Crystalline-amorphous interaction in relation to the phase diagrams of binary polymer blends containing a crystalline constituent

The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.     

Robust Shape Fitting via Peeling and Grating Coresets

Let P be a set of n points in ℝ ^d . A subset of P is called a (k,ε)-kernel if for every direction, the directional width of ε-approximates that of P, when k “outliers” can be ignored in that direction. We show that a (k,ε)-kernel of P of size O(k/ε ^(d−1)/2) can be computed in time O(n+k ²/ε ^d−1). The new algorithm works by repeatedly “peeling” away (0,ε)-kernels from the point set. We also present a simple ε-approximation algorithm for fitting various shapes through a set of points with at most k outliers. The algorithm is incremental and works by repeatedly “grating” critical points into a working set, till the working set provides the required approximation. We prove that the size of the working set is independent of n, and thus results in a simple and practical, near-linear ε-approximation algorithm for shape fitting with outliers in low dimensions. We demonstrate the practicality of our algorithms by showing their empirical performance on various inputs and problems. A preliminary version of this paper appeared in Proceedings of the 17th Annual ACM-SIAM Symposium on Discrete Algorithms, pp. 182–191. P.A. and H.Y. are supported by NSF under grants CCR-00-86013, EIA-01-31905, CCR-02-04118, and DEB-04-25465, by ARO grants W911NF-04-1-0278 and DAAD19-03-1-0352, and by a grant from the U.S.–Israel Binational Science Foundation. S.H.-P. is supported by a NSF CAREER award CCR-0132901.     

Terahertz spectroscopy studies on epitaxial vanadium dioxide thin films across the metal-insulator transition

We present results on terahertz (THz) spectroscopy on epitaxial vanadium dioxide (VO(2)) films grown on sapphire across the metal-insulator transition. X-ray diffraction indicates the VO(2) film is highly oriented with the crystallographic relationship: (002)(film)//(0006)(sub) and [010](film)//[2 ?1 ?10](sub). THz studies measuring the change in transmission as a function of temperature demonstrate an 85% reduction in transmission as the thin film completes its phase transition to the conducting phase, which is much greater than the previous observation on polycrystalline films. This indicates the crucial role of microstructure and phase homogeneity in influencing THz properties.     

Visible light-mediated photocatalyzed synthesis of oxazole via intermolecular C?N and C?O bond formation

An efficient visible light-mediated, eosin Y-catalyzed synthesis of oxazole has been developed from benzil with primary amines, that providing a straightforward, green, and environmentally benign access to a wide variety of substituted oxazole-2-amines under mild reaction conditions.     

DNA binding, nuclease activity and cytotoxicity studies of Cu(II) complexes of tridentate ligands

Cu(II) complexes of three tridentate ligands, L(1), L(2) and L(3), [L(1), N-((1H-imidazole-2-yl)methyl)-2-(pyridine-2-yl)ethanamine; L(2), N-((1-methyl-1H-imidazole-2-yl)methyl)-2-(pyridine-2-yl)ethanamine; L(3), 2-(pyridine-2-yl)-N-((pyridine-2-yl)methyl)ethanamine] respectively, were synthesized and characterized. The single crystal X-ray structure of complex 1 reveals the pseudo octahedral coordination geometry around the copper center. Absorption and fluorescence experimental evidence show good DNA binding propensity (in the order of 10(5) M(-1)) of the complexes. Thermal denaturation and circular dichroism (CD) analyses reveal minor structural changes of calf thymus (CT) DNA in presence of complexes and groove and/or surface binding of the complexes to CT-DNA. Kinetic DNA cleavage assay shows pseudo-first-order kinetic reaction between the complex and supercoiled (SC) DNA. In addition, mechanistic SC DNA cleavage results show higher DNA cleavage activity in presence of reducing agent, due to the presence of hydroxyl radicals. In vitro cytotoxicity assay of the complexes demonstrate that the complexes have low toxicity for different cancer cell lines and IC(50) values were between 37 and 156 μM.     

Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: putative formation of a copper(I)-peroxynitrite intermediate

The reaction of a Cu(II)-nitrosyl complex (1) with hydrogen peroxide at -20 °C in acetonitrile results in the formation of the corresponding Cu(I)-peroxynitrite intermediate. The reduction of the Cu(II) center was monitored by UV-visible spectroscopic studies. Formation of the peroxynitrite intermediate has been confirmed by its characteristic phenol ring nitration reaction as well as isolation of corresponding Cu(I)-nitrate (2). On air oxidation, 2 resulted in the corresponding Cu(II)-nitrate (3). Thus, these results demonstrate a possible decomposition pathway for H(2)O(2) and NO through the formation of a peroxynitrite intermediate in biological systems.     

One-pot stibine modified Co2(CO)8 catalyzed reductive N-alkylation of primary amides with carbonyl compounds

A one-pot stibine modified Co₂(CO)₈ homogeneous catalytic reductive N-alkylation of primary amides using aldehydes/ketones as alkylating agents, is reported. Good to excellent yields of a wide range of secondary amides are obtained (up to 97%) under relative mild conditions.     

(0,1 ;0)-INTERPOLATION ON INFINITE INTERVAL (-∞, +∞)

In this paper, we study the explicit representation and convergence of (0, 1; 0)-interpolation on infinite interval, which means to determine a polynomial of degree ≤ 3n - 2 when the function values are prescribed at two set of points namely the zeros of Hn(x) and H′n(x) and the first derivatives at the zeros of H′n(x).     

Pair correlation functions in nematics: Free-energy functional and isotropic-nematic transition

We develop a free-energy functional for an inhomogeneous system that contains both symmetry conserved and symmetry broken parts of the direct pair correlation function. These correlation functions are found by solving the Ornstein-Zernike equation with the Percus-Yevick closure relation. The method developed here gives the pair correlation functions in the ordered phase with features that agree well with the results found by computer simulations. The theory predicts accurately the isotropic-nematic transition in a system of anisotropic molecules and can be extended to study other ordered phases such as smectics and crystalline solids.