Real-time charge oscillation between monomers in a dimeric system associated with intermolecular vibration induced by an ultrashort pulse

Ultrafast charge resonant (CR) dynamics between two molecules in a dimer system has been studied theoretically and experimentally using 6-fs laser pulses and a thin film of amorphous-phase phthalocyanine tin(IV) dichloride (SnPc). The modulation of the absorbance change in the bleaching spectral range of the CR absorption band was analyzed to obtain the amount of charge resonantly transferred back and forth by a dimeric vibration induced by photoexcitation. The modulation can be explained in terms of a periodic change in the cross section and a periodic energy shift, where both are induced by the change in the overlap integral caused by the accordion-type intermolecular vibration. The associated change in distance between two molecules with the intermolecular vibration was estimated to be 0.09 A, which corresponds to 2.5% of the mean distance between the two SnPc molecules in the dimeric system.     

Carrier-envelope phase-controlled quantum interference in optical poling

We demonstrate the efficiency of the optical poling process that depends on the CE phase-controlled quantum interference. For the experiment we employed our noncollinear optical parametric amplifier system for the self-stabilization of the CE phase, with the f-to-2f spectral interferometry system to control the CE phase.     

New fabrication method for anisotropic gratings formed in photocrosslinkable polymer liquid crystals

We present a new fabrication method, called two-step ultraviolet exposure, to prepare anisotropic gratings in photocrosslinkable polymer liquid crystal films. Using the controllability of the reorientation direction of mesogenic molecules, anisotropic phase gratings, in which the mesogenic molecules were periodically modulated in orthogonal directions, were prepared by the use of one grating photomask. The resultant gratings diffract the light and convert the polarization states at the same time, and have applications as diffraction optical devices. PACS 42.65.Hw; 42.70.Df; 42.70.Nq; 78.20.-e; 78.40.Me     

Reliability of mean transit time obtained using perfusion-weighted MR imaging; comparison with positron emission tomography

The purpose of this project was to assess the reliability of the cerebral mean transit time (MTT) obtained using perfusion-weighted MR imaging by comparing it with the MTT obtained when performing positron emission tomography (PET). Ten patients with chronic occlusive cerebrovascular disease were investigated. They had either unilateral internal carotid artery occlusion or middle cerebral artery occlusion. The regions-of-interest were placed in non-infarcted areas within the territory of the middle cerebral artery on the affected side. Control regions-of-interest were placed in mirrored regions of the contralateral side. Linear regression analyses were performed using the parameters of the MTT obtained with perfusion-weighted MR imaging and the MTT, cerebral blood flow, vascular reactivity, and oxygen extraction fraction obtained with PET. The respective MTTs of the affected and non-affected sides obtained with perfusion-weighted MR imaging versus those with PET were 7.3 +/- 2.2 s and 6.0 +/- 1.2 s versus 8.2 +/- 3.0 s and 6.4 +/- 1.7 s. The MTT obtained using perfusion-weighted MR imaging and PET demonstrated statistically significant correlation (r = 0.87, p < 0.0001). The MTT obtained with perfusion-weighted MR imaging correlated statistically with cerebral blood flow (r = -0.74, p < 0.001), vascular reactivity (r = -0.73, p < 0.001) and oxygen extraction fraction (r = 0.61, p < 0.01). Similarly, the MTT obtained using PET statistically correlated with cerebral blood flow (r = -0.78, p < 0.0001), vascular reactivity (r = -0.51, p < 0.05) and oxygen extraction fraction (r = 0.68, p < 0.01). The reliability of the MTT obtained using perfusion-weighted MR imaging appears to be approximately equal to that obtained with positron emission tomography.     

Simultaneous observation of low temperature 4f-4f and 3d-3d emission spectra in a series of Cr(III)(ox)Ln(III) assembly

We report here the low temperature emission spectra in the heterometal dinuclear 3d-4f assembled molecular system [(acac)₂Cr^III(μ-ox)Ln^III(HBpz₃)₂] (Cr(ox)Ln:acac⁻=acetylacetonate, ox²⁻=oxalate, HBpz₃⁻=hydrotris(pyrazol-1-yl)borate; Ln=La, Nd, Ho, Er , Tm and Yb) in comparison with those of Na[Cr(acac)₂(ox)] and [(HBpz₃)₂Ln(μ-ox)Ln(HBpz₃)₂](Ln=Nd and Er). From 10 to 150 K the Cr(ox)Ln complexes show a broad emission band around 800 nm from the ²E state of Cr(III) moiety. At room temperature no ²E-⁴A₂ emission was observed in the Cr(ox)Ln except for the La and Lu complexes. On warming from 10 to 300 K rapid quenching of the ²E-⁴A₂ emission of Cr(III) is suggested to result from the energy transfer from Cr to Ln in the Cr(ox)Ln. The excitation spectra and the life-time were also measured with monitoring the 4f-4f emission peaks of the Cr(ox)Yb complex.     

Fabrication and optical reflection behavior of a two-dimensional barium titanate ceramic photonic crystal

We demonstrate a method for fabricating a two-dimensional hexagonal array of nanoscale barium titanate ceramic pillars. A precursor array was prepared by introducing a sol solution into an electron-beam resist mold with air holes and subsequently dry etching the unnecessary gel layer formed on the mold. A ceramic array, consisting of barium titanate ceramic pillars with a radius of 85 nm, a lattice constant of 450 nm, and a height of 500 nm, was fabricated by sintering the precursor array at 1073 K. The reflection spectra for the ceramic array in the visible range revealed the underlying photonic band gaps, which were in good agreement with results calculated using a plane-wave method. PACS 77.84.-s; 42.70.-a; 42.70.Qs     

Tetrahedral Co(II) coordination in alpha-type cobalt hydroxide: Rietveld refinement and X-ray absorption spectroscopy

We report a Rietveld refinement analysis and X-ray absorption study on a green-color Cl(-)-intercalated alpha-type cobalt hydroxide phase. The refinement clearly demonstrated that one-fifth to one-sixth of the Co(II) at octahedral sites was replaced by pairs of tetrahedrally coordinated Co(II) on each side of the hydroxide plane, represented by a structural formula of [Co(octa)(0.828)Co(tetra)(0.348)(OH)2](0.348+)Cl(0.348).0.456H2O. X-ray absorption spectroscopy also indicated that the divalent cobalt were in local neighboring environments of both octahedral and tetrahedral coordination. Furthermore, UV-vis spectroscopic measurements elucidate the typical green/blue color of an alpha-type cobalt hydroxide.     

CYP119 plus a Sulfolobus tokodaii strain 7 ferredoxin and 2-oxoacid:ferredoxin oxidoreductase constitute a high-temperature cytochrome P450 catalytic system

The cytochrome P450 superfamily of enzymes catalyzes a broad range of oxidative processes involved in the metabolism of fatty acids, biosynthesis of sterols, and elimination of drugs and xenobiotics. Application of the unique properties of P450 enzymes as fine biocatalysts in biotechnology is limited due to their thermal instability and the requirement for auxiliary electron-donor proteins and cofactors. CYP119, a thermophilic P450 enzyme from Sulfolobus solfataricus, was characterized some time ago, but no high-temperature redox partners have been available for it. Here we report reconstitution of CYP119 with a novel high-temperature electron-donor system consisting of a ferredoxin and 2-oxoacid:ferredoxin oxidoreductase from Sulfolobus tokodaii strain 7 that, unlike all other known P450 electron-donor partners, utilizes coenzyme-A and pyruvic acid rather than NADH or NADPH as the source of electrons. The oxidation of lauric acid by the reconstituted system increased 16-fold as the temperature increased from 25 to 70 degrees C and was functional for more than 30 min at the higher temperature. This first in vitro high-temperature P450 catalytic system is a key step in the development of practical high-temperature monooxygenase systems.