Photochemical control of network structure in gels and photo-induced changes in their viscoelastic properties

Poly(amide acid) gels containing photosensitive azobenzene groups in the main chain have been synthesized and their viscoelastic properties before and after light irradiation have been investigated by dynamic viscoelasticity measurements. It was found that 405 nm light induced a local volume change and a two-fold increase in the storage modulus of the gels. We discuss the change in storage modulus upon light irradiation quite simply in terms of classical rubber elasticity theory, which cannot explain this large increase in storage modulus. The photo-induced increase in storage modulus may result from an increase in entanglement interactions of topological constraints fixed in the network structure, caused by photoisomerization of the azobenzene moieties. We suggest that topological constraints in the network structure of the gels were realized by light irradiation and calculate the resulting slip link ratio (index of the topological constraints) in the gel network.     

Rational method for designing efficient separations by chromatography on polystyrene-divinylbenzene resins eluted with aqueous ethanol

A rational method for designing separation processes by chromatography with polystyrene-divinylbenzene (PS-DVB) resins of different particle diameters (10-400microm) was developed. As model samples, catechin and epigallocatehin gallate (EGCG) were chosen and the mobile phase was an ethanol-water mixture. Linear gradient elution experiments were carried out with different gradient slopes, and the peak ethanol concentration was plotted against the normalized gradient slope. The plots were similar regardless of particle diameter. From these plots the two parameters describing the distribution coefficient K as a function of ethanol concentration I were determined. The K-I curves obtained were verified by isocratic elution experiments, and the conditions at which a baseline separation of the two polyphenols is possible was sought, and confirmed experimentally. Stepwise elution experiments were also designed and performed successfully on the basis of the K-I curve.     

Purification of Two Novel Sugar Acid-binding Lectins from <Emphasis Type="Italic">Haplomitrium Mnioides</Emphasis> (bryophyte,Plantae) and their Preliminary Characterization

Two novel sugar acid-binding lectins were purified from Haplomitrium mnioides (Lindb.) Schust. using a procedure consisting of ammonium sulfate precipitation, G-50 gel filtration, hydroxyapatite chromatography, and HW-50 gel filtration. We reported their partial physicochemical properties: molecular weight, affinity for carbohydrates and organic acids, pH stability, and dependence of their hemagglutination activity on metal ions. We also determined their N-terminal amino acid sequences. H. mnioides lectins (HMLs) were monomers (one with a molecular weight of approximately 27 kDa, and the other with a molecular weight of approximately 105 kDa) under both nonreducing and reducing conditions. They were named HML27 and HML105, respectively. Both HMLs had an affinity for N-acetylneuraminic acid, d-glucuronic acid, d-glucaric acid, bovine submaxillary mucin, heparin, and organic acids, such as citrate, 2-oxoglutaric acid, and d-2-hydroxyglutarate. Furthermore, HML27 had an affinity for α-d-galacturonic acid, d-malate, l-malate, and pyruvate, while HML105 had an affinity for d-gluconic acid. HML27 and HML105 are novel plant lectins: they have an affinity for sugar acids and organic acids and specifically recognize the carboxyl group, and there is no homology between their N-terminal amino acid sequences and those of the previously described lectins and agglutinins.     

Room temperature-stable electride as a synthetic organic reagent: application to pinacol coupling reaction in aqueous media

Room temperature-stable inorganic electride [Ca(24)Al(28)O(68)](4+)4e(-) was employed for a pinacol coupling reaction in aqueous media. Ca-Al-O gel formed by the destruction of the crystal structure of an electride by water media played a key role in transferring the electron to electrophilic aldehydes. Aromatic aldehydes reacted smoothly with moderate to high yields.     

Superconductivity in LaT(M)BN and La3T(M2)B2N3 (T(M) = transition metal) synthesized under high pressure

Various layered boronitrides (LaN)(n)(T(M2)B(2)) (T(M) = transition metal; n = 2, 3) have been prepared using a high-pressure synthesis technique in which an inverse α-PbO-type T(M2)B(2) layer is separated by two or three rock salt-type LaN layers and these layers are connected through linear (BN) units. The electronic states of the distinguishing (BN) unit and intermediate rock salt-type LaN layer are discussed on the basis of density functional theory calculations. Bulk superconductivity has been found in LaNiBN (T(c) ≈ 4.1 K), CaNiBN (T(c) ≈ 2.2 K), and LaPtBN (T(c) ≈ 6.7 K), where the Fermi level E(F) is located in the bands composed of the T(M)(d)-B(2p) antibonding state and the main T(M)(d) band resides well below E(F). The non-superconductive T(M)-based compounds exhibit Pauli paramagnetic behavior, in which the highly itinerant nature of the electrons caused by strong T(M)(d)-B(2p) covalent bonding suppresses the long-range magnetic ordering.     

Size effect on electrochemical property of nanocrystalline LiCoO2 synthesized from rapid thermal annealing method

Nano-sizing of cathode materials for higher power Li-ion rechargeable batteries is an effective method to shorten a Li-ion diffusion path and achieve fast charge transfer. Nanocrystalline LiCoO₂ was synthesized through a combination of rapid thermal annealing method and a sol–gel method assisted with a triblock copolymer surfactant, and the electrochemical properties including the Li-ion chemical diffusion coefficient was investigated. Li-ion deintercalation/intercalation experiments suggested an extreme small amount of cation mixing between Li⁺ and Co³⁺ within a layered structure of LiCoO₂, which was not observable in the Raman spectroscopy. The analysis based on the solution for the diffusion equation of the cylinder model revealed that the cation mixing strongly decelerates the Li-ion diffusion in LiCoO₂.     

Lithium insertion into nanometer-sized rutile-type TixSn1 − xO2 solid solutions

The electrochemical properties of rutile-type Ti_xSn_1?xO₂ solid solutions (x = 0–1.0) as an anode for a lithium–ion battery were investigated using nanosized crystals prepared by an aqueous solution process. The reduction of the crystal size to nanoscale allowed a smooth lithium insertion into the rutile framework at room temperature. The lithium-insertion behavior of TiO₂, SnO₂, and the solid solutions was evaluated without any structural change of the rutile-type crystal structure in the potential range of 1.2–3.5 V (versus Li/Li⁺). The interstitial spaces for lithium ions were found to be derived from the crystal structure of the rutile framework and independent of the metal species.     

Hydrogen permeation of tungsten phosphate glass thin films

Thin films of tungsten phosphate glasses were deposited on a Pd substrate by a pulsed laser deposition method and the flux of hydrogen passed thorough the glass film was measured with a conventional gas permeation technique in the temperature range 300–500 °C. The glass film deposited at low oxygen pressure was inappropriate for hydrogen permeation because of reduction of W ions due to oxygen deficiency. The membrane used in the hydrogen permeation experiment was a 3-layered membrane and consisted of Pd film (~ 20 nm), the glass film (≤ 300 nm) and the Pd substrate (250 µm). When the pressure difference of hydrogen and thickness of the glass layer were respectively 0.2 MPa and ~ 100 nm, the permeation rate through the membrane was 2.0 × 10^? 6 mol cm^? 2 s^? 1 at 500 °C. It was confirmed that the protonic and electronic mixed conducting glass thin film show high hydrogen permeation rate.     

Synthesis of magnetite nanoparticles for AC magnetic heating

Magnetite particles with different average diameter (D_m) suitable for magnetic fluid hyperthermia (MFH) were synthesized by controlled coprecipitation technique. In this method, the reaction pH was stabilized using the pH buffer and the average particle diameter decreased with increasing reaction pH. The size-dependent magnetic behavior of the magnetite nanoparticles was studied and the optimum size range required for magnetic fluid hyperthermia (MFH) has been arrived at. Among the samples studied, the maximum specific absorption rate of 15.7 W/g was recorded for the magnetite sample with D_m of 13 nm, when exposed to an AC magnetic field strength of 3.2 kA/m and a frequency of 600 kHz. The AC magnetic properties suggested that the size distribution of the sample was bimodal with average particle size less than ∼13 nm.     

Heteroepitaxial film growth of layered compounds with the ZrCuSiAs-type and ThCr2Si2-type structures: From Cu-based semiconductors to Fe-based superconductors

FeAs-based layered superconductors such as F-doped LaFeAsO have recently been investigated intensively because of their high superconducting transition temperatures. Epitaxial films of these compounds are important to examine their intrinsic materials properties as well as to transfer them to device applications. In this review, we first present our research route from transparent p-type oxides semiconductors to the Fe-based superconductors. Then we review growth of epitaxial thin films for the layered oxychalcogenides and oxypnictides. Reactive solid-phase epitaxy technique was inevitable to prepare epitaxial thin films of the oxychalcogenides and Zn-based oxypnictides. On the other hand, epitaxial thin films of Mn-based oxypnictides were grown by standard pulsed laser deposition. These techniques, however, did not grow epitaxial thin films for LaFeAsO. Thus, we developed a modified pulsed laser deposition process and succeeded in obtaining epitaxial thin films of FeAs-based superconductors, LaFeAsO and cobalt-doped SrFe₂As₂.