Vinyl polymerization. 179. Effects of substituents on chain transfer reaction of substituted cumenes toward poly(methyl methacrylate) radical

In order to study the effects of substituents on the chain transfer reaction to cumenes, the polymerization of methyl methacrylate in a series of nuclear-substituted cumenes with α,α′-azobisisobutyronitrile as initiator was carried out at 60°C. and the chain transfer constants C were determined. The C values obtained for all substituted cumenes were greater than that (C₀) for unsubstituted cumene, regardless of the electronattracting or -repelling nature of the substituents. Hence the plot of log (C/C₀) against the Hammett σ constants gave no linear relationship. When the plots were made by the modified Hammett equation including resonance effect of the substituents: log (C/C) = ρσ + γE_R, however, a straight line with ρ = 0.03 and γ = 0.9 was obtained. From these results, it may be concluded that the effect of the substitutents on the chain transfer reactivities of cumenes toward attack of a poly(methyl methacrylate) radical is attributable mainly to the resonance contribution in the transition state. These results are also compared with those for polystyryl radical reported previously and discussed.     

Determination of kynurenic acid levels in rat brain microdialysis samples and changes in kynurenic acid levels induced by N‐acetylaspartic acid

The levels of kynurenic acid, an endogenous antagonist of α₇ nicotinic acetylcholine and N‐methyl‐D ‐aspartate receptors, were measured in microdialysis samples obtained from the prefrontal cortices of rats using column‐switching high‐performance liquid chromatography with fluorescence detection. When the perfusate was constantly infused at a rate of 1.0 μ/min, the in vitro recovery of kynurenic acid through the dialysis membrane was approximately 20.4%, and the precision was within 1.31%. Endogenous kynurenic acid in the microdialysis sample was clearly detected using column‐switching high‐performance liquid chromatography. As an application study, N‐acetyl‐L ‐aspartic acid, an endogenous metabolite and precursor of N‐acetyl‐L ‐aspartyl‐L ‐glutamic acid, which is an agonist of metabotropic glutamate receptors, was infused for 120 min through the microdialysis probe. The kynurenic acid level significantly increased during the infusion of N‐acetyl‐L ‐aspartic acid, suggesting that kynurenic acid might have some association with N‐acetyl‐L ‐aspartic acid in vivo. Copyright © 2009 John Wiley & Sons, Ltd.     

Single-molecule reaction and characterization by vibrational excitation

Controlled chemical reaction of single trans-2-butene molecules on the Pd(110) surface was realized by dosing tunneling electrons from the tip of a scanning tunneling microscope at 4.7 K. The reaction product was identified as a 1,3-butadiene molecule by inelastic electron tunneling spectroscopy. Threshold voltage for the reaction is approximately 365 mV, which coincides with the vibrational excitation of the C-H stretching mode. The reaction was ascertained to be caused by C-H bond dissociation by multiple vibrational excitations of the C-H stretching mode via inelastic electron tunneling process.     

Studies of NO adsorption on Pt(110)-(1 x 2) and (1 x 1) surfaces using density functional theory

Adsorption of NO on Pt(110)-(1 x 2) and (1 x 1) surfaces has been investigated by density functional theory (DFT) method (periodic DMol(3)) with full geometry optimization and without symmetry restriction. Adsorption energies, structures, and N-O stretching vibrational frequencies of NO are studied by considering multiple possible adsorption sites and comparing with the experimental data. Adsorption is strongly dependent on both coverage and surface phase. The assignment of adsorption sites has been carried out with precise calculation of vibrational frequencies for NO on various sites. We clearly show the NO site switching on both of the surfaces as found in the experiments: at low coverages, bridge species is formed on the surface, and at high coverages, NO switches to atop sites.     

The first bowl-shaped stable neutral radical with a corannulene system: synthesis and characterization of the electronic structure

[structure: see text] A bowl-shaped neutral radical with a corannulene system has been designed and synthesized for the first time as a stable solid in air. An unequivocal characterization of the electronic properties of the radical shows that an appreciable amount of spin delocalization extends onto the corannulene unit's curved surface.     

Strongly Supercommuting Self-Adjoint Operators

We introduce the notion of strong supercommutativity of self-adjoint operators on a -graded Hilbert space and give some basic properties. We clarify that strong supercommutativity is a unification of strong commutativity and strong anticommutativity. We also establish the theory of super quantization. Applications to supersymmetric quantum field theory and a fermion-boson interaction system are discussed.     

Cloud and aerosol contributions to variation in shortwave surface irradiance over East Asia in July during 2001 and 2007

It is important to clarify the contributions of clouds and aerosols to the variation of surface shortwave irradiance (S) for climatological studies. This study examined the contributions of clouds and aerosols to the variation in S over East Asia (75-135°E, 20-55°N) in July during 2001 and 2007 using the index of potential radiative forcing (PRF) to characterize the temporal and geographical variations. After confirming the validity of PRF for multiyear analyses, we performed several temporal analyses of clouds and aerosols over the whole research domain. Changes in the geographical distribution, contribution histograms, and averaged values were studied. In agreement with previous studies that treated single-year cases, we confirmed that the magnitudes of the temporal changes in S variations due to clouds and aerosols were highly variable geographically. As for domain-averaged S variations, we did not observe defined trends for the research period. It was also found that the temporal variation between one parameter and its S variation was negatively correlated, from the point analyses at two locations. Based on these results, we concluded that PRF is a promising tool for research into long-term S variations. This kind of information will be quite valuable as basic data for use in climate modeling.     

Calorimetric study of the cubic mesogen, ACBC(6)

The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500 K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165 K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30 K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC-cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic-isotropic liquid phase transition.