Oxygen-Binding Profile of the Iron Porphyrin Complex Embedded in Polymerized Liposome: Effect of the Polymerized Liposome on the Stability and the Oxygen-Binding Ability of the Iron Porphyrin Complex

5,10,15,20-Tetra(α,α,α,α, -o-(2′, 2′-dimethyl-20′-(2′ α-trimethylammonioethyl)phosphonatoxyeicosanamido)phenyl)porphinatoiron(II) (lipidheme) complex embedded in polymerized liposome was prepared by polymerizing l-(9-(p-vinylbenzoyl)nonanoyl)-2-O-octadecyl-rac-glycero-3-phosphocholine in the presence of lipid-heme under ultraviolet irradiation. The polymerization proceeded rapidly, and the reduction of the hemin to the heme occurred spontaneously during the polymerization. The lipid-heme complex embedded in the polymerized liposome bound molecular oxygen reversibly under physiological conditions (pH 7, 37°C) and was chemically, physically, and mechanically stable during storage for a long period and even in a high-speed flow system. The oxygen-binding affinity was not affected by the type of medium due to the effect of the rigid polymerized liposome.     

Selective Encapsulation and Unusual Stabilization of cis-Isomers by a Spherical Polyaromatic Cavity

To explore new cavity functions, we herein employed cis-trans stereoisomers with a N=N, C=C, or C=N unit as guest indicators for a polyaromatic capsule. Thanks to the rigid, spherical cavity with a diameter of ∼1 nm, azobenzene and stilbene derivatives are quantitatively encapsulated by the capsule with 100 % cis-selectivity in water. The isomerization of the cis-azo compound is suppressed against heat and light in the cavity, due to the confinement effect. Furthermore, C,N-diphenyl imine derivatives are quantitatively encapsulated by the capsule in water and adopt an otherwise unstable cis-form. The polyaromatic cavity suppresses the hydrolysis of the imines in water, even at elevated temperature, due to the shielding effect. Accordingly, the properties of the cis-trans isomers could be largely altered through supramolecular manipulation.     

Color adjustment algorithm adapted to the spectral reflectance estimation method

We are developing a daily health monitoring system that uses mobile phones with cameras and analyzes physiological conditions from R, G, and B intensity levels. However, since it is affected by various imaging conditions of the image input, color correction is required for accurate health monitoring. Therefore, we developed and validated a colorcorrection algorithm to derive reliable color information by correcting the spectral reflectance using the Wiener estimation and a color chart.     

Invited Lecture. Ferroelectric liquid crystalline polymers and related model compounds with a low–moderate degree of polymerization

Abstract

Ferroelectric liquid crystalline polymers (FLCPs) with a low-moderate degree of polymerization were synthesized. These had a comb structure; the main chain was polyacrylate and the side chain consisted of a flexible spacer, a core and an optically active chiral end group. They exhibited electro-optic switching times ranging from a few milliseconds to a few seconds in the S*_c phase. As the molecular weight M _n increased, the range of the S*_c shifted to higher temperatures. At a given temperature, the switching time increased with M _n .

Spontaneous polarizations P _s , apparent cone angles 2θ, electro-optic switching times τ and rotational viscosities η of some polyoxyethylene FLCPs and corresponding low molecular weight ferroelectric liquid crystal materials (FLCs) were also measured. This is the first report of polyoxyethylene FLCPs. There was no significant difference in P _s and 2θ, which shows that the arrangement of the side chains in the FLCP is similar to that of the molecules in ordinary FLC. On the contrary, τ and η for the FLCPs were 10²–10³ times as large as those for FLCs. The rotational viscosity of the FLCP was mainly dependent on the side chain structure rather than on the spacer. Therefore collisions between adjacent side chains cause large η values in FLCPs rather than hindrance to side chain gyration due to the spacer group. By combining FLCPs with ITO-coated plastic substrates, a large area matrix driven display has been made. Although an improvement in switching time is still needed, a flexible and lightweight display like a sheet of paper will be available in the near future.     

Detection of high-energy gamma rays from winter thunderclouds

A report is made on a comprehensive observation of a burstlike gamma-ray emission from thunderclouds on the Sea of Japan, during strong thunderstorms on 6 January 2007. The detected emission, lasting for approximately 40 sec, preceded cloud-to-ground lightning discharges. The burst spectrum, extending to 10 MeV, can be interpreted as consisting of bremsstrahlung photons originating from relativistic electrons. This ground-based observation provides the first clear evidence that strong electric fields in thunderclouds can continuously accelerate electrons beyond 10 MeV prior to lightning discharges.     

Improvement of basic performances of a nickel-metal hydride battery

To develop a sealed-type nickel-metal hydride battery for use in portable equipment or in electric vehicles, investigations were conducted on negative electrodes using AB₅-type hydrogen storage alloy and positive electrodes. For the cycle life performance of the battery, alkaline treatment of the alloy and the substitution of more than 50% to the alloy with Co were effective. For the positive electrode, zinc as a solid solution in the nickel positive electrode obviously prevented γ-NiOOH from being formed in the charging process of β-Ni(OH)₂ and suppressed the migration of the electrolyte solution in the separator to the active material of the positive electrode. Also, hydrophobic treatment of the surface of the alloy was effective to prevent the elevation of the battery internal pressure of the battery in high rate charge.     

Carbon-13 NMR studies of the biologically active nor-diterpenoid dilactones from Podocarpus plants

Carbon-13 NMR signals of the biologically active norditerpenoid dilactones from Podocarpus plants were fully assigned by using selective ¹H decoupling, coupling constants (²J_CH), spin-lattice relaxation times (T₁) and correlation of the spectra of more than thirty dilactone congeners. The spectra of five nagilactones, B, C, D, E and F, which constitute representative members of three major structural types of the dilactones: (A) 8:14, 9:11-dienolide (α-pyrone) type, (B) 7α:8α-epoxy-9:11-enolide type, and (C) 7:8,9:11-dienolide type, were extensively analysed. Some characteristic steric interactions for the substituents on the ring system can be demonstrated from the spectral properties.