method to understand the microscopic properties of these systems and, fortunately, there are many experimental tools to study orientational relaxation in the condensed phases. However, even after many years of intense research, our understanding of orientational relaxation in dipolar systems has remained largely imperfect. A major hurdle towards achieving a comprehensive understanding is the long range and complex nature of dipolar interactions which also made reliable theoretical study extremely difficult. These difficulties have led to the development of continuum model based theories, which although they provide simple, elegant expressions for quantities of interest, are mostly unsatisfactory as they totally neglect the molecularity of inter-molecular interactions. The situation has improved in recent years because of renewed studies, led by computer simulations. In this review, we shall address some of the recent advances, with emphasis on the work done in our laboratory at Bangalore. The reasons for the failure of the continuum model, as revealed by the recent Brownian dynamics simulations of the dipolar lattice, are discussed. The main reason is that the continuum model predicts too fast a decay of the torque-torque correlation function. On the other hand, a perturbative calculation, based on Zwanzig's projection operator technique, provides a fairly satisfactory description of the single particle orientational dynamics for not too strongly polar dipolar systems. A recently developed molecular hydrodynamic theory that properly includes the effects of intermolecular orientational pair correlations provides an even better description of the single-particle orientational dynamics. We also discuss the rank dependence of the dielectric friction. The other topics reviewed here includes dielectric relaxation and solvation dynamics, as they are intimately connected with orientational relaxation. Recent molecular dynamics simulations of the dipolar lattice are also discussed. The main theme of the present review is to understand the effects of intermolecular interactions on orientational relaxation. The presence of strong orientational pair correlation leads to a strong coupling between the single particle and the collective dynamics. This coupling can lead to rich dynamical properties, some of which are detailed here, while a major part remains yet unexplored.

Surface resistance and residual losses of Ag?doped YBa2Cu3O7?? thin films on sapphire

High?quality Ag?doped YBa2Cu3O7?? thin films have been grown by laser ablation on R?plane ?1102? sapphire without any buffer layer. Thin films have been found to be highly c?axis oriented with Tc=90 K, transition width ?T?1 K, and transport Jc=1.2×106 A?cm?2 at 77 K in self?field conditions. The microwave surface resistance of these films measured on patterned microstrip resonators has been found to be 530 ?? at 10 GHz at 77 K which is the lowest reported on unbuffered sapphire. Improved in?plane epitaxy and reduced reaction rate between the substrate and the film caused due to Ag in the film are believed to be responsible for this greatly improved microwave surface resistance. © 1995 American Institute of Physics.

Residual strength and fatigue life assessment of composite patch repaired specimens

Design, analysis and technology for the integrity enhancement of damaged or underdesigned structures continues to be an engineering challenge. Bonded composite patch repairs to metallic structures is receiving increased attention in the recent years. It offers various advantages over rivetted doubler, particularly for airframe repairs. This paper presents an experimental investigation of residual strength and fatigue crack-growth life of an edge-cracked aluminium specimen repaired using glass epoxy composite patch. The investigation begins with the evaluation of three different surface treatments from bond strength viewpoint. A simple thumb rule formula is employed to estimate the patch size. Cracked and repaired specimens are tested under static and fatigue loading. The patch appears to restore the original strength of the undamaged specimen and enhance the fatigue crack growth life by an order of magnitude. (C) 1999 Elsevier Science Ltd. All rights reserved.

Solvation dynamics of a quadrupolar solute in dipolar liquids

A microscopic calculation of solvation dynamics of dipolar and quadrupolar solutes in liquid water and acetonitrile is presented. The solvation is found to he biphasic. The calculated solvation time correlation function of ionic quadrupolar solute (K+) in water is in good agreement with re cent computer simulation results. Present study reveals some interesting aspects of quadrupolar solvation dynamics which differ significantly from that of ionic and dipolar solvation.

Vector summed sine wave tailored waveforms for dipolar excitation of ions in Paul trap mass spectrometers

A simple method to generate time domain tailored waveforms for excitation of ion axial amplitude in Paul trap mass spectrometers is described. The method is based on vector summation of sine waves followed by time domain sampling to obtain the discrete time domain data. A smoothing technique based on the time domain Kaiser window is then applied to the data so as to minimize the frequency domain Gibb's oscillations. The dynamic range of the time domain signal is controlled by phase modulation and time extension of the time domain waveform. Copyright (C) 1999 John Wiley & Sons, Ltd.

Collapse behaviour of a residual soil

Residually derived red soils occur in Bangalore District of Karnataka State, India. The porous and unsaturated nature of the red soils makes them susceptible to collapse on wetting under load. The present study analyses the collapse behaviour of an unsaturated bonded (undisturbed) red soil from Bangalore referenced to tests on samples in an unbonded (remoulded) state. A filter paper method was used to determine the matric suction of the bonded and unbonded specimens, and mercury intrusion porosimetry (MIP) was used to determine their soil structure. Analysis of the experimental results shows that bonding plays an important role in the collapse behaviour of the unsaturated residual soil. The results of the study also provide insight into the volume change behaviour of unsaturated bonded soils on wetting within and beyond the yield locus.

Cross-polarization from the dipolar reservoir under the mismatched Hartmann-Hahn condition

Cross-polarization from the dipolar reservoir for a range of mismatched Hartmann-Hahn conditions has been considered. Experiment, in general, agrees with the dispersive Lorentzian behavior expected on the basis of quasi-equilibrium theory. It is observed that inclusion of additional mechanisms of polarization transfer lead to an improvment of the fit of the experimental results. The utility of extending the technique to the case of ordered long chain molecules, such as liquid crystals, for the measurement of the local dipolar field is also presented. (C) 2002 Elsevier Science (USA).

Fully Comprehensive Geometrically Non-Linear Dynamic Analysis of Multi-Body Beam Systems with Elastic Couplings

This paper is concerned with the dynamic analysis of flexible,non-linear multi-body beam systems. The focus is on problems where the strains within each elastic body (beam) remain small. Based on geometrically non-linear elasticity theory, the non-linear 3-D beam problem splits into either a linear or non-linear 2-D analysis of the beam cross-section and a non-linear 1-D analysis along the beam reference line. The splitting of the three-dimensional beam problem into two- and one-dimensional parts, called dimensional reduction,results in a tremendous savings of computational effort relative to the cost of three-dimensional finite element analysis,the only alternative for realistic beams. The analysis of beam-like structures made of laminated composite materials requires a much more complicated methodology. Hence, the analysis procedure based on Variational Asymptotic Method (VAM), a tool to carry out the dimensional reduction, is used here.The analysis methodology can be viewed as a 3-step procedure. First, the sectional properties of beams made of composite materials are determined either based on an asymptotic procedure that involves a 2-D finite element nonlinear analysis of the beam cross-section to capture trapeze effect or using strip-like beam analysis, starting from Classical Laminated Shell Theory (CLST). Second, the dynamic response of non-linear, flexible multi-body beam systems is simulated within the framework of energy-preserving and energy-decaying time integration schemes that provide unconditional stability for non-linear beam systems. Finally,local 3-D responses in the beams are recovered, based on the 1-D responses predicted in the second step. Numerical examples are presented and results from this analysis are compared with those available in the literature.