ESR studies of polyacenic semiconductive material

ESR measurements have been performed on the polyacenic material prepared by the pyrolytic treatment of phenol-formaldehyde resin. Six kinds of samples (A)-(F) with various electrical conductivity (σ) were employed for the measurements. Each sample shows a single narrow line, the g-values of which suggest the existence of unpaired electrons of π-type. If the sample (F) (σ = 1 × 10° S cm^?1) the single narrow line becomes drastically diminished in the presence of a small amount of oxygen.     

Cis-trans isomerization of iodine-doped polyacetylene

A quantitative analysis of the cis—trans isomerization of the lightly doped polyacetylene with iodine at room temperature is reported. The cis—trans ratio was determined on the basis of the infrared absorption measurement. The result clearly demonstrates the promotion of the isomerization with increase in the dopant concentration. The degree of the amount of the isomerization, however, is rather small compared with the previous study based on the nuclear magnetic resonance measurement.     

Random field effects in the three dimensional Ising magnet: Fe x Zn1−x F2

We have carried out a comprehensive neutron scattering study of random field effects in the diluted three dimensional Ising antiferromagnet Fe _x Zn_1–x F₂ withx=0.35 and 0.5. Emphasis is on the global trands from the small to the large random field regimes. It is found, as in previous experiments, that when the system is cooled in a field it evolves from the high temperature paramagnetic state to a low temperature domain wall state. The low temperature peaks are well-described by Lorentzian squared profiles although for thex=0.5 sample extinction made the measurements difficult. In both samples, the results show that in the field-cooled state the correlation length varies asH ^–v withv=2.2±0.1. In thex=0.35 sample this power law holds over a length scale varying from 2 to 1500 lattice constants. At low fields pretransitional behavior similar to that observed previously in Fe_0.6Zn_0.4F₂ is found. AtT _N (H=0) it is found that the correlation length also scales algebraically withH but withv=0.86±0.04. Pronounced history-dependent effects are observed below the phase boundary determined by the peak in the critical scattering. For example, on cooling in zero-field, raising the field and then warming, long range order survives up to the phase boundary; at this point it appears to convert abruptly into the finite correlation length field cooled state although elucidation of the explicit nature of this transition is complicated by rounding due to a concentration gradient. These results are discussed in the context of recent theories incorporating metastability effects as well as recent experiments.     

Water-assisted oxo mechanism for heme metabolism

A mechanism of heme metabolism by heme oxygenase (HO) is discussed from B3LYP density functional theory calculations. The concerted OH group attack to the alpha-carbon by the iron-hydroperoxo species is investigated using a model with full protoporphyrin IX to confirm our previous conclusion that this species does not have sufficient oxidizing power for heme oxidation (J. Am. Chem. Soc. 2004, 126, 3672). Calculated activation energies and structures of the intermediates and transition state for this process remain unchanged from those for a small model with porphine in the previous study, which shows that the inclusion of the side chain of the porphyrin ring is not essential in describing the OH group transfer. The activation barrier for a direct oxo attack to the alpha-carbon by an iron-oxo model is calculated to be 49.8 kcal/mol, the barrier height of which looks very high for the enzymatic reaction under physiological conditions. This large activation energy is due to a highly bent porphyrin structure in the transition state. However, a bridging water molecule plays an important role in reducing the porphyrin distortion in the transition state, resulting in a remarkable decrease of the activation barrier to 13.9 kcal/mol. A whole-enzyme model with about 4000 atoms is constructed to elucidate functions of the protein environment in this enzymatic reaction using QM/MM calculations. The key water molecule is fixed in the protein environment to ensure the low-barrier and regioselective heme oxidation. A water-assisted oxo mechanism of heme oxidation by heme oxygenase is proposed from these calculational results.     

Interpolation of contour intervals in Moire topography by phase modulation

A trial has been performed with respect to the interpolation of contour intervals in Moiré topography by making use of phase modulation. A simple mechanical system can bring improved results for the precise measurements of shape of a specimen.