Oxygen inhibition in thiol–acrylate photopolymerizations

The overall effects of oxygen on thiol–acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6‐hexanediol diacrylate with the alkane‐based thiol (1,6‐hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol–acrylate photopolymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2007–2014, 2006     

Graft polymerization of vinyl monomers inside macroporous polyacrylamide gel,cryogel, in aqueous and aqueous‐organic media initiated by diperiodatocuprate(III) complexes

Graft polymerization initiated by diperiodatocuprate(III) complex (Cu(III)) initiator was found to be an effective and convenient method for graft polymerization of vinyl monomers onto macroporous polyacrylamide gels, the so‐called cryogels (pAAm‐cryogels). The effect of time, temperature, monomer and initiator concentration during the graft polymerization in aqueous and aqueous‐organic media was studied. The graft polymerization of water‐soluble monomers as [2‐(methacryloyloxy)ethyl]‐trimethylammonium chloride, 2‐hydroxyethyl methacrylate, N‐isopropylacrylamide, and N,N‐dimethylacrylamide proceeds with higher grafting yield in aqueous medium, as compared with that in aqueous‐organic media. Graft polymerization in aqueous‐organic media such as water–DMSO solutions allows grafting of water‐insoluble monomers such as glycidyl methacrylate and N‐tert‐butylacrylamide with high grafting degrees of 100 and 410%, respectively. It was found that the deposition of initiator on the pore surface of cryogels promoted graft polymerization by facilitating the formation of the redox couple Cu(III)‐acrylamide group. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1952–1963, 2006     

Grafting of silica during the processing of silica‐filled SBR: Comparison between length and content of the silane

The treatment of nanoscopic silica grafted in the blend during the processing of silica‐filled styrene butadiene rubber was performed with silane, introduced at different concentrations, or at a constant concentration with a given length of alkyl chain. From swelling measurements in water and in solvent, the maximum silane content that can be grafted has been calculated as a function of the length of the silane alkyl chains as well as their efficiency to cover the silica surface. The found values are close to the values found in the literature for grafting in solution. Moreover, a direct correspondence between the length of the silane alkyl chains and their concentration has been deduced. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 143–152, 2006     

Synthesis and characterization of ciprofloxacin compounds with cadmium(II) and mercury(II) chlorides

Five new compounds of ciprofloxacin (CfH = C₁₇H₁₈FN₃O₃) with cadmium(II) and mercury(II) chlorides were synthesized. The compounds were characterized by chemical analysis, powder X-ray diffraction, pH-metric titration, UV spectroscopy, and thermal analysis.     

Stability of copper(II) complexes with cellulose complexite in water-dioxane mixtures

The complexing properties of cellulose complexite with respect to copper(II) ions in water-1,4-dioxane (DO) mixtures are determined. The stoichiometry and stability constants of copper(II) complexes with the hydroxamic groups of the polymer are determined. The equilibrium speciation diagrams for the complexes at pH 2.0–6.0 are plotted; stereochemical configurations are suggested. The effect of the solvation parameters of the complexite on complex formation is analyzed.     

Complex formation of dimeric cyclophane zinc diphenylporphyrinates with 1,4-diazabicyclo[2,2,2]octane and pyrazine

The formation of host-guest complexes between dimeric cyclophane zinc diphenylporphyrinates and bidentate ligands of different nature containing two nitrogen atoms has been studied by the spectrophotometric titration method and ¹H NMR spectroscopy in a toluene-methanol (2: 1) binary solvent. The complexation of these dimeric porphyrinates with 1,4-diazabicyclo[2,2,2]octane or pyrazine can lead to 1: 1 or 1: 2 complexes, depending on the metalloporphyrin-to-ligand molar ratio. The stability constants of the porphyrinate-ligand complexes and concentration ranges of their formation have been determined.     

Fluctuations of the energy absorption of electron-photon radiation in a model with collision-grouping elements

In the present work, the general method proposed earlier for calculating the distribution density and moments of the absorbed energy in isolated sensitive regions of absorbers irradiated by ionizing particles is developed and made specific for the electron-photon problem. Electron transfer is considered within the framework of a model using grouping of excitations and slipping ionization; the presence of electron equilibrium in the vicinity of sensitive regions is assumed. Two similar methods of calculating these characteristics are developed. Both reduce the initial problem to two independent problems: determining the electron spectrum in the sensitive region (in one of the methods, the spectrum of electron sources is also needed) and calculating the coefficients characterizing electron transfer in the sensitive region and its immediate vicinity.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 89–94, September.     

Chaotic buffering and its mathematical models

We propose a general idea of obtaining different chains of coupled oscillators with chaotic buffering. As examples, we consider chains of diffusively coupled generalized cubic Schrödinger equations and nonlinear telegraph equations. We also give examples of systems that have an infinite-dimensional chaotic attractor.