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.     

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.     

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.     

New stibines containing acetal and formyl group: Platinum complex and unexpected oxastibol derivative

A new tertiary stibine ligand (1) containing acetal group at the ortho-position has been synthesized. This new stibine was then complexed with to obtain trans-PtCl₂L₂ (2) where stibine acts as a monodentate ligand. The acetal was hydrolyzed in a slightly acidic medium and forms a very new stibine (3) containing formyl group at the ortho-position. When (3) was reduced with NaBH₄ an unusual oxastibol (4) derivative was obtained under the experimental conditions used.All the compounds were characterized by IR, mass, ¹H, ¹³C, COSY and HETCOR NMR spectroscopy. The molecular structures of (2), (3) and (4) were determined. Compound (3) crystallizes in two different polymorphs (3a) and (3b) and both the polymorphs show hypervalent antimony with three Sb?O interactions and the molecule exists in O-cis-exo configuration. Compound (4) shows intramolecular Sb?O interactions. To the best of our knowledge this is the first report on organoantimony compounds containing carbonyl groups though their phosphorus and bismuth analogues are well known. Compound (2) shows helicoidal chirality, which is a very new concept in antimony chemistry     

Gas chromatography electron ionization mass spectrometric analysis of trimethylsilyl derivatives of bis(2-hydroxyethylthio)alkanes and bis(2-hydroxyethylsulfonyl) alkanes

This communication describes GC-MS analysis of bis(trimethylsilyl) (bis-TMS) derivatives of bis(2-hydroxyethylthio)alkanes (BHETAs) and bis(2-hydroxyethylsulfonyl) alkanes (BHESAs) which are important markers of sulfur mustard class of chemical warfare agents. The study was undertaken with a view to develop spectral database of these compounds for verification analysis of Chemical Weapons Convention (CWC). Based on the obtained mass spectra of bis-TMS derivatives of BHETAs and BHESAs, the fragmentation routes are proposed, which explain most of the characteristic ions.     

Direct calculation of solid-vapor coexistence points by thermodynamic integration: application to single component and binary systems

We present a new thermodynamic integration method that directly connects the vapor and solid phases by a reversible path. The thermodynamic integration in the isothermal-isobaric ensemble yields the Gibbs free energy difference between the two phases, from which the sublimation temperature can be easily calculated. The method extends to the binary mixture without any modification to the integration path simply by employing the isothermal-isobaric semigrand ensemble. The thermodynamic integration, in this case, yields the chemical potential difference between the solid and vapor phases for one of the components, from which the binary sublimation temperature can be calculated. The coexistence temperatures predicted by our method agree well with those in the literature for single component and binary Lennard-Jones systems.     

Microemulsion mediated in situ derivatization-extraction and gas chromatography-mass spectrometric analysis of alkylphosphonic acids

Detection and identification of environmental signatures of chemical warfare agents is an important aspect of verification program of Chemical Weapons Convention (CWC). Alkylphosphonic acids (APAs) are ultimate and persistent degradation products of nerve agents. Their identification in a sample submitted for off-site analysis infers possible indication of contamination with nerve agents. This paper describes the development of a new sample preparation method which involves 'in situ derivatization and extraction' (INDEX) of acids from water. Derivatization is performed by alkylation of APAs with alkylbromides in surfactant less microemulsion (SLME). The derivatized analytes were analyzed by gas chromatography coupled with mass spectrometry. The developed method involves simultaneous derivatization (alkylation) and extraction of acidic analytes mediated by surfactant less microemulsion. Various derivatization-extraction parameters such as solvent, reaction time and temperature, base and alkyl bromides were optimized. Pentyl bromide in the presence of potassium carbonate and diisopropylamine at 100 degrees C derivatized the selected acids efficiently. Kinetic data for alkylation of methylphosphonic acids and some carboxylic acids were obtained to assess their relative susceptibility for alkylation in microemulsion. Methylphosphonic acid and isopropyl methylphosphonic acid took 140-150 min to reach completion while carboxylic acids took 100 min to complete the reaction. INDEX could be successfully performed even in the presence of interfering Ca(2+) and Mg(2+) ions.