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.     

Syntheses and properties of dithia‐tetrahomodiaza‐calix[4]arenes bridged by cystine unit

Dithia‐tetrahomodiaza‐calix[4]arenes were synthesized by the cyclization reactions of bis(3‐(chloro‐methyl)‐2‐hydroxyphenyl)sulfide with cystine peptides in moderate yields. Conformational analysis of the macrocycles by using nmr spectroscopy reveled that the cyclophanes adopt a cone‐like form as a preferable conformation and the cystine bridge moiety is incorporated in the cavity. The calixarene analogs can extract transion metals such as Zn²⁺ and Cu²⁺ ions from an aqueous phase into chloroform.     

Reaction of phosgene with the tricycle related to the minor base of phenylalanine transfer ribonucleic acids

1-Benzylwye (8) underwent electrophilic substitution at the 7-position in the presence of phosgene and pyridine in tetrahydrofuran (THF) to afford the 1,4-dihydropyridines (11, 10, and 14) together with the carboxylic acid 6 and its methyl ester 2 after short treatment of the reaction mixture with methanol and then with water. When triethylamine was used instead of pyridine, phosgene reacted with triethylamine rather than 8, producing (E)-3-(diethylamino)propenoyl chloride (17) and diethylcarbamoyl chloride (18).     

Overproduction of riboflavin by anArthrobacter sp. mutant resistant to 5-fluorouracil

Effects of pH and dissolved oxygen concentration on batchwise riboflavin production by a 5-fluorouracil (5-FU)-resistant mutant ofArthrobacter sp. were investigated. The reaction was carried out in a jar fermentor. The optimal pH of culture medium was around 7.3. Dissolved oxygen concentration was almost constant during fermentation at 600 rpm of agitation rate. Production of riboflavin reached a maximum of 160 mg/L after 70 h fermentation under the agitation rate of 600 rpm, aeration rate of 1.0 L/min, and pH 7.0.     

Depolymerization and ionic conductivity of enzymatically deproteinized natural rubber having epoxy group

Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (T_g) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH₄)₂S₂O₈ in the presence of propanal. The resulting liquid epoxidized rubber (M_n≈10⁴) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li⁺ as an ionic conducting medium, that is, solid polymer electrolyte.     

Gelation in free-radical terpolymerization of poly(allyl methacrylate) crosslinked polymer nanosphere with allyl benzoate and vinyl benzoate

Microgel-like poly(allyl methacrylate) (PAMA nanosphere) was prepared by the emulsion polymerization of AMA as the reactive crosslinked polymer nanosphere with abundant pendant allyl groups. The terpolymerization of PAMA nanosphere with allyl benzoate (ABz) and vinyl benzoate (VBz) was conducted in bulk using benzoyl peroxide as initiator at 80 °C. The gelation depended on the feed ABz/VBz molar ratio since the molecular weights of resulting poly(ABz-co-VBz)s that act as the bridges increased with an increase in the mole fraction of VBz in the feed monomer. Beyond the gel point, the sol was rapidly incorporated into the gel and the increasing tendency of the gel fraction became steeper from 70 to 95 mol% of VBz as a reflection of increased chain length of bridge between PAMA nanospheres. Moreover, the swelling ratio became lower with increasing the mole percentage of VBz in the feed monomer. These results would support the preferential incorporation of PAMA nanosphere into the gel and the longer bridge can capture more nanospheres to give a much shrunken gel.     

The origin of unidirectional charge separation in photosynthetic reaction centers: nonadiabatic quantum dynamics of exciton and charge in pigment–protein complexes

Exciton charge separation in photosynthetic reaction centers from purple bacteria (PbRC) and photosystem II (PSII) occurs exclusively along one of the two pseudo-symmetric branches (active branch) of pigment–protein complexes. The microscopic origin of unidirectional charge separation in photosynthesis remains controversial. Here we elucidate the essential factors leading to unidirectional charge separation in PbRC and PSII, using nonadiabatic quantum dynamics calculations in conjunction with time-dependent density functional theory (TDDFT) with the quantum mechanics/molecular mechanics/polarizable continuum model (QM/MM/PCM) method. This approach accounts for energetics, electronic coupling, and vibronic coupling of the pigment excited states under electrostatic interactions and polarization of whole protein environments. The calculated time constants of charge separation along the active branches of PbRC and PSII are similar to those observed in time-resolved spectroscopic experiments. In PbRC, Tyr-M210 near the accessary bacteriochlorophyll reduces the energy of the intermediate state and drastically accelerates charge separation overcoming the electron–hole interaction. Remarkably, even though both the active and inactive branches in PSII can accept excitons from light-harvesting complexes, charge separation in the inactive branch is prevented by a weak electronic coupling due to symmetry-breaking of the chlorophyll configurations. The exciton in the inactive branch in PSII can be transferred to the active branch via direct and indirect pathways. Subsequently, the ultrafast electron transfer to pheophytin in the active branch prevents exciton back transfer to the inactive branch, thereby achieving unidirectional charge separation.

Essential factors leading to unidirectional charge separation in photosynthetic reaction centers are clarified via nonadiabatic quantum dynamics calculations.