Isotropic models for a heat transfer in periodic composites

A macroscopic model for the non – stationary heat transfer processes in a periodic honeycomb – type anisotropic rigid conductor is formulated. The main aim of this contribution is to show that the macroscopic properties of this conductor are isotropic. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

(2,2′‐Bipyridine)bis(tri‐tert‐butoxysilanethiolato‐κS)lead(II) and (4,7‐diphenyl‐1,10‐phenanthroline‐κ2N,N′)bis(tri‐tert‐butoxysilanethiolato‐κS)lead(II) benzene hemisolvate

In the title mononuclear lead silanethiolates, [Pb(C₁₂H₂₇O₃SSi)₂(C₁₀H₈N₂)], (I), and [Pb(C₁₂H₂₇O₃SSi)₂(C₂₄H₁₆N₂)]·0.5C₆H₆, (II), the Pb atom shows a distorted square‐pyramidal coordination with a PbON₂S₂ core in which one S atom lies in an axial position. Intermolecular π–π and C—H...π interactions stabilize the structures. The benzene solvent molecule in (II) lies on an inversion centre.     

Mediated electron transfer of cellobiose dehydrogenase and glucose oxidase at osmium polymer-modified nanoporous gold electrodes

Nanoporous and planar gold electrodes were utilised as supports for the redox enzymes Aspergillus niger glucose oxidase (GOx) and Corynascus thermophilus cellobiose dehydrogenase (CtCDH). Electrodes modified with hydrogels containing enzyme, Os-redox polymers and the cross-linking agent poly(ethylene glycol)diglycidyl ether were used as biosensors for the determination of glucose and lactose. Limits of detection of 6.0 (±0.4), 16.0 (±0.1) and 2.0 (±0.1) μM were obtained for CtCDH-modified lactose and glucose biosensors and GOx-modified glucose biosensors, respectively, at nanoporous gold electrodes. Biofuel cells composed of GOx- and CtCDH-modified gold electrodes were utilised as anodes, together with Myrothecium verrucaria bilirubin oxidase (MvBOD) or Melanocarpus albomyces laccase as cathodes, in biofuel cells. A maximum power density of 41 μW/cm² was obtained for a CtCDH/MvBOD biofuel cell in 5 mM lactose and O₂-saturated buffer (pH 7.4, 0.1 M phosphate, 150 mM NaCl).     

Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.     

A Functional Role for Aβ in Metal Homeostasis? N‐Truncation and High‐Affinity Copper Binding

Accumulation of the β‐amyloid (Aβ) peptide in extracellular senile plaques rich in copper and zinc is a defining pathological feature of Alzheimer′s disease (AD). The Aβ1–x (x=16/28/40/42) peptides have been the primary focus of Cu^II binding studies for more than 15 years; however, the N‐truncated Aβ4–42 peptide is a major Aβ isoform detected in both healthy and diseased brains, and it contains a novel N‐terminal FRH sequence. Proteins with His at the third position are known to bind Cu^II avidly, with conditional log K values at pH 7.4 in the range of 11.0–14.6, which is much higher than that determined for Aβ1–x peptides. By using Aβ4–16 as a model, it was demonstrated that its FRH sequence stoichiometrically binds Cu^II with a conditional K_d value of 3×10^?14 M at pH 7.4, and that both Aβ4–16 and Aβ4–42 possess negligible redox activity. Combined with the predominance of Aβ4–42 in the brain, our results suggest a physiological role for this isoform in metal homeostasis within the central nervous system.     

Curing of dicyanate ester/epoxy copolymers modified with polysiloxane and butadiene-acrylonitrile rubbers

The cyanate ester (CE) and epoxy (EP) resins were cured together at various mass compositions. The curing behavior of CE and CE/EP systems was studied by means of differential scanning calorimetry (DSC) in non-isothermal conditions. The DSC measurements indicated that the curing reactions were dependent on the stoichiometric ratio of the mixtures and showed the dilution effect of the EP resin in the cyclotrimerization of the catalyzed CE resin. The CE and CE/EP (70/30) systems were modified using reactive liquid butadiene-acrylonitrile copolymer (ETBN) and polysiloxane core?Cshell (PS) elastomer. The influence of ETBN and PS on the curing process and glass transition temperature (T _g) of CE/EP systems was determined. The impact resistance characteristics of the completely cured systems indicated the influence of the modifiers and the EP content in the mixtures on its impact resistance.     

Does dehydrocyclization of 4-benzoylthiosemicarbazides in acetic acid lead to s-triazoles or thiadiazoles?

Ever since the recognition of strong pharmaceutical activities of triazoles and thiadiazoles, these scaffolds have been the subject of vigorous studies. One of the best strategies for synthesis of these azoles is dehydrocyclization of 1,4-disubstituted thiosemicarbazides, which leads to s-triazoles in alkaline media, whereas in strong acidic media 1,3,4-thiadiazoles are formed. However, the literature is riddled with contradictory communications regarding the nature of the products of such reactions under mild acidic conditions. As these compounds are not amenable to X-ray analysis, we have resorted to NMR and theoretical modelling to resolve this discrepancy. In this article, we present arguments indicating that dehydrocyclization of 4-benzoylthiosemicarbazides in glacial acetic acid leads to thiadiazole derivatives. These structural findings are augmented by studies of bioactivity of a few members of the studied class of compounds.     

Copper removal by carbon nanomaterials bearing cyclam-functionalized silica

The synthesis of metal (Fe, Co, Ni)-encapsulated carbon nanomaterials coated with cyclam-bonded silica has been described. The organic layer was identified by Fourier transform infrared spectroscopy and elemental analysis. The functionalized magnetic nanomaterials were employed to extract the divalent cations: copper, calcium, cobalt, manganese and nickel from aqueous solutions. Their adsorption capacities were studied by the batch procedure. The concentration of cations extracted was determined by inductively coupled plasma mass spectrometry. Influence of different parameters viz. pH, amount of the compound studied, contact time, on the cation extraction was investigated. Under optimum conditions copper extraction was significantly more efficient when compared with other coexisting ions.      

Intramolecular Interactions of Trityl Groups

Trityl group, Tr, is a molecular dynamic rotor of which the conformation and helicity depend on other groups in the close vicinity. Interactions with another covalently linked Tr group and with other substituents are analyzed in terms of transfer of chirality to the trityl group. Two trityl groups in a molecule can mutually interact at a distance of two, three, or five bonds. Despite its size, a Tr group attached to a cyclohexane or cyclopentane ring through an oxygen or nitrogen atom adopts either an axial or equatorial position, depending on additional stabilizing interactions, such as hydrogen bonding.     

Trianglamines--readily prepared, conformationally flexible inclusion-forming chiral hexamines

Trianglamines, macrocyclic heteraphanes, were readily synthesised through a [3+3] cyclocondensation of (R,R)-1,2-diaminocyclohexane with terephthalaldehyde, followed by NaBH4 reduction and N-alkylation. The macrocyclic ring shows a remarkable ability to change its conformation, as a consequence of rotation about the C-N bonds or nitrogen inversion due to protonation or N-alkylation, as revealed by circular dichroism spectra, computational modelling and X-ray diffraction analysis. The flexible natures of the trianglamine macrocycles allow ready accommodation of a variety of guest molecules to form crystalline inclusion complexes of highly diversified interpenetrating structures.