Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior

Anionic polymerizations of three 1,3‐butadiene derivatives containing different N,N‐dialkyl amide functions, N,N‐diisopropylamide (DiPA), piperidineamide (PiA), and cis‐2,6‐dimethylpiperidineamide (DMPA) were performed under various conditions, and their polymerization behavior was compared with that of N,N‐diethylamide analogue (DEA), which was previously reported. When polymerization of DiPA was performed at ?78 °C with potassium counter ion, only trace amounts of oligomers were formed, whereas polymers with a narrow molecular weight distribution were obtained in moderate yield when DiPA was polymerized at 0 °C in the presence of LiCl. Decrease in molecular weight and broadening of molecular weight distribution were observed when polymerization was performed at a higher temperature of 20 °C, presumably because of the effect of ceiling temperature. In the case of DMPA, no polymer was formed at 0 °C and polymers with relatively broad molecular weight distributions (M_w/M_n = 1.2) were obtained at 20 °C. The polymerization rate of PiA was much faster than that of the other monomers, and poly(PiA) was obtained in high yield even at ?78 °C in 24 h. The microstructure of the resulting polymers were exclusively 1,4‐ for poly(DMPA), whereas 20–30% of the 1,2‐structure was contained in poly(DiPA) and poly(PiA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3714–3721, 2010     

Oxygen‐sensing properties of 5,10,15,20‐tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate)

A novel methacrylate monomer bearing 5,10,15,20‐tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a ) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2‐trifluoroethyl methacrylate (TFEM) to give poly (IBM‐co‐TFEM) bearing PdTPP (copolymer 2a ) as a dye‐conjugated oxygen‐permeable polymer for pressure‐sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV–vis spectroscopy and extended X‐ray absorption fine structure analysis. The Stern–Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM‐co‐TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b ) previously reported. The plots were successfully fitted with a two‐site model to give two distinct Stern–Volmer constants (K_SV1 and K_SV2) and the partition ratio f₁. Interestingly, the f₁ values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM‐co‐TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature‐dependent and the other temperature‐independent, in the mixture of PdTPP and poly(IBM‐co‐TFEM). The dye‐conjugation approach effectively eliminates the temperature‐dependent, but not the temperature‐independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature‐dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature‐independent one appears to be inherent nature in PdTPP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663–670, 2010     

Structural development of ultra‐high strength polyethylene fibers: Transformation from kebabs to shishs through hot‐drawing process of gel‐spun fibers

Structural development of ultra‐high strength polyethylene fibers via hot‐drawing processes of as‐spun gel fibers was investigated by means of transmission electron microscopy. It is found that the shish‐kebabs developed in both the as‐spun and drawn fibers can be transformed continuously into the micro‐fibril structure composed mostly of the shish structure through the hot‐drawing process. The structure transformation involves a drastic decrease in diameter of the kebab plus the shish but almost no change in the shish diameter. This result suggests that the chains in the kebabs are incorporated into the shishs and consumed to extend the longitudinal dimension of the shishs during the drawing process. The proposed new deformation model well explains the relationship between the fiber morphology and their mechanical properties: the tensile strength and modulus of the fibers can be determined by the number of the shish in the fiber and the macroscopic diameter of the fiber, which are apriori determined at the spinning process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1861–1872, 2010     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

Gauss’ law of error revisited in the framework of Sharma-Taneja-Mittal information measure

We reformulate the Gauss’ law of error in presence of correlations which are taken into account by means of a deformed product arising in the framework of the Sharma-Taneja-Mittal measure. Having reviewed the main proprieties of the generalized product and its related algebra, we derive, according to the Maximum Likelihood Principle, a family of error distributions with an asymptotic power-law behavior.      

Development of Polarized HD Target for Future LEPS Experiments at Spring-8

We are carrying out hadron photoproduction experiments by using polarized photon beams at SPring-8 in Japan.In 2005,we started developing a polarized HD target for future experiments using both the polarized photon beams and the polarized target.The polarized HD target is an idealistic target for experiments observing reactions with small cross sections because the HD does not include heavy nuclei which produce many background events.The measurement of double polarization asymmetries is expected to give much important information to investigate the nucleon hidden structure,hadron photoproduction dynamics,and exotic hadron property.We report on the present status of the development of the polarized HD target al RCNP.     

Flattened chromatic dispersion in square photonic crystal fibers with low confinement losses

This research presents a simple index-guiding square photonic crystal fibers (SPCFs) that has a silica core surrounded by air hole with two different diameters. It is demonstrated that the designed two-different-size hole-arrayed index-guiding SPCFs has a ultra-flattened chromatic dispersion of 0 ± 0.9 ps/(nm·km) in a wavelength range of 1.34 to 1.61 μm and low confinement loss of less than 10⁻⁷ dB/m in a wavelength range of 1.2 to 1.7 μm. It has also been shown that the proposed SPCFs show reasonable dispersion tolerance.     

Emittance measurement & optimization for the photocathode RF gun with laser profile shaping

The Laser Undulator Compact X-ray source(LUCX) is a test bench for a compact high brightness X-ray generator,based on inverse Compton Scattering at KEK,which requires high intensity multi-bunch trains with low transverse emittance.A photocathode RF gun with emittance compensation solenoid is used as an electron source.Much endeavor has been made to increase the beam intensity in the multi-bunch trains.The cavity of the RF gun is tuned into an unbalanced field in order to reduce space charge effects,so that the field gradient on the cathode surface is relatively higher when the forward RF power into gun cavity is not high enough.A laser profile shaper is employed to convert the driving laser profile from Gaussian into uniform.In this research we seek to find the optimized operational conditions for the decrease of the transverse emittance.With the uniform driving laser and the unbalanced RF gun,the RMS transverse emittance of a 1 nC bunch has been improved effectively from 5.46 πmm.mrad to 3.66 πmm.mrad.     

Ab initio molecular orbital study on three feasible mechanisms for substitution of the vinylic carbon in F2C=C(OMs)BMe3−

A substitution on 2,2-difluorovinylic carbon was investigated by using ab initio molecular orbital calculations. Three feasible mechanisms, which are the S_N1-like, the S_N2-type and the addition-elimination mechanisms, were ex- amined for a model borate, 2,2-difluoro-1-mesyloxyvinyl(trimethyl)borate. Four TSs were obtained depending on the position of Li⁺ around the vinylborate although activation energies in the gas phase are rather high (ca. 30–40 kcal mol⁻¹) in comparison with that expected from the experimental conditions. It was confirmed at the SCRF-IPCM calculations that the solvent effect reduces the acti- vation energy of one S_N2-type mechanism very much (4. l kcal mol⁻¹ at the B3LYP/6-31+G^*//RHF/6-31+G^/s* level of theory) while those for the other mechanisms do not change very much. Therefore, the S_N2-type mechanism is applicable to the substitution reaction observed for the vinylborate.