Polyamide 6‐polycaprolactone multiblock copolymers: Synthesis,characterization, and degradation

This work describes the synthesis and characterization of polyamide 6 (PA 6)‐polycaprolactone (PCL) multiblock copolymers. Low molar mass, fully amine end‐capped PA 6 was prepared by the addition of a diamine monomer during ε‐caprolactam polymerization. A low molar mass PCL was selected to be incorporated as the biodegradable block and was fully end‐capped with toluene 2,4‐diisocyanate. End group analysis and molecular weight characterizations were performed for both end‐functionalized polymers by SEC, NMR and titration analysis. Incorporation of PCL into PA 6 was mainly achieved by solution mixing of the two end‐functional blocks and, was continued after the removal of the solvent with solid state polymerization (SSP) by gradual heating until about 40 °C below the melting temperature of the PA 6. Molecular weights started to grow immediately during solution mixing and only increased marginally during the SSP treatment. FTIR and SEC studies confirmed the reaction between the two components. DSC data, in combination with the enhanced molar mass during solution mixing pointed to a blocky microstructure, for which distinct melting and crystallization temperatures were observed for the PCL and the PA 6 blocks. Hydrolytic and enzymatic degradation studies were performed at 25 °C where the degree of degradation was followed by weight loss analysis, SEM and SEC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Conversion of carbon dioxide to cyclic carbonates using diimine Ru(II) complexes as catalysts

Cationic diimine Ru(II) complexes were synthesized and tested as catalysts for the formation of cyclic organic carbonates from CO₂ and liquid epoxides (propylene oxide, epichlorohydrine, 1,2‐epoxybutane and styrene oxide) which served as both reactant and solvent. The reaction rates not only depended on the type of ligand, but also on reaction conditions such as temperature, pressure, base, the epoxide substrates and the use of an additional solvent. Reaction rates in terms of turnover frequencies up to 4050 mol_product mol_cat.^?1 h^?1 at 99% selectivity were achieved by optimizing the diimine ligand as well as the reaction temperature and CO₂ pressure. Consistent with CV measurements, the electron donating group on the p‐position of the aryl ring accelerated the reaction rate. Copyright © 2008 John Wiley & Sons, Ltd.     

Linear and Nonlinear Optical Properties in Spherical Quantum Dots

We calculate the energy eigenvalues and the sate functions of one-electron Quantum Dot （QD） by using a combination of Quantum Genetic Algorithm （QGA） and Hartre-Fock-Roothaan （HFR） method. The linear and the third-order nonlinear optical absorption coefficients for the 1s-1p, 1p-1d, and 1d-1f transitions are examined as a function of the incident photon energy for three different values of the stoichiometric ratio. The results show that the stoichiometric ratio, impurity, relaxation time, and dot size have great influence on the optical absorption coefficients of QDs.     

Mass attenuation coefficients for n-type InSe, InSe:Gd, InSe:Ho and InSe:Er single crystals

Measurements have been made to determine the mass attenuation coefficients of undoped n-type InSe, and Gd, Ho, Er doped n-InSe single crystals using a Si(Li) detector in the energy region 15.746–40.930 keV X-ray energies with energy dispersive X-ray fluorescence systems. InSe, InSe:Gd, InSe:Ho and InSe:Er single crystals were grown by using the stockbarger method. The measured values are graphically compared with the theoretical ones obtained using WinXcom.     

Palladium(II)?NHC complexes containing benzimidazole ligand as a catalyst for C?N bond formation

The reaction of 2‐(2‐bromoethyl)‐1,3‐dioxane with 1‐alkylbenzimidazole derivatives results in the formation of the new benzimidazolium salts (1). The reaction of Pd(OAc)₂ with 1,3‐dialkylbenzimidazolium salts (1a–c) yields palladium N‐heterocyclic carbene (NHC) complexes (2a–c). All synthesized compounds were characterized by ¹H NMR, ¹³ C NMR, IR and elemental analysis techniques which support the proposed structures. As catalysts, these new palladium complexes offer a simple and efficient methodology for the synthesis of triarylamines and secondary amines from anilines and amines and in a single step with potassium tertiary butoxide as a base. Copyright © 2010 John Wiley & Sons, Ltd.     

Use of bis(benzimidazolium)–palladium system as a convenient catalyst for Heck and Suzuki coupling reactions of aryl bromides and chlorides

Six new, sterically demanding bis(benzimidazolium) salts (2a–f) as NHC precursors have been synthesized and characterized. These salts, in combination with palladium acetate, provide active catalysts for the cross‐coupling of aryl chlorides and bromides under mild conditions in aqueous media. Copyright © 2006 John Wiley & Sons, Ltd.     

Benzimidazolin‐2‐ylidene–palladium‐catalysed coupling reactions of aryl halides

The in situ prepared three‐component system Pd(OAc)₂–1,3‐dialkylbenzimidazolium chlorides ( 2a – f ) and Cs₂CO₃ catalyses, quantitatively, the Suzuki cross‐coupling of deactivated aryl chlorides and Heck coupling reactions of aryl bromide and iodide substrates. The 1,3‐dialkylbenzimidazolium salts ( 2a – f ) were characterized by conventional spectroscopic methods and elemental analysis. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and self‐catalyzed phase transfer reaction of novel methacrylate polymers

Ethyl α‐chloromethylacrylate was converted to an ester derivative using 5‐chlorovaleric acid in a single step. The homopolymerization of the new monomer (CEMA) and its copolymerization with methyl methacrylate were performed using photoinitiator Irgacure 651. The polymers were reacted with N,N‐dimethyldodecylamine to obtain polymers with pendant quaternary ammonium (QA) moieties. The polymers with pendant QA groups were used in self‐catalyzed phase transfer reactions with sodium phenoxide and 1‐dodecanethiol. The syntheses of the monomer and polymers were followed by FTIR, ¹H NMR, and ¹³C NMR. The average polymer molecular weights and polydispersities were determined by size exclusion chromatography. Thermal analysis was carried out using thermogravimetric analysis and differential scanning calorimetry. The copolymer composition, degree of quaternization, and degree of conversion in phase transfer reaction were determined by ¹H NMR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5844–5854, 2005