Electroninitiated polymerization of bis(trichlorophenoxo)-tetramethylethylene diamine copper(II)

Electroninitiated polymerization of bis(trichlorophenoxo)-N,N,N′,N′-tetramethylethylene diamine copper(II) was achieved in acetonitrile at various peak potentials of the monomer. A constant potential approach was selected in polymerization reactions. Electrolyses were carried out under air, nitrogen, and oxygen atmospheres. Structural analyses of the polymers were done by ¹H-NMR and ¹³C-NMR FT–IR spectroscopy. Molecular weights of the polymers were determined by vapor pressure (isopiestic) method.     

A new and efficient chemoenzymatic route to both enantiomers of 4-hydroxycyclohex-2-en-1-one

[reaction: see text] A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting 4-hydroxycyclohex-2-en-1-one in three steps starting from 3-methoxycyclohex-2-en-1-one is described. Manganese(III) acetate-mediated acetoxylation followed by enzyme-mediated hydrolysis of alpha-acetoxy enone affords acetoxy enone 3 and hydroxy enone 4 with high enantiomeric excesses and in good yields. The reduction of the acetoxy and hydroxy enones furnished both enantiomers of 4-hydroxycyclohex-2-en-1-one in high enantiomeric excess.     

Electroinitiated Polymerization of N-Vinylcarbazole by Direct Electron Transfer

Electroinitiated polymerization of N-vinylcarbazole has been accomplished by constant potential electrolysis. It was found that direct electron transfer from the monomer to the anode initiates the polymerization even at a potential as low as +0.95 V versus Ag^?/ Ag⁺. Dichloromethane was used as the solvent, and the electrolyte was tetrabutylammonium fluoroborate. Conversions as high as 86% were reached even when a microelectrode was used. Effects of electrode area, temperature, and electrode potential on polymerization were studied. Percent conversion was followed by cyclic voltammetry.     

89Zr Labeled Fe3O4@TiO2 Nanoparticles: In Vitro Afffinities with Breast and Prostate Cancer Cells

In this study, Fe₃O₄@TiO₂ nanoparticles were synthesized as a new Positron Emission Tomography/Magnetic Resonance Imaging (PET/MRI) hybrid imaging agent and radiolabeled with ⁸⁹Zr. In addition, Fe₃O₄ nanoparticles were synthesized and radiolabeled with ⁸⁹Zr. Df-Bz-NCS was used as bifunctional ligand. The nanoconjugates were characterized with transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. Radiolabeling yields were 100%. Breast and prostate cancer cell affinities and cytotoxicity were determined using in vitro cell culture assays. The results demonstrated that Fe₃O₄@TiO₂ nanoparticles are promising for PET/MR imaging. Finally, unlike Fe₃O₄ nanoparticles, Fe₃O₄@TiO₂ nanoparticles showed a fluorescence spectrum at an excitation wavelength of 250 nm and an emission wavelength of 314 nm. Therefore, in addition to bearing the magnetic properties of Fe₃O₄ nanoparticles, Fe₃O₄@TiO₂ nanoparticles display fluorescence emission. This provides them with photodynamic therapy potential. Therefore multimodal treatment was performed with the combination of PDT and RT by using human prostate cancer cell line (PC3). The development of ⁸⁹Zr-Df-Bz-NCS-Fe₃O₄@TiO₂ nanoparticles as a new multifunctional PET/MRI agent with photodynamic therapy and hyperthermia therapeutic ability would be very useful.     

Polypyrrole Grafts Synthesized via Electrochemical Polymerization

Abstract

Electrically conducting polypyrrole grafts with poly[(methyl meth-acrylate)-co-(2-(N-pyrrolyl) ethyl methacrylate)] (PMMA-co-PEMA) were synthesized by constant potential electrolysis. Cyclic Voltammetry, DSC, TGA, SEM and elemental analysis were used in order to characterize the free standing films. Conductivities of the polymers were measured by a four-probe technique.     

Surface characterization and radical decay studies of oxygen plasma‐treated PMMA films

Polymethylmethacrylate (PMMA) films were modified by RF oxygen plasma with various powers applied for different periods, and the effects of these parameters on the surface properties such as hydrophilicity, surface free energy (SFE), chemistry, and topography were investigated by water contact angle, goniometer, X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy, and the types of the created free radicals and their decay were detected by electron spin resonance spectroscopy (ESR). SFE and contact angle results varied depending on the plasma parameters. Oxygen plasma treatment (100 W–30 min) enhanced the hydrophilicity of PMMA surface as shown by decreasing the water contact angle from 70° to 26°. XPS analysis showed the change in the amounts of the present functionalities as well as formation of new groups as free carbonyl and carbonate groups. The roughness of the surface increased considerably from ~2 nm to ~75 nm after 100 W–30 min oxygen plasma treatment. ESR analysis indicated the introduction of peroxy radicals by oxygen plasma treatment, and the intensity of the radicals increased with increasing the applied power. Significant decrease in radical concentration was observed especially for the samples treated with higher powers when the samples were kept under the atmospheric conditions. As a conclusion, RF plasma, causes changes in the chemical and physical properties of the materials depending on the applied parameters, and can be used for the creation of specific groups or radicals to link or immobilize active molecules onto the surface of a material. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of solvent on TEOS hydrolysis kinetics and silica particle size under basic conditions

In-situ liquid-state ²⁹Si nuclear magnetic resonance was used to investigate the temporal concentration changes during ammonia-catalyzed initial hydrolysis of tetraethyl orthosilicate in different solvents (methanol, ethanol, n-propanol, iso-propanol and n-butanol). Dynamic light scattering was employed to monitor simultaneous changes in the average diameter of silica particles and atomic force microscopy was used to image the particles within this time frame. Solvent effects on initial hydrolysis kinetics, size and polydispersity of silica particles were discussed in terms of polarity and hydrogen-bonding characteristics of the solvents. Initial hydrolysis rate and average particle size increased with molecular weight of the primary alcohols. In comparison, lower hydrolysis rate and larger particle size were obtained in the secondary alcohol. Exceptionally, reactions in methanol exhibited the highest hydrolysis rate and the smallest particle size. Ultimately, our investigation elaborated, and hence confirmed, the influences of chemical structure and nature of the solvent on the formation and growth of the silica particles under applied conditions.     

Determination of radiological hazard parameters and radioactivity concentrations in bauxite samples: the case of the Sutlegen Mine Region (Antalya,Turkey)

Journal of Radioanalytical and Nuclear Chemistry - Iron phosphate glasses with melting temperatures of?~?1300 °C were developed to immobilize spent nuclear fuels. The...