Synthesis and characterization of poly(ethylene oxide) star polymers possessing a tertiary amino group at each arm end by organized polymerization using macromonomers

Functional poly(ethylene oxide) star polymers possessing a tertiary amino group at each arm end were prepared by free-radical copolymerization of poly(ethylene oxide) macromonomers with divinylbenzene (DVB) in water or ethanol. The poly(ethylene oxide) arm was prepared by anionic polymerization using 2-[2-(N,N-dimethylamino)ethoxy]ethanol potassium alkoxide as the initiator. The star polymers had narrow molecular weight distribution. The arm number was controlled by varying the feed ratio [DVB]/[M], the initial concentration of macromonomer [M], and solvent media. The branching factor g' in methanol ([eta]S/[eta]L are the intrinsic viscosities of the star and linear molecules, respectively) exhibited a power-law dependence on the arm number, f, with a negative exponent. This means that the dimensions of a star were in agreement with the Daoud-Cotton scaling model.     

Significance of anti-HBc IgM in acute hepatitis and hepatitis B associated chronic liver disease

To determine the diagnostic value of anti-HBc IgM in acute viral hepatitis or chronic liver disease B, Anti-HBc IgM was measured by a RIA and an ELISA in 32 patients with acute hepatitis (4 with type A, 15 with type B and 13 with type non A non B), 18 patients with chronic hepatitis and 19 patients with liver cirrhosis. In acute hepatitis B, anti-HBc IgM (both RIA and ELISA) was positive in 14(93%) of 15 patients and its cut-off index value was very high. However, anti-HBc IgM was always negative in one patient with typical course of type B. In 1 of 4 patients with acute hepatitis A and 2 of 13 with non A non B, anti-HBc IgM (RIA and/or ELISA) was positive. These 3 patients were positive for anti-HBs at the onset of disease, so we could not made the diagnosis of acute hepatitis B. Anti-HBc IgM was positive in 21(51%) of 37 patients with HBsAg-positive chronic liver disease by RIA and in 11 (30%) by ELISA, and its cut-off index value was relatively low. These results suggest that when adequate cut-off index value is established, anti-HBc analysis is useful for differentiating recent and current infections from remote infections.     

Interactions between temperature-sensitive hydrogel microspheres and granulocytes

Poly(N-isopropylacrylamide) (PNIPAM) has a low critical solution temperature (LCST) at 32°C in water and the hydrophilicity changes through the LCST. The microspheres whose surface was composed of PNIPAM exhibited phase transition behavior around 32°C. Therefore, the interactions between PNIPAM micropheres and granulocytes depended on the temperature. That is, the oxygen consumption and active oxygen production by cells in contact with PNIPAM-containing microspheres and adhesion of the microspheres to the cell surface were more enhanced above the LCST of PNIPAM than below it, whereas no significant temperature dependence of cell–microspheres interaction was observed in nonthermosensitive microsphere systems. It was suggested that the function of cells could be controlled with temperature using the temperature-sensitive microspheres.     

Total synthesis of brevetoxin-B

Brevetoxin-B (BTX-B), produced by the red tide organism, Gymnodium breve Davis, is the first member of marine polycyclic ethers to be structurally elucidated and one of the most potent neurotoxins. The structural feature is a trans-fused polycyclic ether ring system with 23 stereocenters. Its unique, complex structure and potent biological activity have attracted the attention of synthetic organic chemists. Total synthesis of BTX-B has been accomplished via the coupling of the ABCDEFG and IJK-ring segments, each ether ring of which was stereoselectively and efficiently constructed on the basis of SmI2-induced intramolecular cyclization, 6-endo-cyclization of hydroxy epoxide, ring-closing olefin metathesis, and SmI2-induced intramolecular Reformatsky-type reaction. Several kinds of double reactions at the left and right sides were efficiently used through the synthesis.     

Silicon hydrides and nickel complexes : III. Hydrosilylation of olefins with dichloro[1,2-bis-(dimethylphosphino)-1,2-dicarba-closo-dodecaborane]-nickel(II) as catalyst

The hydrosilylation of olefins catalyzed by nickel(II) chloride complexed with 1,2-bis(dimethylphosphino)-1,2-dicarba-closo-dodecaborane produces terminal and internal adducts in comparable amounts. This unusual feature of the reaction is explained in terms of the electron-accepting nature of the carboranyl group.     

Anthocyanins protect against A2E photooxidation and membrane permeabilization in retinal pigment epithelial cells

The pyridinium bisretinoid A2E, an autofluorescent pigment that accumulates in retinal pigment epithelial cells with age and in some retinal disorders, can mediate a detergent-like perturbation of cell membranes and light-induced damage to the cell. The photodynamic events initiated by the sensitization of A2E include the generation of singlet oxygen and the oxidation of A2E at carbon-carbon double bonds. To assess the ability of plant-derived anthocyanins to modulate adverse effects of A2E accumulation on retinal pigment epithelium (RPE) cells, these flavylium salts were isolated from extracts of bilberry. Nine anthocyanin fractions reflecting monoglycosides of delphinidin, cyanidin, petunidin and malvidin were obtained and all were shown to suppress the photooxidation of A2E at least in part by quenching singlet oxygen. The anthocyanins tested exhibited antioxidant activity of variable efficiency. The structural characteristics relevant to this variability likely included the ability to form a stable quinonoidal anhydro base at neutral pH, a conjugated diene structure in the C (pyrane) ring, the presence of hydroxyl groups on the B (benzene) ring and the relative hydrophobicity conferred by the arrangement of substituents on the B ring. Cells that had taken up anthocyanins also exhibited a resistance to the membrane permeabilization that occurs as a result of the detergent-like action of A2E.     

Excited states of porphyrin isomers and porphycene derivatives: a SAC-CI study

Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds.     

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.     

Metal-insulator transition in VnO2n−1

Research on phase relationships and structure studies by electron diffraction confirm V_nO_2n?1 (n = 3–9) phases between V₂O₃ and VO₂. Metal-insulator phase transitions have been found in all phases but V₃O₅ and V₇O₁₃. Electrical, magnetic and thermodynamic properties associated with the transitions are reported for sintered samples or for single crystals prepared by a vapor-transport method. The results are collated and reviewed in summarized form.     

Two-dimensional self-organization of phthalocyanine and porphyrin: dependence on the crystallographic orientation of Au

By immersing Au substrate into a benzene solution containing both cobalt(II) phthalocyanine (CoPc) and copper(II) tetraphenyl-21H,23H-porphine (CuTPP), a two-dimensional alternate bimolecular structure was formed on the reconstructed Au(100)-(hex) surface.