Synthesis of novel phosphinic acid-containing polymers

Three arylene difluoride monomers containing phosphine oxide ( 1 ), phosphinic acid ( 2 ), or phosphinate ester ( 3 ) groups were prepared and polymerized with bisphenol A to give novel poly-(arylene ether)s ( 4 , 5 , and 6 ). The polymers obtained had moderate molecular weights (η_inh: 0.14–0.30 dL g⁻¹ in N-methylpyrrolidinone) and glass-transition temperatures (T_g: 102–200 °C), depending on the phosphine group in the main chain. Using bis(4-fluorophenyl)sulfone as a comonomer improved the polymerization to give copolymers with higher solution viscosities. The stoichiometric investigation revealed that 7 mol % excess of fluoride monomer gave the highest molecular weight copolymer 8 with η_inh of 0.78 dL g⁻¹, which had a T_g of 176 °C, a T of 432 °C, and formed a hard film by casting from solution. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1854–1859, 2001     

Direct determination of the permanent dipole moments and structures of Al-CH(3)CN and Al-NH(3) by using a 2-m electrostatic hexapole field.

The supersonic beams of the (1-1) metal-ligand complexes of Al-CH(3)CN and Al-NH(3) were produced by a laser evaporation method. Nondestructive structure selection of the complexes and the dipole moment determination were performed by using a 2-m electrostatic hexapole field. The experimentally determined permanent dipole moments are 1.2 +/- 0.1 D for Al-CH(3)CN and 2.7 +/- 0.2 D for Al-NH(3). We find that the dipole moment of Al-NH(3) becomes larger than that of neat NH(3), while the formation of the Al-CH(3)CN complex produces a smaller dipole moment than that of neat CH(3)CN on the other hand. We performed the ab initio calculations to draw out plausible complex structures and to clarify the bonding character after formation of the complex, and we made comparisons with the computational results done by several groups. The Mulliken population analysis suggests the Al-->CH(3)CN charge flow, but on the other hand the Natural population analysis indicates very little charge flow. For the Al-NH(3) complex, the polarization effect of NH(3) and the N-->Al sigma donation would enhance the dipole moment strength. However, there still remains a controversial disagreement between the theoretical predictions and the experimental results. Further experimental determination using the hexapole method for various metal-ligand complexes and clusters could reveal the basic nature of interaction in the complex systems in general, and this method would complement theoretical calculations.     

Strain energy function of an uncross-linked butadiene rubber estimated from planar extension

The derivatives of the strain energy function u with respect to the invariants of the strain tensor (I₁ and I₂) are estimated for uncross-linked butadiene rubber by using the BKZ constitutive equation. The derivatives at small deformations show anomalous behavior; namely, an upturn for ∂u/∂I₁ and a downturn for ∂u/∂I₂ take place, as is the case of cross-linked rubbers. At large deformations, u is well described by u = A₁(I₁ −3) + A₂(I₂ −3) with numerical constants A₁ and A₂. This behavior is also quite similar to that for cross-linked rubbers. The non-zero positive constant A₂ for the melt suggests that the non-zero value is due to neither the inhomogeneity in network structure nor high extension of constituent polymer chains.     

Determination of Permeability Distributions Using NMR Velocity Imaging

This study develops a methodology for determining the absolute permeability distribution in a porous media sample using velocity data obtained from NMR imaging experiments. An objective function describing the discrepancy between observed and simulated data is reduced by iteratively updating the permeability. This parameter estimation scheme is based on an iterative method which uses optimal control theory to refine the estimates. Although this theory is developed for both isotropic and anisotropic porous media, the permeability reconstructions examined in this paper are restricted to the isotropic case. Synthetic data are used to investigate the impact of varying the noise in the experimental data, the degree of parameterization, the relative weighting of the regularization term in the objective function, and the amount and type of data required to obtain a satisfactory permeability reconstruction. These synthetic data are extracted from the solution of numerical experiments that have utilized an assumed permeability distribution. The methodology is also applied to data gathered in laboratory experiments for water flow in a sandstone sample.     

Smoothing Property for Schrödinger Equations¶with Potential Superquadratic at Infinity

We prove a smoothing property for one dimensional time dependent Schr?dinger equations with potentials which satisfy at infinity, k≥ 2. As an application, we show that the initial value problem for certain nonlinear Schr?dinger equations with such potentials is L ₂ well-posed. We also prove a sharp asymptotic estimate of the L ^p -norm of the normalized eigenfunctions of H=−Δ+V for large energy. Dedicated to Jean-Michel Combes on the occasion of his Sixtieth Birthday Received: 10 October 2000 / Accepted: 29 March 2001     

Coulometric titrations of electrolytes in water by a solid state ionic device using Nafion and Tosflex membranes

A solid state ionic device to titrate electrolytes in water was produced, and the performance of the device was examined. The device named the coulometric titration apparatus is a three-component electrochemical cell like an electrodialyzer. The central component, the analyzing room, is a container of the sample solution. The sample solution, 10⁻¹ M H₂SO₄, NaOH, Na₂SO₄, or 10⁻⁷–10⁻² M Na₂SO₄, is separated from the cathode and the anode room solutions, 10⁻² M H₂SO₄, NaOH, or Na₂SO₄, by Nafion-117 and Tosflex IE-SF34 membranes working as the anion and the cation blocking electrodes, respectively. The quantity of electricity to extract whole electrolytes in the sample solution is evaluated from the peak area of the titration curve. The sample concentration is successfully determined by the calibration curve method, with the quantity of electricity and the sample volume (6 ml) in the range from 10⁻¹ to 10⁻⁵ M.     

Development of an in vitro Batch-type Closed Gas Exposure Device with an Alveolar Epithelial Cell Line, A549, for Toxicity Evaluations of Gaseous Compounds

To simply evaluate toxicity for various types of exhaust-gas samples collected in various locations, we developed a small-scale (150 mL) batch-type completely closed gas exposure device incorporated with an air-liquid interface culture of a human alveolar epithelial cell line, A549. On the basis of cell viability tests using an acid phosphatase assay after 48 h of gas exposure, the developed device was able to measure clear dose-response relationships for volatile organic and inorganic compounds, such as benzene, trichloroethylene (TCE), acetone, SO(2) and NO(2) gases, but not CO gas. Although the 50% effective concentration values in the device were much higher than 50% lethal concentration values reported in animal experiments, the tendency of the toxic intensity observed in the former was roughly consistent with that of the acute toxicity in the latter. We further applied the device to evaluate the toxicity of cigarette smoke as an example of actual environmental gases, and successfully measured acute cell death from the gas after 48 h of exposure. The present small device is expected to be one of good tools not only in simultaneously assessing various gaseous chemicals or samples, but also in studying acute toxicity expression mechanisms in human lung epithelia.     

Synthesis and characterization of highly fluorescent polythiophene derivatives containing polystyrene sidearms

In this study, macroinitiators with different content of atom‐transfer radical polymerization (ATRP) functional group on polythiophene backbone were first prepared by the copolymerization of 3‐[1‐ethyl‐2‐(2‐bromopropionate)]thiophene and 3‐hexylthiophene with various feed ratio. Then poly [3‐hexyl‐2,5‐thienylene‐co‐3‐[1‐ ethyl‐2‐(2‐[poly(styrene)]propionate)]‐2,5‐thienylene] (PTTBr‐PS) with different graft density were obtained by ATRP of styrene from these macroinitiators in anisole. The degree of polymerization of PS sidearm (DP_PS) was controlled by polymerization time. The structures of obtained graft copolymers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (¹H NMR) and differential scanning calorimetry (DSC). Introduction of the PS sidearms onto the backbone of polythiophene was an attempt to trap the polythiophene backbone in a “solution‐like” conformation, thus inhibit the packing of polythiophene backbone and result in the improvement of fluorescent property in solid state. This was verified by the UV–vis and fluorescence analyses. Besides, it was also found that the optical property of PTTBr‐PS graft copolymer was dominated by its graft density and independent on the degree of polymerization of its PS sidearm. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1003–1013, 2008     

<Emphasis Type="Italic">p</Emphasis>-Adic Brownian motion over ℚ<Subscript><Emphasis Type="Italic">p</Emphasis></Subscript>

In this paper, we generalize the result of Bikulov and Volovich (1997) and construct a p-adic Brownian motion over ℚ _p . First, we construct directly a p-adic white noise over ℚ _p by using a specific complete orthonormal system of (ℚ _p ). A p-adic Brownian motion over ℚ _p is then constructed by the Paley-Wiener method. Finally, we introduce a p-adic random walk and prove a theorem on the approximation of a p-adic Brownian motion by a p-adic random walk.     

New estimation methods of erase band width and track-edge noise in perpendicular magnetic recording

In order to realize higher track density, improving recording resolution and noise at track edge is one of the crucial issues. It has been considered that the erase band (EB), which appears at track-edge, can suppress the cross-talk noise from the adjacent track. On the other hand, the EB consists of a randomly magnetized area that may emanate track-edge noise. In this study, we estimated the accurate EB width by a newly proposed technique and derived analytical formula of the 747 curve with large EB noise. As a result, we found that the peak of track-edge noise was outside the EB and the EB was enough of a noise source at track edge and may be obstructive to the improvement of track density. A bump of 747 curve was produced in the case of little noise of EB. There is a close relationship between the shape of the 747 curve and the EB noise.