Ab initio calculations of isomerization reaction of diphosphene 1-sulfide to thiadiphosphirane

Ab initio Calculations of the isomerization reaction of diphosphene 1-sulfide (2′) to thiadiphosphirane (3′) suggest that the energy barrier of the reaction in the ground state is 25 kcal/mol and that 2′ lies 21 kcal/mol above 3′, while the calculations show that there exists one local minimum on the lowest triplet energy surface.     

Affinity chromatographic purification of bovine lung endothelin receptor using biotinylated endothelin and avidin-agarose.

Endothelin receptor was purified from bovine lung by affinity chromatography using biotinylated endothelin and avidin-agarose. Endothelin was biotinylated with sulphosuccinimidyl 2-(biotinamido)ethyl-1,3-dithiopropionate, a reactive form of biotin with a cleavable spacer arm containing a disulphide bond designed for a simple elution by thiols. Starting from 3.5 kg of bovine lung, about 200 micrograms of pure receptor were obtained.     

Drug-plasma protein binding assay by electrokinetic chromatography-frontal analysis

We developed a rapid, microscale and reliable analytical method for binding of drugs to plasma proteins using capillary electrophoresis (CE) with ionic cyclodextrins (CD) combined with frontal analysis. These CDs were used as pseudostationary phases of electrokinetic chromatography (EKC). The CD-modified EKC (CDEKC) approach allowed us to separate anionic drugs from plasma proteins, whereas CZE could not separate these drugs from plasma proteins because they had a similar mobility like plasma proteins. CDs uniquely interact with these drugs but not with plasma proteins. Therefore, CDEKC could be coupled with frontal analysis to measure the binding of anionic drugs to plasma proteins. The binding values obtained by CDEKC were highly consistent with those determined by the ultrafiltration method. Our CDEKC approach should expand the applicability of CE to protein binding analysis.     

Specific interaction between polyethylenimine and azo dyes carrying hydroxyl groups

The binding of acid azo dyes having phenolic hydroxyl groups such as orange I ( I ), orange II ( II ), chrome violet ( III ), 4-hydroxyazobenzene-4′-sulfonate ( IV ), and 2,4-dihydroxyazobenzene-4′-sulfonate ( V ) by polyethylenimine was studied by equilibrium dialysis and spectroscopic methods. The results obtained indicate that dyes ( III ) and ( V ) with two OH groups are bound much more strongly than dyes ( I ), ( II ), and ( IV ) with one OH group. Also polyethylenimine is far superior to any other polymers which have been examined, including bovine serum albumin, polyvinylpyrrolidone, and poly-L -lysine, in its ability to form complexes with these dyes ( III ) and ( V ). The OH groups involved participate preferentially in complex formation with polyethylenimine. The unusual affinity of polyethylenimine for the dyes carrying OH groups is discussed.     

Sol-Gel Preparation and Photoelectrochemical Properties of Fe2TiO5 Thin Films

Polycrystalline Fe₂TiO₅ films were prepared on nesa silica glass substrates by the sol-gel method, and their photoanodic properties were measured in a three-electrode wet cell with an aqueous buffer solution of pH = 7. Gel films were crystallized into Fe₂TiO₅ when fired at 500°C. The photoanodic current significantly increased when the films were fired at 700°C, and then decreased with increasing firing temperature. Thicker films obtained by repeating the gel film deposition and firing showed smaller photocurrent, and the 50 nm thick film prepared via non-repetitive deposition exhibited the maximum photocurrent. Although the photoresponse was extended to wavelengths near 500 nm, the maximum quantum yield was as low as 0.12 at a wavelength of 340 nm.     

Sol–gel preparation and properties of hydroxypropylcellulose–titania hybrid thin films

Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC₃H₇ ⁱ )₄ was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO₂/(HPC + TiO₂) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC₃H₇ ⁱ )₄ is converted into TiO₂. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where cracking did not occur at higher HPC contents even when the substrate was bent.     

Complex formation of amphiphilic polymers with azo dyes and their photoviscosity behavior

The hydrophobic interaction of amphiphilic copolymers, which contain 2-hydroxyethyl methacrylate(HEMA) and 1vinyl-2-pyrrolidone (VPy), with Methyl Orange (MO) was compared with that of HEMA-acrylamide (AAm) copolymers to deduce the correlation between their complexation ability in a photochromic azo dye and the photoviscosity effect in aqueous copolymer/dye complex solution. On the basis of the dialysis data and fluorometric analysis it appeared that the complexation dependence on HEMA content in the copolymers was due to the hydrophobic interaction between the polymer and the dye. For a comparable HEMA content AAm copolymers bound less MO than VPy copolymers. It was confiied by photoviscosity measurements that the conformation of the complex composed of photochromic azo dye and HEMA copolymer changed reversibly in response to the photo- and thermal isomerization of the dye. In HEMA-AAm copolymer systems the photoviscosity effect was small compared with that of HEMA-VPy copolymer systems. From these results it was concluded that the complexation ability of polymers due to the hydrophobic interaction was an important factor in producing a large photoinduced conformational change in water.     

Studies on palytoxins

The complete structure of palytoxin (1) was elucidated by us in 1982.¹ Our continuous interests in palytoxin led us to examine minor constituents of Okinawan Palythoa tuberculosa. In this paper, we describe successful isolation and structural elucidation of four minor toxins, which were named homopalytoxin (2), bishomopalytoxin (3), neopalytoxin (4) and deoxypalytoxin (5).     

Photoreactions of benzosilacyclobutenes with carbonyl compounds. SH2 reaction on SiC bond by triplet carbonyl compounds

Photoreaction of 2,3-benzo-1,1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with an aldehyde or ketone results in 1:1 cycloadduct of [4+2] type, the formation of which is accountd for in terms of S_H2 process, i.e., attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene.     

Photoreaction of anthracenyl phosphine oxides: Usual reversible photo- and heat-induced emission switching,and unusual oxidative PC bond cleavage

Anthracenyl(diphenyl)phosphine oxide and dianthracenylphenylphosphine oxide as photoactive compounds have been synthesized. Anthracenyl group of these compounds indicate the multi-functional roles such as an emission component, a photodimerization component, and a leaving group. When the light irradiation was performed under an oxygen atmosphere, photo-oxidative PC bond cleavage to leave the antharacenyl group was observed. Moreover, phosphonyl radical was produced and then PP bond formation to form diphosphane was observed.