Vinyl polymerization by metal complexes. XXV. Photopolymerization of vinyl monomers by porphyrin–iron(III) complex

Photopolymerization of methyl methacrylate was studied in the presence of the system of the tetraphenylporphine–iron(III) complex, free amine, and carbon tetrachloride at 0°C in methanol solution. It was found that the activity of the complex for polymerization does not depend upon the structure of the free amines added. The effect of the polymeric amines on the polymerization was also examined. The photochemical reaction process among the iron(III) complex, amine, and carbon tetrachloride was followed also under similar conditions by ultraviolet and visible spectroscopy. The scheme for the initiation species presented is supported by the results on the posteffect of the photopolymerization.     

Graft copolymerization of methyl methacrylate to poly(vinyl alcohol) initiated by ferric ion-hydrogen peroxide system

The reaction occurring on treatment of samples of poly(vinyl alcohol) previously oxidized by sodium hypochlorite with ferric ion and hydrogen peroxide was studied. The graft copolymerization taking place on adding methyl methacrylate to the above system was also studied. Early in the reaction there was a period during which hydrogen peroxide was greatly reduced by the poly(vinyl alcohol), and this corresponded with a rapid cleavage reaction of the main chain of the polymer. Moreover, it was found that the reaction was quantitatively proportional to the formation of carbonyl groups in the sample. On the other hand, very few grafts were scarcely formed during this period; they formed by a mild reaction which took place immediately after this period. It seems that this behavior is quite different from that observed with the ceric ion initiating system. It is presumed that the formation of grafts is due to radicals formed by the cleavage of the main chain, and that the structure of the copolymer so formed is something like a block polymer.     

Particle monolayer formation at the air–water interface by silica particle with well‐defined grafted polymer

Particle monolayer formation at the air–water interface by polymer‐grafted colloidal silica was investigated. Methyl methacrylate (MMA) was polymerized from initiative bromide groups at colloidal silica surface by atom transfer radical polymerization. We obtained polymer‐grafted silica particle (SiO₂‐PMMA) with relative narrow polydispersity of PMMA. For the polymer‐grafted particle with high graft density, particle monolayer formation was confirmed by π‐A isotherm measurement and SEM observation. Interparticle distance was controllable by surface pressure. Furthermore, grafted polymer chains were suggested to be fairly extended at the air–water interface. However, for the polymer‐grafted particle with low graft density, monolayer structure on substrate showed aggregation and voids. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2789–2797, 2006     

Spatially-resolved observation of glow discharge plasma for atomic emission spectrometry.

An imaging spectrograph equipped with a CCD detector was employed to measure two-dimensional emission images from a glow discharge plasma in atomic emission spectrometry. The emission images at Zn I 334.50 nm for a zinc sample and at Cu I 324.75 nm for a copper sample could be obtained. Their emission intensities were not uniform in the radial direction of the plasma region but became weaker at larger distance from the central zone. The two-dimensional distribution would result from a spatial variation in the excitation efficiency of the plasma and thus provide useful information for understanding the excitation processes occurring in the plasma.     

Palladium–Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination

Metal–Lewis acid cooperation provides new opportunities in catalysis. In this work, we report a new type of palladium–borane cooperation involving anionic Pd⁰ species. The air‐stable DPB palladium complex 1 (DPB=diphosphine‐borane) was prepared and reacted with KH to give the Pd⁰ borohydride 2 , the first monomeric anionic Pd⁰ species to be structurally characterized. The boron moiety acts as an acceptor towards Pd in 1 via Pd→B interaction, but as a donor in 2 thanks to B‐H‐Pd bridging. This enables the activation of C?Cl bonds and the system is amenable to catalysis, as demonstrated by the hydro‐/deutero‐dehalogenation of a variety of (hetero)aryl chlorides (20 examples, average yield 85 %).     

High preconcentration of ultra-trace metal ions by liquid–liquid extraction using water/oil/water emulsions as liquid surfactant membranes

A high preconcentration method by liquid–liquid extraction using liquid surfactant membranes was developed. The water-in-oil (w/o) emulsion containing dilute hydrochloric acid, 2-ethylhexyl hydrogen 2-ethylhexylphosphonate (PC-88A), liquid paraffin, and kerosene was used for the extraction. In a resulting volume of 1000 cm³ of an aqueous sample solution (pH 5.0) containing less than 1 mg of each metal ion, 2 cm³ of w/o emulsion droplets coated with sorbitan monooleate were dispersed. The analyte metal ions in the outer bulk aqueous phase were extracted into the organic phase to form a complex with PC-88A and successively back-extracted into the inner aqueous phase. The analytes in the resulting inner aqueous phase were determined subsequently by graphite furnace atomic absorption spectrometry applied as a detector. By this procedure, concentration factors of 570, 820, 750, 970, 860, and 880 were achieved for chromium(III), manganese(II), cobalt(II), nickel(II), copper(II), and cadmium(II), respectively, and also the respective detection limits (3σ) of 0.4, 20, 1.2, 18, 18, and 0.7 pg cm⁻³ were obtained.     

Crystal structure and physical properties of Fe1.5Pb5.5In10S22

A new compound, Fe2+(1.5)Pb2+(5.5)In3+(10)S2-(22), was found in the Fe-Pb-In-S system. The crystals had a shiny metallic gray luster and were obtained in a barlike shape. The melting and recrystallizing points are 1098 and 1090 K, respectively. The crystal structure determined by X-ray diffraction is P2/m, a = 14.558(1) A, b = 3.8556(3) A, c = 15.558(1) A, beta = 96.876(1) degrees , V = 867.0(1) A(3), Z = 1, Dc = 5.893 g/cm(3), and R1 = 3.78%, which is an isostructure with Sn(5.5)In(11)S(22). In the structure, lead atoms exist at three crystallographically independent sites, and one of them, Pb1, is occupied by a quarter of indium atoms. All of the Fe ions are randomly distributed at six indium sites. This compound is a semiconductor with a band gap, E(a) = 0.95 eV. The dominant magnetic interaction is antiferromagnetic, but magnetic orderings are not observed down to 2 K.     

Analyzing atomic liquids and solids by means of two-dimensional Raman spectra in frequency domain

A practical method to evaluate the contributions of the nonlinear polarizability and anharmonicity of potentials from the experimental and simulation data by using double Fourier transformation is presented. In a Lennard-Jones potential system, an approximated expression of the fifth-order response function using the ratio between nonlinear polarizability and anharmonicity exhibits a good agreement with the results of the molecular dynamics simulation. In a soft-core case, the fifth-order Raman signal indicates that the system consists of the delocalized and localized modes, and only the delocalized mode affects the dramatic change of the fifth-order Raman response functions between solid and liquid phases through nonlinear polarizability.