Nucleation studies and characterization of potassium thiocyanate added KDP crystals grown by seed rotation technique

The effect of the addition of potassium thiocyanate on potassium dihydrogen phosphate (KDP) crystals, grown from aqueous solution by the temperature lowering method using a microcontroller based seed rotation technique has been studied. As part of nucleation studies, metastable zone width, induction period and crystal growth rate of additive added KDP are determined and analyzed with the pure system. Dielectric measurements were carried out on pure and doped crystals at various temperatures ranging from 313 to 423 K and compared. The crystalline perfection of the grown crystal was studied by the high resolution X-ray diffraction analysis. The crystal grown from additive added solution was subjected to structural, optical transmission, second harmonic generation and hardness studies and the effect of additive on pure system is investigated.     

Low regularity global well-posedness for the Zakharov and Klein-Gordon-Schrödinger systems

We prove low regularity global well-posedness for the 1d Zakharov system and the 3d Klein-Gordon-Schrödinger system, which are systems in two variables and . The Zakharov system is known to be locally well-posed in and the Klein-Gordon-Schrödinger system is known to be locally well-posed in . Here, we show that the Zakharov and Klein-Gordon-Schrödinger systems are globally well-posed in these spaces, respectively, by using an available conservation law for the norm of and controlling the growth of via the estimates in the local theory.

     

Weighted enumeration of spanning subgraphs in locally tree‐like graphs

Using the theory of negative association for measures and the notion of unimodularity for random weak limits of sparse graphs, we establish the validity of the cavity method for counting spanning subgraphs subject to local constraints in asymptotically tree‐like graphs. Specifically, the normalized logarithm of the associated partition function (free energy) is shown to converge along any sequence of graphs whose random weak limit is a tree, and the limit is directly expressed in terms of the unique solution to a limiting cavity equation. On a Galton–Watson tree, the latter simplifies into a recursive distributional equation which can be solved explicitly. As an illustration, we provide a new asymptotic formula for the maximum size of a b‐matching in the Erd?s–Rényi random graph with fixed average degree and diverging size, for any $b\in\mathbb{N}Using the theory of negative association for measures and the notion of unimodularity for random weak limits of sparse graphs, we establish the validity of the cavity method for counting spanning subgraphs subject to local constraints in asymptotically tree‐like graphs. Specifically, the normalized logarithm of the associated partition function (free energy) is shown to converge along any sequence of graphs whose random weak limit is a tree, and the limit is directly expressed in terms of the unique solution to a limiting cavity equation. On a Galton–Watson tree, the latter simplifies into a recursive distributional equation which can be solved explicitly. As an illustration, we provide a new asymptotic formula for the maximum size of a b‐matching in the Erd?s–Rényi random graph with fixed average degree and diverging size, for any $b\in\mathbb{N}$. To the best of our knowledge, this is the first time that correlation inequalities and unimodularity are combined together to yield a general proof of uniqueness of Gibbs measures on infinite trees. We believe that a similar argument is applicable to other Gibbs measures than those over spanning subgraphs considered here. © 2012 Wiley Periodicals, Inc. Random Struct. Alg., 2013     

Analysis of carbenoxolone by ultra‐high‐performance liquid chromatography tandem mass spectrometry in mouse brain and blood after systemic administration

Carbenoxolone is a derivative of glycyrrhetinic acid found in the root of Glycyrrhiza glabra, colloquially known as licorice. It has been used as a treatment for peptic and oral ulcers. In recent years, carbenoxolone has been utilized in basic research for its ability to block gap junctional communication. Better understanding the distribution of carbenoxolone after systemic administration can lead to a better understanding of its potential sites of action. Presented is an ultra high‐performance liquid chromatography tandem mass spectrometer (UHPLC–MS/MS) method for the identification and quantification of carbenoxolone in mouse blood and brain tissue. Twenty mice were injected intraperitoneally with 25 mg/kg carbenoxolone and brain tissue and blood were collected for analysis. Blood concentrations (mean ± SD) at 15, 30, 60 and 120 min were determined to be (n = 5) 5394 ± 778, 2636 ± 836, 1564 ± 541 and 846 ± 252 ng/mL, respectively. Brain concentrations (mean ± SD) at 15, 30, 60 and 120 mins were determined to be (n = 5) 171 ± 62, 102 ± 35, 55 ± 10 and 27 ± 9 ng/g, respectively. The analysis of these specimens at the four different time points resulted in blood and brain half‐lives in mice of ~43 and 41 min, respectively. The UHPLC–MS/MS method was determined to be sensitive and robust for quantification of carbenoxolone.     

Characterization of a highly stable zwitterionic hydrophilic interaction chromatography stationary phase based on hybrid organic–inorganic particles

We have characterized a sulfobetaine stationary phase based on 1.7 μm ethylene-bridged hybrid organic–inorganic particles, which is intended for use in hydrophilic interaction chromatography. The efficiency of a column packed with this material was determined as a function of flow rate, demonstrating a minimum reduced plate height of 2.4. The batch-to-batch reproducibility was assessed using the separation of a mixture of acids, bases, and neutrals. We compared the retention and selectivity of the hybrid sulfobetaine stationary phase to that of several benchmark materials. The hybrid sulfobetaine material gave strong retention for polar neutrals and high selectivity for methyl groups, hydroxy groups, and configurational isomers. Large differences in cation and anion retention were observed among the columns. We characterized the acid and base stability of the hybrid sulfobetaine stationary phase, using accelerated tests at pH 1.3 and 11.0, both at 70°C. The results support a recommended pH range of 2–10. We also investigated the performance of columns packed with this material for metal-sensitive analytes, comparing conventional stainless steel column hardware to hardware that incorporates hybrid surface technology to mitigate interactions with metal surfaces. Compared to the conventional columns, the hybrid surface technology columns showed a greatly improved peak shape.     

Nanostructural organization and anion effects in the optical Kerr effect spectra of binary ionic liquid mixtures

This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).     

Synthesis, EPR spectrum and X-ray structure of tetra-n-butylammonium bis(benzene-1,2-dithiolato(2−)-κS,S′)platinate(III)

The new salt, tetra-n-butylammonium bis(benzene-1,2-dithiolato(2−)-κ²S,S′)platinate(III), [NBu₄][Pt(C₆H₄S₂)₂] (1), has been synthesized in ethanol/water, and fully characterized by single crystal X-ray structure determination. The central platinum in the complex ion [Pt(bdt)₂]⁻ is tetracoordinated by the S atoms of the bdt²⁻ ligands (bdt²⁻ is benzene-1,2-dithiolate) in a square-planar geometry. The well-resolved frozen solution EPR spectrum exhibits rhombic symmetry. The room temperature effective magnetic moment (μ_eff = 1.80 Bohr magneton) is in line with this spectrum and strongly supports the Pt(III) oxidation state in 1. This observation is in excellent agreement with previous results reported on closely related Ni(III), Pd(III) and Pt(III) species.     

An interface comprising molecular wires and poly(ethylene glycol) spacer units self-assembled on carbon electrodes for studies of protein electrochemistry

The characterization and application of a modified electrode interface for protein electrochemistry is reported. This generic interface is composed of a mixed monolayer of oligo(phenylethynylene) molecular wires (MWs) and poly(ethylene glycol) (PEG) deposited on glassy carbon electrodes by reductive adsorption of the respective aryl diazonium salts. Electrochemistry and scanning electron microscopy demonstrate that the PEG component exhibits a distinct decrease in nonspecific adsorption of blood serum and the proteins bovine serum albumin (BSA) and horseradish peroxidase (HRP) relative to a bare glassy carbon electrode. The ability of the MWs to facilitate efficient electron transfer through the PEG layer to the underlying electrode was demonstrated by covalently attaching ferrocenemethylamine to the end of the MWs. The calculated rate constant for this system was 229 +/- 30 s(-1). Covalent attachment of HRP to the MWs allowed direct electron transfer to the redox protein with almost ideal electrochemistry, indicating a specific interaction between the MW and HRP, with a rate constant of 13.4 +/- 2.3 s(-1). This rate constant is more rapid than previously reported for HRP shown to still be catalytically active. Retained catalytic activity of HRP was demonstrated by the enzyme responding to the addition of hydrogen peroxide. Similarly, by attaching myoglobin to the end of the MWs, a rate constant for this protein of 2 s(-1) was measured. The rigidity of the MWs, as well as it being longer than the PEG diluent, means this generic interface can be employed to investigate the electrochemistry of a wide range of redox proteins.