Pyridine-catalyzed addition of diaryl-1,2-diones to dimethyl butynedioate leading to the formation of 1,2-diaroyl dimethyl maleates via an unprecedented rearrangement

[reaction: see text] Pyridine catalyzes the reaction of 1,2-diaryl diones with dimethyl butynedioate to afford diaroyl maleates. This unprecedented rearrangement involves a unique benzoyl migration and proceeds with complete stereoselectivity.     

Model for heat conduction in nanofluids

A comprehensive model has been proposed to account for the large enhancement of thermal conductivity in nanofluids and its strong temperature dependence, which the classical Maxwellian theory has been unable to explain. The dependence of thermal conductivity on particle size, concentration, and temperature has been taken care of simultaneously in our treatment. While the geometrical effect of an increase in surface area with a decrease in particle size, rationalized using a stationary particle model, accounts for the conductivity enhancement, a moving particle model developed from the Stokes-Einstein formula explains the temperature effect. Predictions from the combined model agree with the experimentally observed values of conductivity enhancement of nanofluids.     

Elastic deformation of polycrystals

We propose a framework to model elastic properties of polycrystals by coupling crystal orientational degrees of freedom with elastic strains. Our model encodes crystal symmetries and takes into account explicitly the strain compatibility induced long-range interaction between grains. The coupling of crystal orientation and elastic interactions allows for the rotation of individual grains by an external load. We apply the model to simulate uniaxial tensile loading of a 2D polycrystal within linear elasticity and a system with elastic anharmonicities that describe structural phase transformations. We investigate the constitutive response of the polycrystal and compare it to that of single crystals with crystallographic orientations that form the polycrystal.     

Metal nanoplasmas as bright sources of hard X-ray pulses

We report significant enhancements in light coupling to intense-laser-created solid plasmas via surface plasmon and "lightning rod" effects. We demonstrate this in metal nanoparticle-coated solid targets irradiated with 100 fs, 806 nm laser pulses, focused to intensities approximately 10(14)-10(15) W cm(-2). Our experiments show a 13-fold enhancement in hard x-ray yield (10-200 keV) emitted by copper nanoparticle plasmas formed at the focal volume. A simple model explains the observed enhancement quantitatively and provides pointers to the design of structured surfaces for maximizing such emissions.     

Measurements of electron-transfer rates of charge-storage molecular monolayers on Si(100). Toward hybrid molecular/semiconductor information storage devices

Redox kinetics were measured for two electroactive molecules attached to Si(100) surfaces, a ferrocene (Fc-BzOH) and a Zn(II) trimesitylporphyrin (Por-BzOH). Each molecule was derivatized with a benzyl alcohol linker for attachment to the Si surface via the formation of a Si-O bond. A complete protocol was developed for the preparation of stable Si(100) surfaces derivatized with the electroactive molecules. The redox-kinetic measurements were performed on the resulting Fc-BzOH and Por-BzOH monolayers to probe (1) the rate of electron transfer (k0) for oxidation in the presence of applied potentials and (2) the rate of charge dissipation after the applied potential is disconnected (in the form of a charge-retention half-life t1/2). The k0 values for the two types of monolayers were found to be similar to one another as were the t1/2 values. Perhaps more importantly, the electron-transfer rates for both the Fc-BzOH and the Por-BzOH monolayers differ from the charge-dissipation rates by approximately 6 orders of magnitude and are strongly dependent on the surface concentration of the electroactive species. For the Por-BzOH monolayers on Si(100), the k0 and t1/2 values and their trends as a function of surface coverage were determined to be similar to those previously measured for the analogous thiol-derivatized molecule assembled on Au(111). In contrast, the Fc-BzOH monolayers on Si(100) were found to exhibit much slower electron-transfer and charge-dissipation rates than those in the corresponding thiol-Au(111) case. Two alternative hypotheses are advanced to explain both the diminution in rates with increased surface coverage and the contrasting behavior with the analogous thiols on Au, one based on space-charge effects at the monolayer-solution interface, and a second relying on changes in distance of the redox centers from the surface as modulated by the orientation of the linking chains. Collectively, the ability to prepare and study stable, electroactive molecular media on Si(100) is likely to be key in the development of hybrid molecular/semiconductor devices.     

Utilization of the BARC critical facility for ADS related experiments

The paper discusses the basic design of the critical facility, whose main purpose is the physics validation of AHWR. Apart from moderator level control, the facility will have shutdown systems based on shutoff rods and multiple ranges of neutron detection systems. In addition, it will have a flux mapping system based on 25 fission chambers, distributed in the core. We are planning to use this reactor for experiments with a suitable source to simulate an ADS system. Any desired sub-criticality can be achieved by adjusting the moderator level. Apart from perfecting our experimental techniques, in simple configurations, we intend to study the one-way coupled core in this facility. Preliminary calculations, employing a Monte Carlo code TRIPOLI, are presented.      

Bubbles in DNA by random force

We model single strand binding (SSB) proteins as agents exerting randomly oriented force on the bonds in DNA unzipping. The fluctuating force is found to unzip the double stranded DNA (dsDNA) via opening of bubbles along the chain.     

Room temperature ferromagnetism and magnetotransport properties of the layered manganite system La1.2Ba1.8Mn2−xRuxO7 (0≤x≤1.0)

The dc magnetization and ac susceptibility measurements on two dimensional layered manganite La_1.2Ba_1.8Mn₂O₇ samples reveal the occurrence of ferromagnetism above room temperature with ferromagnetic (FM) to paramagnetic (PM) transitions at 338 K. The bifurcation temperatures shown by the zero-field cooled (ZFC) and field cooled (FC) dc magnetization curves at high temperatures shift towards lower temperatures as the applied field is increased from 100 to 2500 Oe. The data are suggestive of a large magnetic anisotropy due to the strong competing ferromagnetic and antiferromagnetic interactions resulting in a spin-glass-like state. Ru doping is found to enhance the ferromagnetism and metallicity of the system in a remarkable way. The magnetoresistance (MR) values obtained are very high and about 40% even at 260 K for the undoped sample.     

A canonical formulation of dissipative mechanics using complex-valued hamiltonians

We show that a large class of dissipative systems can be brought to a canonical form by introducing complex co-ordinates in phase space and a complex-valued hamiltonian. A naive canonical quantization of these systems lead to non-hermitean hamiltonian operators. The excited states are unstable and decay to the ground state. We also compute the tunneling amplitude across a potential barrier by solving the dissipative version of the Schrödinger equation. We then generalize the formalism to cases where the configuration space is a curved Riemannian manifold.     

Cotunnite-Structured Titanium Dioxide and the Hardest known Oxide

Combined theoretical and experimental investigations led to the discovery of a new polymorph of titanium dioxide with titanium nine-coordinated to oxygen in the cotunnite (PbCl 2 ) structure. Hardness measurements on the cotunnite-structured TiO 2 synthesized at pressures above 60 GPa and temperatures above 1000 K reveal that this material is the hardest oxide yet discovered. Furthermore, it is one of the least compressible (with a measured bulk modulus of 431 GPa) and hardest (with a microhardness of 38 GPa) polycrystalline materials studied thus far.