Intramolecular nitrone cycloaddition reaction on carbohydrate-based precursors: application in the synthesis of spironucleosides and spirobisnucleosides

A simple synthesis of chiral spironucleosides and spirobisnucleosides is described. Intramolecular 1,3-dipolar nitrone cycloaddition reaction of d-glucose-derived precursors having olefin at C-3 and nitrone at C-5, C-1, or C-2 (in nor-series) furnished bisisoxazolidinospirocycles 4-7, 11, and 12 in good yields. Reductive ring opening of the isoxazolidine moieties in 4-6 followed by construction of a nucleoside base upon the generated amino groups smoothly yielded spirobisnucleosides 17 and 18 and spironucleosides 20 and 21.     

Influence of branch length asymmetry on the electrophoretic mobility of rigid rod-like DNA

The electrophoretic mobility of three-arm asymmetric star DNA molecules, produced by incorporating a short DNA branch at the midpoint of rigid-rod linear DNA fragments, is investigated in polyacrylamide gels. We determine how long the added branch must be to separate asymmetric star DNA from linear DNA with the same total molecular weight. This work focuses on two different geometric progressions of small DNA molecules. First, branches of increasing length were introduced at the center of a linear DNA fragment of constant length. At a given gel concentration, we find that relatively small branch lengths are enough to cause a detectable reduction in electrophoretic mobility. The second geometric progression starts with a small branch on a linear DNA fragment. As the length of this branch is increased, the DNA backbone length is decreased such that the total molar mass of the molecule remains constant. The branch length was then increased until the asymmetric branched molecule becomes a symmetric three-arm star polymer, allowing the effect of molecular topology on mobility to be studied independent of size effects. DNA molecules with very short branches have a mobility smaller than linear DNA of identical molar mass. The reason for this change in mobility when branching is introduced is not known, however, we explore two possible explanations in this article. (i) The branched DNA could have a greater interaction with the gel than linear DNA, causing it to move slower; (ii) the linear DNA could have modes of motion or access to pores that are unavailable to the branched DNA.     

Study of approximate coupled cluster methods for first-order static properties

In this paper, we analyse the algebraic structure of the equations for calculating the first order static properties using several approximate versions of Coupled Cluster (CC) methods. In particular, the non-variational and the variational method using a CC wavefunction corresponding to an appropriately defined perturbed Hamiltonian as well as the simple expectation value expression using a CC stationary state are studied under different approximations. Two different models are proposed: (a) use of maximum overlap orbitals where the pertinent approximations are TT ₂, T ⁽¹⁾ T ₂ ⁽¹⁾, (b) use of Hartree-Fock orbitals and T(T ₁+T ₂), T ⁽¹⁾(T ₁ ⁽¹⁾ +T ₂ ⁽¹⁾ ) approximations. It is analytically shown that in both these models certain approximate versions of the methods under purview yield identical results for first order static properties.NCL Communication No. 3725     

Sunlight assisted solvent free synthesis of tert-butylperesters

Abstract

A green and efficient methodology has been developed for the direct conversion of aryl aldehydes to the corresponding tert-butyl peresters. The reaction has been carried out in absence of any solvent and the sunlight is used as the green source of energy. In this reaction tetrabutylammonium iodide (TBAI) acts as the mild organo catalyst and tert-butyl hydroperoxide (TBHP) serve as the source of tert-butyl group.     

A variational coupled cluster theory for closed shells using a propagator modification procedure

A general partial summation method for including arbitrary classes of diagrams to all orders in the coupled cluster based size consistent energy functional for closed shell states is developed. Since the various reduced density matrices which appear in the energy functional are essentially the time-independent analogues of the corresponding many body Green functions, it is possible to derive Dyson-like equations for these quantities. By expanding the associated proper self energy parts in terms of the T-amplitudes, one can carry out partial summations in the reduced density matrices and thus in energy. At a higher level, higher order terms in a proper self energy can also be generated by renormalizing the internal propagators in it, and considering only the irreducible self-energy terms.     

Electrophoretic dynamics of large DNA stars in polymer solutions and gels

We have developed a procedure for synthesizing large stable branched DNA structures that enables visualization via fluorescence microscopy. Using this procedure we have synthesized large DNA stars and observed their electrophoretic behavior in polymer solutions and gels. In dilute polyacrylamide solutions, the DNA stars move as random coils and appear to experience only brief collisions with the polymer chains in solution. The effect of polymer solution concentration on the electrophoretic mobility of stars in the dilute regime is found to be in good accord with predictions of the transient entanglement coupling (TEC) model. In semidilute polymer solutions, the star arms extend in the field direction and drag the core through the matrix. The star arms form several U-shaped conformations as they collide and engage with polyacrylamide chains. The U-shaped conformations occasionally evolve into J-shaped conformations as the star arms slide off the matrix chains they engage during electrophoretic migration. In concentrated polymer solutions, the arms of the star extend and form V-shaped structures with the core as the apex. The arms then pull the core through the matrix. These V-shaped conformations are much longer-lived than U-shaped ones and, unlike the latter, do not transform to J-shaped conformations. In polyacrylamide and agarose gels, where matrix entanglements are fixed, DNA stars become trapped when entanglements with matrix molecules prevent the core from being pulled through the matrix by the extended arms. This trapping was observed at all gel concentrations and electric fields studied.     

Strain rate effects on the mechanical behavior of two Dual Phase steels in tension

This paper presents an experimental investigation on the strain rate sensitivity of Dual Phase steel 1200 (DP1200) and Dual Phase steel 1400 (DP1400) under uni-axial tensile loads in the strain rate range from 0.001?s^?1 to 600?s^?1. These materials are advanced high strength steels (AHSS) having high strength, high capacity to dissipate crash energy and high formability. Flat sheet specimens of the materials having gauge length 10?mm, width 4?mm and thickness 2?mm (DP1200) and 1.25?mm (DP1400), are tested at room temperature (20^°C) on electromechanical universal testing machine to obtain their stress-strain relation under quasi-static condition (0.001?s^?1), and on Hydro-Pneumatic machine and modified Hopkinson bar to study their mechanical behavior at medium (3?s^?1, and 18?s^?1) and high strain rates (200?s^?1, 400?s^?1, and 600?s^?1) respectively. Tests under quasi-static condition are performed at high temperature (200^°C) also, and found that tensile flow stress is a increasing function of temperature. The stress-strain data has been analysed to determine the material parameters of the Cowper-Symonds and the Johnson-Cook models. A simple modification of the Johnson-Cook model has been proposed in order to obtain a better fit of tests at high temperatures. Finally, the fractographs of the broken specimens are taken by scanning electron microscope (SEM) to understand the fracture mechanism of these advanced high strength steels at different strain rates.