Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

The first vapochromic organic crystals are described with respect to their preparation, color change, adsorption/desorption properties, crystal structures, and color‐change mechanism. Non‐solvatochromic, 1,4,5,8‐naphthalene‐tetracarboxylic diimide (NDI) derivatives 1 a bearing two pyrrole imine (PI) tethers have been used as a motif for the crystal packing template. Red‐purple vapochromic solid 3 was prepared by evacuation of orange crystals 2 (equivalent to 1 a ?2 MeOH), obtained by recrystallization of 1 a from MeOH. Solid 3 showed high‐adsorption ability and unprecedented vapor‐dependent color changes upon exposure to a variety of organic vapors, whereas light brown amorphous solid 1 a , did not show vapo‐ or solvatochromic behavior toward any organic solvent. The strong adsorption capability of 3 was confirmed by TGA experiments and adsorption/desorption isotherms. Analysis of the solid‐state UV/Vis analysis revealed that the vapor‐dependent color changes of 3 were owed to the specific interference of solvent vapors with its broad CT absorbance at λ=450–650 nm. Packing structures of 1 a in orange crystals 2 , red‐purple solid 3 , and regenerated orange solid 2 were unequivocally established by single crystal and synchrotron powder X‐ray diffraction, respectively. Molecular structures and arrays of 1 a in these materials indicated that 1) unit 1 a had an S‐shaped folded conformation in 2 and 3 by intramolecular donor–acceptor interactions between NDI and two PI units; 2) inclusion of the guest vapor into the S‐shaped template decreased the intramolecular PI‐NDI interactions, accompanied by increasing intermolecular NDI‐NDI and PI‐PI interactions; and 3) such flexible, open–close motions of the S‐shaped template could be repeated during reversible adsorption/desorption processes without degradation of crystal packing. The adsorption properties and mechanism of molecular shape‐dependent vapochromic behavior of 3 are discussed with reference to experimental results, crystallographic data, and theoretical calculations.     

Fast image enlargement using predefined codebook and eigenspace backprojection for lost pixel

In this paper, a new image enlargement method applying the backprojection for lost pixel (BPLP) to the predefined codebook-based method is proposed. BPLP is a method for image restoration. In BPLP, the eigenspace reflecting the characteristics of an input image is generated from the remained pixels and is used to restore the missing pixels. In the proposed method, the eigenspace is replaced by one generated from the predefined codebook (PDC). PDC represents edge-blurring properties in a small image patch and consists of pairs of low- and high-frequency image patches on various edge patterns. By replacing the PDC-based estimation of lost high-frequency components with BPLP, a fast image enlargement method retaining its performance can be developed. Through some experiments, the effectiveness of the proposed method was demonstrated. Especially, it was confirmed that the processing time of the proposed method was shortened to about 1/50 that of the PDC-based method.     

Polarity determination of wurtzite-type crystals using hard x-ray photoelectron diffraction

The surface structure of a single-crystal ZnO wafer was studied by angle-resolved x-ray photoelectron spectroscopy (ARXPS) using synchrotron radiation. As a result, well-defined x-ray photoelectron diffraction (XPD) patterns were obtained for the (0001) and (000$\overline{1}$) polar surfaces using the photoemission from the Zn 2p_3/2 and O 1s core levels. The XPD patterns were indexed assuming forward scattering of photoelectrons by neighboring ions. Further, the XPD patterns for the (0001) and (000$\overline{1}$) surfaces were different from each other, indicating the possibility for using the XPD technique for polarity determination.     

An efficient optical resolution of nitrogen-centered chiral β-hydroxy-tetraalkylammonium salts via complexation with (R)-BINOL

The optical resolution of nitrogen-centered chiral β-hydroxy-tetraalkylammonium bromides is demonstrated by using chiral BINOL as a complexing agent. Determination of the enantiopurities and absolute configurations of the resolved N-chiral tetraalkylammonium salts are described.     

Optimization of mark edge recording waveform for a phase change rewritable optical disk using a 680 nm laser diode

A high density mark edge recording method on a phase change rewritable disk is reported. A carrier-to-noise ratio of 55 dB for a mark length of 0.55,μm is obtained by using a 680 nm, NA 0.6 head and a phase change rewritable disk. In mark edge recording, it is necessary to record each mark in correct length. A new laser power modulation pattern is proposed. This pattern consists of a first-pulse, a multi-pulse chain and a last-pulse. Both positions of the first-ptilse and the last-pulse are movable. By adjusting these positions, a jitter, σ/T_w (T_w is window margin), is improved to 6.5% in high density EFM (Eight to Fourteen Modulation) recording of 0.4 μm/bit.     

Effects of strain path shapes on non-proportional cyclic plasticity

The title problem was discussed to facilitate the formulation of constitutive models of cyclic plasticity under general states of loading. A series of plastic strain controlled cyclic tests was performed by applying combined axial force and torque to thin-walled tubular specimens of Type 316 stainless steel at room temperature. These tests consist of cyclic loading along uniaxial, torsional, cruciform, stellate in eight directions, square and circular plastic strain paths with a constant amplitude of equivalent plastic strain.The results of these tests showed that the strain-hardening depends markedly on the shape of the plastic strain path, and that the strain-hardening (measured by equivalent stress amplitudes) in the saturated state is significant in the order of circular, square, stellate, cruciform and proportional paths. It was also observed that these saturated values were independent of the less significant plastic strain cycles experienced in the past. Finally, the characteristic features of strain-hardening mechanisms under non-proportional loadings were discussed in some detail on the basis of the present results.     

Standing Pulse Solutions in Reaction-Diffusion Systems with Skew-Gradient Structure

The purpose of this paper is to introduce a reaction-diffusion system with skew-gradient structure and discuss the stability of standing pulse solutions. In short, the skew-gradient system is a reaction-diffusion system which resembles a gradient system but has nonlinearities with different sign. We assume the existence of a standing pulse solution and define its orientation in some geometrical manner. Then we show that the stationary solution becomes unstable if time constants satisfy some inequality. The Evans function plays a crucial role for the stability analysis.     

Classification of the structure of positive radial solutions to\Delta u + K(|x|)u^p = 0inR n

Positive radial solutions to the semilinear elliptic equation \(\Delta u + K(|x|)u^p = 0\) inR ⁿ are studied, wherep > 1,n > 2 andK ≧ 0. It is shown that, under a general condition onK(r) andp, the structure of positive radial solutions becomes one of three types. We give sharp criteria to classify the type of the structure, and apply the result to the conformal scalar curvature equation.     

Preparation of highly dispersible and tumor-accumulative, iron oxide nanoparticles Multi-point anchoring of PEG-b-poly(4-vinylbenzylphosphonate) improves performance significantly

This paper describes the preparation of iron oxide nanoparticles, surface of which was coated with extremely high immobilization stability and relatively higher density of poly(ethylene glycol) (PEG), which are referred to as PEG protected iron oxide nanoparticles (PEG-PIONs). The PEG-PIONs were obtained through alkali coprecipitation of iron salts in the presence of the PEG-poly(4-vinylbenzylphosphonate) block copolymer (PEG-b-PVBP). In this system, PEG-b-PVBP served as a surface coating that was bound to the iron oxide surface via multipoint anchoring of the phosphonate groups in the PVBP segment of PEG-b-PVBP. The binding of PEG-b-PVBP onto the iron oxide nanoparticle surface and the subsequent formation of a PEG brush layer were proved by FT-IR, zeta potential, and thermogravimetric measurements. The surface PEG-chain density of the PEG-PIONs varied depending on the [PEG-b-PVBP]/[iron salts] feed-weight ratio in the coprecipitation reaction. PEG-PIONs prepared at an optimal feed-weight ratio in this study showed a high surface PEG-chain surface density (≈0.8 chainsnm(-2)) and small hydrodynamic diameter (<50 nm). Furthermore, these PEG-PIONs could be dispersed in phosphate-buffered saline (PBS) that contains 10% serum without any change in their hydrodynamic diameters over a period of one week, indicating that PEG-PIONs would provide high dispersion stability under in vivo physiological conditions as well as excellent anti-biofouling properties. In fact we have confirmed the prolong blood circulation time and facilitate tumor accumulation (more than 15% IDg(-1) tumor) of PEG-PIONs without the aid of any target ligand in mouse tumor models. The majority of the PEG-PIONs accumulated in the tumor by 96 h after administration, whereas those in normal tissues were smoothly eliminated by 96 h, proving the enhancement of tumor selectivity in the PEG-PION localization. The results obtained here strongly suggest that originally synthesized PEG-b-PVBP, having multipoint anchoring character by the phosphonate groups, is rational design for improvement in nanoparticle as in vivo application. Two major points, viz., extremely stable anchoring character and dense PEG chains tethered on the nanoparticle surface, worked simultaneously to become PEG-PIONs as an ideal biomedical devices intact for prolonged periods in harsh biological environments.