Estimation of monomer reactivity ratios by nonlinear least-squares procedure with consideration of the weight of experimental data

To obtain the optimum values of the monomer reactivity ratios for the copolymerization systems with largely different reactivities between both monomers, a nonlinear least-squares procedure which took into account the weights of experimental data, was proposed and discussed. The weights of the data were treated for the errors arisen from the amounts of monomers charged, the densities of monomers, the weights of copolymer formed, and the composition of copolymer. The least-squares procedure with the consideration of the weights was applicable to both differentiated equation and integrated equation derived by Lewis and Mayo. This procedure was applied to radical copolymerizations of α-substituted crotonic esters with styrene, and reasonable monomer reactivity ratios were obtained. It was noted that errors from the copolymer composition were more important than those from the other factors and that the use of the integrated equation was recommended even when the copolymers were isolated at low conversions.     

Development of high-radiation-sensitive polymer gel for magnetic resonance imaging in three-dimensional dosimetry

We developed a high radiation sensitive polymer gel by modifying the amounts of the gel components and the temperature for the gel preparation. We evaluated its relaxation time linearity against dose and compared the measured dose distribution with the calculated one. For the relaxation time-dose linearity, irradiations were carried out with a linear accelerator using 6 MV photons and doses ranging from 0-5.0 Gy. The relationship between dose and R(2) value (reciprocal of T(2) relaxation time) was measured and it had good linearity over a wide range (0.3-5 Gy). The measured dose distributions were in good agreement with calculated ones. Since the present gel has higher sensitivity and it is synthesized more easily at lower cost than conventional polymer gels, we expect to see improved three-dimensional (3D) dosimetry using it.     

Oxygen vacancy promoting catalytic dehydration of formic acid on TiO2(110) by in situ scanning tunneling microscopic observation

The catalytic dehydration reaction processes of formic acid on a TiO2(110) surface at 350 K have been studied to visualize reaction intermediates and their dynamic behaviors by scanning tunneling microscopy. Three types of configurations of adsorbed formates on the surface were identified by their shapes and positions in STM images. Successive STM observations revealed transformations among the three configurations, i.e., bridge formate on a 5-fold coordinated Ti4+ row, bridge formate on an oxygen vacancy site with an oxygen atom of formate and on a 5-fold coordinated Ti4+ ion and with the other formate oxygen atom, and a monodentate formate on an oxygen vacancy site with an oxygen atom of formate. The decomposition of the monodentate formate to carbon monoxide and hydroxyl was also imaged, which is a rate-determining step in the catalytic dehydration of formic acid. Combined with first-principle DFT calculations, the overall reaction processes of the catalytic dehydration of formic acid on the surface have been elucidated. Oxygen vacancies on the surface that can be produced by dehydration of two hydroxyls in situ under the catalytic reaction conditions are essential for the reaction.     

Spontaneous racemization and epimerization behavior in solution of chiral nitroxides

[reaction: see text] Enantiomerically enriched samples of chiral cyclic nitroxides with a 4-hydroxyphenyl group on the stereogenic center bearing the NO radical group undergo unprecedented spontaneous racemization and/or epimerization in aprotic solvents, which can be well accounted for by the multistep equilibrations involving planar quinoid intermediates.     

Exact analysis of ESR shift in the spin-1/2 Heisenberg antiferromagnetic chain

A systematic perturbation theory is developed for the ESR shift and is applied to the spin-1/2 Heisenberg antiferromagnetic chain with a general anisotropic exchange interaction. Using the Bethe ansatz technique, the resonance shift is obtained exactly for the whole range of temperature and magnetic field in the first order of the anisotropy. The obtained g shift strongly depends on magnetic fields at low temperature, showing a significant deviation from the previous classical result.     

Mechanism of stabilization of ballooning modes by toroidal rotation shear in tokamaks

A ballooning perturbation in a toroidally rotating tokamak is expanded by square-integrable eigenfunctions of an eigenvalue problem associated with ballooning modes in a static plasma. Especially a weight function is chosen such that the eigenvalue problem has only the discrete spectrum. The eigenvalues evolve in time owing to toroidal rotation shear, resulting in a countably infinite number of crossings among them. The crossings cause energy transfer from an unstable mode to the infinite number of stable modes; such transfer works as the stabilization mechanism of the ballooning mode.     

Observation of B0-->pi0pi0

We report the observation of the decay B0-->pi(0)pi(0), using a 253 fb(-1) data sample collected at the Upsilon(4S) resonance with the Belle detector at the KEKB e(+)e(-) collider. The measured branching fraction is B(B0-->pi(0)pi(0))=(2.3(+0.4+0.2)(-0.5-0.3))x10(-6), with a significance of 5.8 standard deviations including systematic uncertainties. We also make a measurement of the direct CP violating asymmetry in this mode.     

Age-dependent plasticity in the superior temporal sulcus in deaf humans: a functional MRI study

Background  

Sign-language comprehension activates the auditory cortex in deaf subjects. It is not known whether this functional plasticity in the temporal cortex is age dependent. We conducted functional magnetic-resonance imaging in six deaf signers who lost their hearing before the age of 2 years, five deaf signers who were >5 years of age at the time of hearing loss and six signers with normal hearing. The task was sentence comprehension in Japanese sign language.