Effect of amount of monomer on radiation-induced polymerization of styrene adsorbed on silica gel

The effect of amount of monomer on radiation-induced polymerization of styrene adsorbed on silica gel was investigated with the monomer amounting from less than monolayer adsorption to more than the equilibrium adsorption. The rate of graft polymerization and the molecular weight of the polymer changed with the amount of monomer adsorbed on silica gel. Maximum grafting efficiency was obtained at monolayer adsorption. The molecular weight of graft polymer was higher than that of homopolymer in both radical and cationic polymerizations, and the ratio in molecular weight of graft polymer to that of homopolymer tends to be unity with increasing amount of adsorbed monomer. These results can mainly be explained in terms of the number of initiating species (radical and cation) that change in relation to the amount of adsorbed monomer. Propagation and termination change with amount of adsorbed monomer in relation to the molecular mobility of adsorbed monomer. A very high-molecular-weight graft polymer is formed only with a small amount of adsorbed monomer in the initial stage. The grafting percent with a large amount of adsorbed monomer increased after most of the monomer has been polymerized. Secondary effect of radiation on the graft and homopolymers due to energy transfer from silica gel is suggested from the complicated phenomena in the later stage of the reaction.     

Enhancement of sonochemical reaction of terephthalate ion by superposition of ultrasonic fields of various frequencies

The ultrasonic reactor with dual frequency was used and the effect of frequency on the fluorescence intensity of terephthalate ion was experimentally investigated in the frequency range from 176 to 635 kHz. The sonochemical reaction fields were visualized by using sonochemical luminescence of luminol solution. Compared with the fluorescence intensity of terephthalate ion for single frequency, the fluorescence intensity for dual frequency increased. The fluorescence intensity ratio of dual frequency to single frequency had maximum value when the frequency of transducer attached at the bottom wall was comparable in magnitude to that at the side wall. In the case of dual frequency, the sonochemical reaction fields became more extensive in the reactor and more intensive around the center of the reactor.     

Synthesis,Redox Properties,and Electronic Spectra of Sterically Crowded Triarylphosphines Conjugated with Electron Acceptors

Abstract

Synthesis, redox properties, and electronic spectra of the sterically crowded triarylphosphines conjugated with π-electron systems, especially electron acceptors such as carbonyl group, are briefly reviewed. The sterically crowded triarylphosphines conjugated with various π-electron systems were synthesized from the common synthetic intermediate, (bromoaryl)phosphine, by conventional manner. The sterically crowded triarylphosphines conjugated with the electron acceptors exhibit visible absorption and fluorescence with large Stokes shift. Large solvent effect, redshift in polar solvent, and good correlation with the difference of the oxidation potential of the phosphine moiety and the reduction potential of the acceptor moiety suggest polar excited state resulting from HOMO-LUMO transition.     

Radiation-Induced Polymerization and Pressure-Volume Behavior of Acrylonitrile at High Pressure

Radiation-induced polymerization and pressure-volume (P-V) measurements of acrylonitrile (AN) were studied up to 8000 kg/cm² in the temperature range of 6–72°C. P-V isotherms of AN have several small breaks, A phase diagram of AN was obtained from the breaking pressures and temperatures. Liquid phases were named L_I, L_II, and L_III, from low to high pressure. The polymerization behavior and volume contraction on polymerization changed in L_I, L_II, and L_III. The difference in entropy between original and activated states decreased with increasing pressure at the same phase, but increased with phase change in L_I to L_II and L_II to L_III. It was concluded from these results and from IR data on PAN that molecular packing of AN in liquid changed in L_I, L_II, and L_III. In L_II and L_III, AN molecules aligned in a less suitable geometry for polymerization than in L_I.     

Vinyl Polymerization by Metal Complexes. XXXII. Formation of Glycolchitosan-Copper(II) Complex and the Initiation of Vinyl Polymerization by Using the Complex

The formation of the water-soluble glycolchitosan-copper (II) complex was studied by ultraviolet and visible spectroscopy and by viscosity measurement. The structure of the polymer complex in question was found to change with pH value of the system. The glycolchitosan-copper (II) complex was active as a free-radical initiator for the polymerization of methyl methacrylate and acrylonitrile in the presence of carbon tetra- chloride. The maximum conversion was observed at neutral pH, and was influenced by the presence of neutral salts. Relation- ship between the activity of the polymer complex for initiating the polymerization and its structure was discussed.     

Influences of aging on thermal decomposition mechanism of high performance oxidizer ammonium dinitramide

Ammonium dinitramide (ADN) is one of the several promising new solid propellant oxidizers. ADN is of interest because its oxygen balance and energy content are high, and it also halogen-free. One of the most important characteristics of a propellant oxidizer, however, is stability and ADN is known to degrade to ammonium nitrate (AN) during storage, which will affect its performance. This study focused on the effects of aging on the thermal decomposition mechanism of ADN. The thermal behaviors of ADN and ADN/AN mixtures were studied, as were the gases evolved during their decomposition, using differential scanning calorimetry (DSC), thermogravimetry–differential thermal analysis-infrared spectrometry (TG–DTA-IR), and thermogravimetry–differential thermal analysis-mass spectrometry (TG–DTA-MS). The results of these analyses demonstrated that the decomposition of ADN occurs via a series of distinct stages in the condensed phase. The gases evolved from ADN decomposition were N₂O, NO₂, N₂, and H₂O. In contrast, ADN mixed with AN (to simulate aging) did not exhibit the same initial reaction. We conclude that aging inhibits early stage, low temperature decomposition reactions of ADN. Two possible reasons were proposed, these being either a decrease in the acidity of the material due to the presence of AN, or inhibition of the acidic dissociation of dinitramic acid by NO ₃ ^? .     

KCTD20, a relative of BTBD10, is a positive regulator of Akt

Background

BTBD10 binds to Akt and protein phosphatase 2A (PP2A) and inhibits the PP2A-mediated dephosphorylation of Akt, thereby keeping Akt activated. Previous studies have suggested that BTBD10 plays an important role in preventing motor neuronal death and accelerating the growth of pancreatic beta cells. Because levels of BTBD10 expression are much lower in many non-nervous tissues than nervous tissues, there may be a relative of BTBD10 that has BTBD10-like function in non-neuronal cells.

Results

A 419-amino-acid BTBD10-like protein, named KCTD20 (potassium channel tetramerization protein domain containing 20), was to found to bind to all Akt isoforms and PP2A. Overexpression of KCTD20 increased Akt phosphorylation at Thr308, as BTBD10 did, which suggests that KCTD20 as well as BTBD10 positively regulates the function of Akt. KCTD20 was ubiquitously expressed in non-nervous as well as nervous tissues.

Conclusions

KCTD20 is a positive regulator of Akt and may play an important role in regulating the death and growth of some non-nervous and nervous cells.

     

Ni-catalyzed α-arylation of secondary α-bromo-α-fluoro-β-lactam: cross-coupling of a secondary fluorine-containing electrophile

A highly diastereoselective cross-coupling reaction of an α-bromo-α-fluoro-β-lactam with a wide range of aryl Grignard reagents was catalyzed by Ni/bis(oxazoline) in yields of up to 98%. The product was obtained diastereoselectively as an anti-isomer. This is the first successful α-arylation of an α-fluoro-β-lactam to produce diverse α-aryl-α-fluoro-β-lactams.