Observation on meta-stability of thulium nitrate crystal by using electric measurements

Frequency dependence of ac conductivity from 1 to 10⁵ Hz and time series of the conductivity at 2 kHz were measured along c-axis of thulium nitrate crystal, Tm(NO₃)₃6H₂O at temperatures from 203.15 to 293.15 K. The meta-stability was observed. The frequency spectra of the conductivity were similar to those in disorder system. Aging effect was observed. Non-periodic instability (burst) was found. Non-linear dynamical property was characterized by 1/f noise spectrum, limit cycle in return map and dependence of correlation exponent on embedding dimension.     

Nitroxide‐mediated radical polymerization in miniemulsion: Bimolecular termination in monomer‐free model systems

Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007     

Influence of shell strength on shape transformation of micron-sized,monodisperse, hollow polymer particles

Micron-sized, monodisperse, non-spherical polymer particles with "rugby ball" and "red blood corpuscle"-like shapes were produced by seeded polymerization of the dispersion of (divinylbenzene/vinylbiphenyl/xylene)-swollen polystyrene particles prepared by utilizing the dynamic swelling method which the authors proposed in 1991. Their non-spherical shapes were based on buckling of the shell of the resultant hollow particles. In this article, the reversible shape transformation of the hollow composite polymer particle between spherical and such non-spherical shapes was studied in detail by controlling the shell strength. A part of the shell was buckled by external pressure which was caused by evaporation of xylene from the hollow when the shell had the tensile modulus below the critical value calculated from the pressure-buckling relationship of a spherical shell proposed by Uemura. The plasticization of the shell by a good solvent was one of key factors for the shape transformation.     

Enhancement of electronic excitation energy transfer in the colloidal crystals of colloidal silica suspensions doped with fluorescent dyes

The efficiency of electronic excitation energy transfer from photo-excited rhodamine 110 (Rh110, energy donor) to rhodamine B (RhB, energy acceptor) in an exhaustively deionized colloidal silica suspension has been studied. This colloidal suspension shows Bragg reflection due to the formation of colloidal crystals and the Bragg-peak wavelength is controllable by the volume fraction of the silica spheres. When the Bragg-peak wavelength matches with the fluorescence band of Rh110, a depletion was observed in the Rh110 fluorescence spectrum. This means the fluorescence of Rh110 is partially trapped due to the Bragg reflection inside the crystal lattice. In the coexistence of RhB, the enhancement of RhB fluorescence intensity was observed. These facts clearly indicate the trapped photon energy of Rh110 is efficiently transferred to RhB within the colloidal crystals. The quantitative measurements showed that the enhancement of the transfer efficiency is 20% (or slightly more) in the present experimental conditions.     

Production of submicron-size monodisperse polymer particles having aldehyde groups by seeded aldol condensation polymerization

Submicron-size monodisperse polystyrene/polyglutaraldehyde composite particles having aldehyde groups at the surfaces were produced by seeded aldol condensation polymerization of glutaraldehyde in the presence of polystyrene particles prepared by emulsifier-free emulsion polymerization. This technique is expected to be useful for the production of size-controlled polymer particles having aldehyde groups.Part CXXXVI of the series Studies on Suspension and Emulsion     

Phase separation in the formation of hollow particles by suspension polymerization for divinylbenzene/toluene droplets dissolving polystyrene

Phase-separation behavior within polymerizing divinylbenzene/toluene droplet dissolving polystyrenes (PS) was investigated to clarify the formation mechanism of the hollow polymer particles by suspension polymerization. No hollow particles were obtained at a low content of low-molecular-weight PS where phase separation occurred at high conversion. On the other hand, hollow particles were obtained at a high content of high-molecular-weight PS where phase separation occurred at low conversion. The phase separation in an early stage of the polymerization, which was promoted by the presence of PS and cross-links of polydivinylbenzene, was a key factor for the formation of the hollow structure.     

Spin-lattice relaxation time as a useful indicator for the 13CNMR assignment of terminal cis- and trans-methyls in 2-methyl-1-propenyl moiety

T₁ gives a clue to assign cis- and trans-methyl carbons in 2-methyl-1-propenyl moiety.     

Evaporation behavior of water from aqueous dispersions of multihollow particles prepared by the stepwise alkali/acid method

In order to clarify the formation mechanism of multihollow structures inside styrene–methacrylic acid copolymer particles prepared by the stepwise alkali/acid method, which we proposed in 1990, the evaporation behavior of water from aqueous dispersions of the original carboxylated particles and those after the alkali treatment and the stepwise alkali/acid treatments was examined. It is concluded that the particle after the alkali treatment had a number of small water pools inside. Received: 22 February 2001 Accepted: 20 June 2001     

Synthesis and self-aggregation of cyclic alkynes containing helicene

[structure: see text]. All stereoisomers of a cyclic alkyne containing three helicene units, 1,12-dimethylbenzo[c]phenanthrene, are synthesized using a building block. Isomeric [3 + 3]cycloalkynes aggregate in organic solvents. Vapor pressure osmometry reveals dimer formation of (M,M,M)-[3 + 3]cycloalkynes in chloroform and benzene at concentrations above 2 mM. No higher aggregation is observed. The chirality of helicenes plays an important role in self-aggregation, and diastereomeric (M,P,M)-[3 + 3]cycloalkyne forms a dimer only above 15 mM. Aggregation of racemic (M,M,M)-[3 + 3]cycloalkyne or (M,P,M)-[3 + 3]cycloalkyne is much weaker than that of a single enantiomer.     

Sedimentation and drying dissipative structures of colloidal silica (1.2 μm in diameter) suspensions in a glass dish and a polystyrene dish

Sedimentation and drying dissipative structural patterns formed in the course of drying colloidal silica spheres (1.2 μm in diameter) in aqueous suspension have been studied in a glass dish and a polystyrene dish. The broad ring patterns are formed within a short time in suspension state by the convection flow of water and colloidal spheres. The broad ring patterns are not formed when a dish is covered with a cap, which demonstrates the important role of the convectional flow of silica spheres and water accompanied with the evaporation of water on the air-suspension interface. The sedimentary spheres always move by the convectional flow of water, and the broad ring patterns became sharp with time. Broad ring and microscopic fine structures are formed in the solidification processes on the bases of the convectional and sedimentation patterns. Drying patterns of the colloidal suspensions containing sodium chloride are star-like ones, which strongly supports the synchronous cooperative interactions between the salt and colloidal spheres.