Heterotactic‐specific radical polymerization of N‐isopropylacrylamide and phase transition behavior of aqueous solution of heterotactic poly(N‐isopropylacrylamide)

Radical polymerization of N‐isopropylacrylamide (NIPAAm) in toluene at low temperatures, in the presence of fluorinated‐alcohols, produced heterotactic polymer comprising an alternating sequence of meso and racemo dyads. The heterotacticity reached 70% in triads when polymerization was carried out at ?40 °C using nonafluoro‐tert‐butanol as the added alcohol. NMR analysis revealed that formation of a 1:1 complex of NIPAAm and fluorinated‐alcohol through C?O···H? O hydrogen bonding induces the heterotactic specificity. A mechanism for the heterotactic‐specific polymerization is proposed. Examination of the phase transition behavior of aqueous solutions of heterotactic poly(NIPAAm) revealed that the hysteresis of the phase transition between the heating and cooling cycles depended on the average length of meso dyads in poly(NIPAAm). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2539–2550, 2009     

Evaluation of pyridoindoles, pyridylindoles and pyridylpyridoindoles as matrices for ultraviolet matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

In an effort to gain an understanding of the processes governing ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI), direct comparison was made of the mass spectra of proteins, carbohydrates and synthetic polymers (polyethylene glycol, polyester and polyamide) by using pyridylindoles, pyridoindoles and pyridylpyridoindoles as UV (337 nm)-MALDI-TOFMS matrices in positive and negative ion mode. In order to study the combined effect of the indole N-H and the pyridine nitrogen of the MALDI matrix on the desorption/ionization process in MALDI, compounds were selected that include either or both of these functions in their structure. Within the compounds studied only those that possess simultaneously both functions in a 1,4-relation behave as very good matrices for proteins. These compounds also work as matrices for some carbohydrates and synthetic polymers used as analytes in the present study. Some of the compounds were also found to be useful for the post-source decay (PSD) analysis of cyclodextrins in positive and negative ion mode. In several cases we also examined the matrix behavior of the corresponding N-methylindole derivatives.     

Stereospecific radical polymerization of N‐tert‐butoxycarbonylacrylamide in the presence of fluorinated alcohols

Radical polymerization of N‐tert‐butoxycarbonylacrylamide (NBocAAm) in toluene at low temperatures in the presence of the fluorinated alcohols, 2,2,2‐trifluoroethanol, 1,1,1,3,3,3‐hexafluoro‐2‐propanol, and nonafluoro‐tert‐butanol, afforded atactic, heterotactic, and syndiotactic polymers, respectively. NMR analysis revealed that the fluorinated alcohols formed hydrogen bonding‐assisted complexes with NBocAAm, with different structures. The difference in the structures of the complexes was responsible for the differences in the induced stereospecificities. Based on the structures of the complexes between NBocAAm and the fluorinated alcohols, mechanisms for the three kinds of stereospecific radical polymerizations are proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Global existence and nonexistence of solutions for second-order nonlinear differential equations

This paper deals with the global existence and nonexistence of solutions of the second-order nonlinear differential equation (φ(x^′))^′+λφ(x)=0${(\phi (x^{\prime }))}^{\prime }+\lambda \phi (x)=0$ satisfying x(0)=_x0$x(0)=x_0$ and x^′(0)=_x1$x^{\prime }(0)=x_1$, where λ   is a positive parameter and φ:(−ρ,ρ)→(−σ,σ)$\phi :(-\rho ,\rho )\to (-\sigma ,\sigma )$ with 0<ρ?∞$0<\rho ?\infty$ and 0<σ?∞$0<\sigma ?\infty$ is strictly increasing odd bijective and continuous on (−ρ,ρ)$(-\rho ,\rho )$. Necessary and sufficient conditions are obtained for the initial value problem to have a unique global solution which is oscillatory and periodic. Examples are given to illustrate our main result. Finally, a nonexistence result for the equation with a damping term is discussed as an application to our result.     

Experimental and modeling studies of grain size and moisture content effects on radon emanation

Some models have already been developed to explain the effect of moisture content on the radon emanation fraction of soil. For this purpose, “microscopic” soil models, which are easy to deal with mathematically but cannot take grain size into consideration, have been designed. These previous models consist basically of two opposite grain surfaces and pores between the grains. In the present study, in order to study the effect of not only moisture content but also grain size, we present a simple modeling approach based on two “macroscopic” soil models: (1) a single-grain model and (2) a multiple-grain model. The latter model represents a configuration of spherical grains packed in a simple cubic structure. Based on these soil models and general assumptions, the radon emanation fraction was calculated as a function of grain size or moisture content by Monte Carlo simulation. The results for the multiple-grain model show that the radon emanation fraction is markedly increased with grain sizes ranging from 10 to 100 μm and reaches a constant value of 50% when moisture content is 0% and the radium is uniformly distributed on the grain surface. Moreover, a drastic increase is seen at smaller grain sizes with increasing moisture content. From these results, we concluded that the calculation of radon emanation depends greatly on the pore size between a Ra-bearing grain and a neighboring grain. The validity of the model was also evaluated by comparison to experimental data.     

Oscillation constant of second-order non-linear self-adjoint differential equations

Our concern is to solve the oscillation problem for the non-linear self-adjoint differential equation (a(t)x’)’+b(t)g(x)=0, where g(x) satisfies the signum condition xg(x)>0 if x≠0, but is not assumed to be monotone. Sufficient conditions and necessary conditions are given for all non-trivial solutions to be oscillatory. The obtained results show that the number 1/4 is a critical value for this problem. This paper takes a different approach from most of the previous research. Proof is given by means of phase plane analysis of systems of Liénard type. Examples are included to illustrate the relation between our theorems and results which were given by Cecchi, Marini and Villari. Received: January 5, 2001?Published online: June 11, 2002     

Metal-free C-H cross-coupling toward oxygenated naphthalene-benzene linked biaryls

The intermolecular C-H cross-coupling between aromatic ethers has been achieved for the first time using perfluorinated hypervalent iodine(III) compounds as extreme single-electron-transfer (SET) oxidants. The demonstrations of this specific coupling could provide a direct route to valuable oxygenated mixed naphthalene-benzene biaryls 3 only, without formation of other biaryl-derived byproducts.     

Strong coupling between 4f valence instability and 3d ferromagnetism in Yb(x)Fe4Sb12 studied by resonant x-ray emission spectroscopy

We have investigated the temperature and pressure dependency of the electronic structure of Yb-filled skutterudites, YbFe(4)Sb(12) and Yb(0.88)Fe(4)Sb(12), using x-ray absorption and emission spectroscopies. An anomalous increase of the Yb valence, which is beyond the conventional Anderson model picture, is found to coincide with the onset of the ferromagnetic order in the x=0.88 sample below 20 K. In contrast, the nearly stoichiometric YbFe(4)Sb(12) is paramagnetic down to 2 K and the Yb valence is independent of temperature. This evidences a close interplay between the magnetic instability of the Fe 3d electrons and valence instability of the Yb 4f electrons. Under pressure, a sudden increase in the valence is found to occur around 13 GPa for YbFe(4)Sb(12) and 17 GPa for Yb(0.88)YbFe(4)Sb(12).     

Synthesis of skeletal analogues of saxitoxin derivatives and evaluation of their inhibitory activity on sodium ion channels Na(V)1.4 and Na(V)1.5

Skeletal analogues of saxitoxin (STX) that possess a fused-type tricyclic ring system, designated FD-STX, were synthesized as candidate sodium ion channel modulators. Three kinds of FD-STX derivatives 4a-c with different substitution at C13 were synthesized, and their inhibitory activity on sodium ion channels was examined by means of cell-based assay. (-)-FD-STX (4a) and (-)-FD-dcSTX (4b), which showed moderate inhibitory activity, were further evaluated by the use of the patch-clamp method in cells that expressed Na(V)1.4 (a tetrodotoxin-sensitive sodium channel subtype) and Na(V)1.5 (a tetrodotoxin-resistant sodium channel subtype). These compounds showed moderate inhibitory activity towards Na(V)1.4, and weaker inhibitory activity towards Na(V)1.5. Uniquely, however, the inhibition of Na(V)1.5 by (-)-FD-dcSTX (4b) was "irreversible".