Borderline of hydrogen bonding of silanols

Two new silanols bearing very bulky silyl groups, (i-Pr₃ Si)₃SiOH and (t − BuMe₂Si)₃SiOH were prepared by peracidoxidation of their respective silanes. The X − ray crystallographic analysis revealed that (t − BuMe₂Si)₃ SiOH forms a dimeric structure with hydrogen bonding, while (i − Pr₃ Si)₃ SiOH exists as a monomer in the crystal. The effects of the size of the substituents as well as the reactivity of these silanols are discussed.     

Thermochromic and solvatochromic zinc biladienones: dynamic equilibria of a metal complex having a flexible framework sensitive to environment

Dehydration of zinc biladienone was catalyzed by zinc acetate, while the reverse reaction was catalyzed by triethylamine. The transformation can be performed thermally without catalyst, and the ratio of the hydrated form to the dehydrated form depended on the solvents: the dehydrated form is favored in CHCl₃ and CH₂Cl₂, while the hydrated form is favored in hexane, pyridine, and DMF. Kinetic studies on the thermal transformation of zinc biladienone from its hydrated blue form to the dehydrated yellow-brown form were performed in toluene and THF. The rate law was half order with respect to the zinc biladienone concentration in toluene, while first order in THF, leading to a slow transformation in concentrated solution in toluene.     

Substituent effects on the kinetics for the chemiluminescence reaction of 6-arylimidazo[1,2-a]pyrazin-3(7H)-ones (Cypridina luciferin analogues): support for the single electron transfer (SET)-oxygenation mechanism with triplet molecular oxygen

Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O₂) in the oxygenation process.     

Pyrene-azacrown ether hybrid: cation-π interaction

A pyrene-modified lariat ether was synthesized in order to observe the cation-π interaction in solution.     

Gamma-ray polymerization of phospholipids having diene or triene groups as liposomes

Small unilamellar liposomes were prepared in an aqueous medium by the sonication of phospholipids containing diene or triene groups in their hydrocarbon acyl chains. These liposomes were polymerized by gamma-ray irradiation. Conversion of polymerization was successively followed by UV spectrometry. Diene-type lipid liposomes were revealed for which a gamma-ray dose of 0.8 Mrad was required for complete polymerization and which were polymerized more easily than triene-type lipid liposomes. Triene-type lipids required 2.3 Mrad gamma ray to polymerize them completely. Contrary to UV-irradiation polymerization, there was no concentration dependence on the polymerization. Structure of the polymerized liposomes were confirmed by electron microscopy as small unilamellar liposomes. Study on the leakage of fluorescein from inner aqueous phase of the polymerized liposomes revealed that polymerized triene-type liposomes were relatively more stable than the polymerized diene-type liposomes.     

Synthesis of 3-substituted 4H-1-benzothiopyran-4-ones

3-Substituted 2-phenyl-4H-1-benzothiopyran-4-ones (thioflavones) were prepared to test antimicrobial activity. It was found that 3-(phenyl)thiochromone derivatives (isothioflavones) were prepared by the Meerwein reaction of thiochromone with p-nitrobenzenediazonium ion. 3-(Formyl)thioflavone exhibits weak antimicrobial activity against Trichophytons and Candida.     

Spin-lattice relaxation time as a useful indicator for the 13CNMR assignment of terminal cis- and trans-methyls in 2-methyl-1-propenyl moiety

T₁ gives a clue to assign cis- and trans-methyl carbons in 2-methyl-1-propenyl moiety.     

Structure of Sol-Gel-Derived Sodium Dititanate Glass

The sodium dititanate, Na₂O·2TiO₂ glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti⁴⁺ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti⁴⁺ ions are rather in five-fold coordination state, forming TiO₅ pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass.