Synthesis and properties of hyperbranched poly(ether sulfone)s prepared by self‐polycondensation of novel AB2 monomer

Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB₂ monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling ¹³C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Officinatrione: an unusual (17S)-17,18-seco-lupane skeleton,and four novel lupane-type triterpenoids from the roots of Taraxacum officinale

Novel 5 lupane-type of triterpenois, i.e., 3β-acetoxy-18α,19α-epoxylupan-21β-ol (1), 18α,19α-epoxy-21β-hydroxylupan-3-one (2), lup-18-ene-3,21-dione (3), lupa-18,21-dien-3β-yl acetate (4), and (17S)-17,18-seco-lup-19(21)-ene-3,18,22-trione (5), named officinatrione, as well as 16 known compounds from the roots of Taraxacum officinale collected in Takatsuki city, Osaka, Japan. Of the above compounds, 5 was the first lupane-type triterpene, of which the D-ring was open to form a nine-membered ring. Compounds 2 and 5 exhibited moderate cytotoxic activities against L1210 cell line (IC₅₀ 10.5 and 10.1 μM).     

Design of sugar–oligonucleotide conjugates installed gold nanoparticle for effective delivery to hepatic parenchymal cells

A novel oligonucleotide delivery system that is based on oligonucleotide–nanoparticle conjugates has been described. Installed oligonucleotides were modified with the carbohydrate at the 3′ terminus, accordingly, constructed nanoparticles display clustered carbohydrates on their outer layer for the targeted delivery of oligonucleotides. The method for the construction of ligand-functionalized nanoparticle was simple and reproducible. The stability of the nanoparticles displaying clustered carbohydrates greatly increased in serum compared to nanoparticles without carbohydrates. In order to investigate the targetability of oligonucleotide–nanoparticle conjugates into primary hepatic parenchymal cells, freshly isolated rat hepatocytes were incubated with nanoparticles and the amount of internalized gold nanoparticles was evaluated by an inductively coupled plasma mass spectroscopy analysis. Nanoparticles displaying clustered carbohydrates internalized more efficiently than nanoparticles without carbohydrate modifications. In particular, the cellular uptakes of oligonucleotide-conjugated gold nanoparticle increased 1.7 ～2.0-fold by galactose modification. Competition assay revealed that clustered galactose enhanced the internalization of the nanoparticle into primary hepatic parenchymal cells by a receptor-mediated process.

Preparation of various Janus composite particles with two components differently combined

Janus composite particles with a combination of organic and inorganic substances were synthesized by soap-free emulsion polymerization in which an amphoteric initiator of 2,2′-azobis[N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was employed to introduce a polystyrene (PSt) lobe onto silica cores surface-modified with 3-methacryloxypropyltrimethoxy silane (MPTMS). Thermogravimetric analysis and X-ray photoelectron spectroscopy were used to characterize the surface-modified silica particles and showed that a small amount of MPTMS introduced onto the surface of silica particles could successfully prepare SiO₂–PSt Janus particles. The oxide part of SiO₂–PSt Janus particles obtained with the polymerization was further surface-modified with 3-aminopropyltriethoxysilane (APS) to introduce positively charged amino groups on the silica surface. The silica surface modified with APS was covered with gold by electroless deposition in which a gold precursor of auric chloride was reduced with ascorbic acid in the presence of polyvinylpyrrolidone. The electroless deposition of gold successfully produced Janus particles with a combination of gold and PSt surfaces. Furthermore, dissolution of the polymer component of the Au–PSt Janus particles in tetrahydrofuran led to another Janus type of particles with an inorganic combination of Au and SiO₂.     

Direct Synthesis of 1,4‐Diols from Alkenes by Iron‐Catalyzed Aerobic Hydration and C?H Hydroxylation

Various 1,4‐diols are easily accessible from alkenes through iron‐catalyzed aerobic hydration. The reaction system consists of a user‐friendly iron phthalocyanine complex, sodium borohydride, and molecular oxygen. Furthermore, the effect of additional ligands on the iron complex was examined for a model reaction. The second hydroxy group is installed by direct C(sp³) H oxygenation, which is based on a [1,5] hydrogen shift process of a transient alkoxy radical that is formed by formal hydration of the olefin.     

Structure of tecophilin,a tri-caffeoylanthocyanin from the blue petals of Tecophilaea cyanocrocus, and the mechanism of blue color development

The pigment, tecophilin, in blue flowers of Tecophilaea cyanocrocus was isolated and the structure was determined to be 3-O-(6-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-7-O-(6-O-(4-O-(2-O-(4-O-β-d-glucopyranosyl-(E)-caffeoyl)-6-O-(4-O-β-d-glucopyranosyl-(E)-caffeoyl)-β-d-glucopyranosyl)-(E)-caffeoyl)-β-d-glucopyranosyl)delphinidin. The reproduction experiment of the same color as petals according to the results of chemical analysis and measurement of vacuolar pH of blue cells clarified that the blue color solely develops by tecophilin without interaction of metal ions nor co-pigments. ¹H NMR analysis and CD spectrum indicate the co-existence of clockwise intermolecular self-association of the delphinidin nuclei and intramolecular π–π stacking between the chromophore and caffeoyl residues to derive bathochromic shift of the absorption spectrum and stabilize the color by preventing hydration reaction.     

Serine‐Selective Aerobic Cleavage of Peptides and a Protein Using a Water‐Soluble Copper–Organoradical Conjugate

The site‐specific cleavage of peptide bonds is an important chemical modification of biologically relevant macromolecules. The reaction is not only used for routine structural determination of peptides, but is also a potential artificial modulator of protein function. Realizing the substrate scope beyond the conventional chemical or enzymatic cleavage of peptide bonds is, however, a formidable challenge. Here we report a serine‐selective peptide‐cleavage protocol that proceeds at room temperature and near neutral pH value, through mild aerobic oxidation promoted by a water‐soluble copper–organoradical conjugate. The method is applicable to the site‐selective cleavage of polypeptides that possess various functional groups. Peptides comprising D ‐amino acids or sensitive disulfide pairs are competent substrates. The system is extendable to the site‐selective cleavage of a native protein, ubiquitin, which comprises more than 70 amino acid residues.