Involvement of electron transfer in the photoreaction of zebrafish Cryptochrome-DASH

Photoreaction of a blue-light photoreceptor Cryptochrome-DASH (Cry-DASH), a new member of the Cryptochrome family, from zebrafish was studied by UV-visible absorption spectroscopy in aqueous solutions at 293 K. Zebrafish Cry-DASH binds two chromophores, a flavin adenine dinucleotide (FAD) and a N5,N10-methenyl-5,6,7,8-tetrahydrofolate (MTHF) noncovalently. The bound FAD exists in the oxidized form (FAD(ox)) in the dark. Blue light converts FAD(ox) to the neutral radical form (FADH*). Formed FADH* is transformed to the fully reduced form FADH(2) (or FADH(-)) by successive light irradiation, or reverts to FAD(ox). FADH(2) (or FADH(-)) reverts to FADH* or possibly to FAD(ox) directly. The effect of dithiothreitol suggests a possible electron transfer between FAD in zebrafish Cry-DASH and reductants in the external medium. This is the first report on the photoreaction pathway and kinetics of a vertebrate Cry-DASH family protein.     

Zirconium-promoted epoxide rearrangement-alkynylation sequence

Additions of terminal alkynes to electrophiles are important transformations in organic chemistry. Generally, activated terminal alkynes react with epoxides in an S(N)2 fashion to form homopropargylic alcohols. We have developed a new synthetic method to form propargylic alcohols from epoxides and terminal alkynes via 1,2-shifts. This method involves cationic zirconium acetylides as both the activator of epoxides and nucleophiles. Due to the mild conditions to pre-activate alkynes with silver nitrate, this synthetic method is useful for both electron-rich and electron-deficient alkynes with other acid- and base-sensitive functional groups.     

Catalytic Reductive Cross-Coupling between Aromatic Aldehydes and Arylnitriles

A reductive cross-coupling reaction between aromatic aldehydes and arylnitriles using a copper catalyst and a silylboronate as a reductant is reported. This protocol represents an unprecedented approach to the chemoselective synthesis of α-hydroxy ketones by electrophile–electrophile cross-coupling.     

Fiber-Optic Ammonia Sensors Utilizing Rectangular-Cladding Eccentric-Core Fiber

A new fiber-optic ammonia sensor utilizing rectangular-cladding eccentric-core fiber and a sensitive film containing an indicator dye is demonstrated. The sensitive film is a SiO₂-GeO₂ gel film including an indicator dye of bromocresol purple or bromocresol green, which is dip-coated by a sol-gel technique. The attenuation of this sensor changes depending on the concentration of ammonia at the wavelength range of 500–700 nm. This sensor can detect several ppm of gaseous ammonia. Various factors determining the sensitivity to detect the ammonia gas and time response of the sensor are also studied.     

Synthesis and optical properties of new conjugated polymers composed of 1,3,4‐thiadiazole and 2,5‐dialkoxybenzene rings

Intramolecular cyclization of precursor polyhydrazides derived from hydrazine and four 2,5‐dialkoxyterephthalic acids by direct polycondensation with Lawesson's reagent afforded new conjugated polymers constituted of 1,3,4‐thiadiazole and 2,5‐dialkoxybenzene units. The polymers emitted bluish green light in solution and green light in solid state in spite of the coexistence of non‐cyclized hydrazide linkage in the backbones, the Stokes shifts being 91–138 nm in the solid state. It was suggested that these polymers have appropriate lengths of conjugation backbones based on the 1,3,4‐thiadiazole moiety.