γ-Radiolysis of 5-fluorouracil and 5-fluorouridine derivatives having sulfur-containing substituents

γ-Radiolysis reactions of eight 5-fluorouracil (5-FU) derivatives having sulfonyl group-containing substituents at the 1-position and five 5-fluorouridine (5-FUR) derivatives having thioureido group-containing substituents were studied under the conditions where hydrated electron (e_aq^?) and hydroxyl radical (HO·) become the principal reactive species. The 5-FU and 5-FUR derivatives were radiolyzed to give 5-FU and 5-FUR, respectively. The efficiency of the reactions depended upon the nature of reactive species and also upon the nature of substituents. The reactivity features of the γ-radiolysis reactions are discussed.     

Cellulose Synthesized by Acetobacter Xylinum in the Presence of Acetyl Glucomannan

Acetobacter xylinum was cultured in Hestrin-Schramm medium (control medium) and Hestrin-Schramm medium containing acetyl glucomannan (mannan medium). Loose bundles of the cellulose microfibrils are formed in the mannan medium in contrast to the normal ribbons being produced in the control medium. Rapid-freeze and substitution method followed by metal-shadowing revealed the droplet-like structures around the microfibril synthesized in the mannan medium. The cellulose synthesized in the mannan medium was stained heavily by the periodic acid-thiocarbohydrazide-silver proteinate (PATAg) method, while the cellulose synthesized in the control medium was not stained. X-ray diffractometry and FT-IR spectroscopy indicated that the addition of mannan induced a change in the crystal structure from the algal-bacterial type to the cotton-ramie type. Thus the presence of acetyl glucomannan in the medium prevents the assembly of cellulose microfibrils and changes the crystal structure of cellulose.     

Syntheses of fluorine-containing fused polycyclic compounds: photo-cycloaddition of indene to cyclic fluoro-olefins and some reactions concerning the adducts

Acetophenone photo-sensitized addition of indene to cyclic fluoro-olefins (1,2-dichlorohexafluorocyclopentene-1, 1,2-dichlorotetrafluorocyclobutene-1 and hexafluorocyclobutene) gave the corresponding cycloadducts in satisfactory yields. The cycloadducts obtained predominantly had exo configuration.Some reactions such as reduction, oxidation, dechlorination and halogenation, of the cycloadducts were also studied.     

Preparation and photochromism of diarylethene covalently bonded onto layered sodium-magadiite surfaces

Diarylethene derivatives (DE) covalently bonded to silanol oxygens of layered silicate surfaces, i.e., magadiite (Mag), were synthesized and investigated for their photochromic behavior. The DE-Mag layered hybrids were found to undergo reversible color change by alternating UV and visible light irradiation. A more highly efficient, reproducible photochromic behavior was realized with DE-Mag than with a corresponding DE-Si possessing silyl substituents on DE in place of the Mag surface. Moreover, the present covalently bonded DE exhibited an improvement over DE hybrids incorporated in layered double hydroxide (LDH) clays, in which the repetitive photochromic behavior decreased during alternating irradiation, due to the accumulation of the photochemically inert parallel isomers of DE.     

Protonation-induced structural change of lyotropic liquid crystals in oley- and alkyldimethylamine oxides/water systems

Lyotropic phase behavior of the nonionic and the half-ionized oleyldimethylamine oxide (OlDMAO)/water systems was investigated using polarized light microscopy, small-angle X-ray diffraction, and differential scanning calorimetry. Nonionic OlDMAO formed isotropic micellar solution, nematic, hexagonal, cubic, and lamellar liquid crystalline phases as the surfactant concentration increased. In contrast, half-ionized OlDMAO (i.e., 1:1 mixture of the nonionic and the protonated species) had a greater tendency to form bilayer structures, and the phase diagram became quite similar to those of double-chained ionic surfactants rather than single-chained ones, despite the introduction of positive charges to the nonionic one. The preference of the bilayer structures in the half-ionized OlDMAO was interpreted in terms of the dimers stabilized by the hydrogen bond between the nonionic and protonated species. For alkyldimethylamine oxides with a saturated hydrocarbon chain (CnDMAO, chain length: n = 14, 16, and 18), the phase sequence of lyotropic liquid crystals was hardly affected by the protonation, but an elongation of the cylinders of the hexagonal phase was observed for the half-ionized C14DMAO. Consequently, it can be considered that the dominant bilayer formation of the half-ionized OlDMAO is attributed to the combined effect of the hydrogen-bonded dimer formation and the cis-double-bond configuration of the alkyl chain.     

Cyclic dimer of a fused porphyrin zinc complex as a novel host with two pi-electronically coupled binding sites

Upon complexation with 4,4[prime or minute]-bipyridine, a cyclic dimer of a fused porphyrin zinc complex, having two pi-electronically coupled binding sites, shows a strong negative cooperativity in the second guest binding, to allow stepwise formation of 1 : 1 and 1 : 2 inclusion complexes.     

Polymer-supported bases. IX. Synthesis and catalytic activity of polymer-bound 4-(1-pyrrolidino)pyridine moieties

Polystyrene-bound 4-(1-pyrrolidino)pyridine moieties were prepared by the reaction of chloromethylated polystyrene resins with pyrrolidinopyridine derivatives containing hydroxyl groups. The supported amines were effective catalysts for acylations of tert-alcohols or enols, acylrearrangements, and diester synthesis from epoxides and anhydrides. Some of the low ring-substituted (8–15%) catalysts exhibited high activity comparable to that of 4-(N,N-dimethylamino)pyridine, though the activity was a little lower than that of 4-(1-pyrrolidino)pyridine. The recovered catalysts can be re-used, except for acyl rearrangements, without significant decrease in activity.     

Reactivity of cobaloxime bound to polystyrene chain by carbon–cobalt σ bond

The (alkyl)-bis(dimethylglyoximato)pyridinecobalt attached to polychloromethylstyrene by a cobalt–carbon bond was prepared by the reaction of Co(II)(DH)₂Py with polychloromethylstyrene in benzene. The fraction of p-vinylbenzyl·Co(DH)₂Py introduced to the polymer was 8.1 and 2.1 mole %. The photodecomposition of the polymer-bonded cobaloxime was investigated by following the change of the visible spectrum. The rate constant k_dec of the polymer-bonded cobaloxime was 1.1 × 10^?2 sec^?1 in benzene; it is one-fourth of that of its monomeric analog, benzyl·Co(DH)₂Py. The k_dec values of the cobaloximes were also measured in benzene–dimethyl sulfoxide mixed solvents, and the polymer effects were discussed. The dependence of the photodecomposition on energy of the irradiation light was investigated, and it was found that the absorption band near 470 nm is important for the photodecomposition of the cobalt–carbon bond. Spectroscopic measurements of the ligand exchange reaction of polymer-bonded cobaloxime with pyridine in dimethyl sulfoxide gave a larger equilibrium constant (1.2 × 10⁴ liter/mole) than that of benzyl·Co(DH)₂Py (9.4 × 10² liter/mole). The kinetic data of the ligand exchange reaction indicated that the larger equilibrium constant for the polymeric system is due to the smaller rate constant of the reverse reaction. The thermodynamic parameters were also obtained.     

Synthesis,structure, and magnetic properties of dinuclear cobalt(II) complexes with a new phenol-based dinucleating ligand with four hydroxyethyl chelating arms

A new end-off type acyclic ligand with four hydroxyethyl arms, 2,6-bis[bis(2-hydroxyethyl)aminomethyl]-4-methylphenol [H(bhmp)], formed dinuclear cobalt(II) complexes [Co(2)(bhmp)(OAc)(2)]BPh(4) (1) and [Co(2)(bhmp)(OBz)(2)]BPh(4) (2). The complex 1.2.5CH(3)CN (C(50)H(62.5)BCo(2)N(4.5)O(9)) crystallizes in the monoclinic space group C2/c with dimensions a = 25.424(5) A, b = 13.376(2) A, c = 29.913(6) A, beta = 105.930(3) degrees, and V = 9781(3) A(3) and with Z = 8. X-ray diffraction analysis revealed a mu-phenoxo-bis(mu-acetato)dicobalt(II) core structure containing two octahedral cobalt(II) ions. Electronic spectra were investigated for 1 and 2 in the range 400-1800 nm, and the data were typical for the octahedral high-spin cobalt(II) complexes. Magnetic susceptibility was measured for 1 and 2 over the temperature range 4.5-300 K, and the data were analyzed well using our theoretical method. The best fitting parameters were kappa = 0.77, lambda = -116 cm(-1), Delta = 572 cm(-1), and J = -0.44 cm(-1) for complex 1 and kappa = 0.96, lambda = -93 cm(-1), Delta = 616 cm(-1), and J = -0.33 cm(-1) for complex 2.