36 research outputs found

    Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates

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    Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronate

    Copper(I)-Catalyzed Asymmetric Monoborylation of 1,3-Dienes: Synthesis of Enantioenriched Cyclic Homoallyl- and Allylboronates

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    Copper(I)-Catalyzed Asymmetric Monoborylation of 1,3-Dienes: Synthesis of Enantioenriched Cyclic Homoallyl- and Allylboronate

    Copper-Catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron:  An Efficient Route to Optically Active α-Chiral Allylboronates

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    A method for the synthesis of α-chiral allylboronates featuring the Cu(I)-catalyzed enantioselective substitution of readily available allylic carbonates with a diboron is described. Using this method, various α-chiral allylboronates, including functionalized allylboronates, were successfully synthesized, with high enantiomeric purity

    Supplementary Data from Impairment of Plasmacytoid Dendritic Cells for IFN Production by the Ligand for Immunoglobulin-Like Transcript 7 Expressed on Human Cancer Cells

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    Supplementary Data from Impairment of Plasmacytoid Dendritic Cells for IFN Production by the Ligand for Immunoglobulin-Like Transcript 7 Expressed on Human Cancer Cell

    Direct bioethanol production from brown macroalgae by co-culture of two engineered <i>Saccharomyces cerevisiae</i> strains

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    <p>A co-culture platform for bioethanol production from brown macroalgae was developed, consisting of two types of engineered <i>Saccharomyces cerevisiae</i> strains; alginate- and mannitol-assimilating yeast (AM1), and cellulase-displaying yeast (CDY). When the 5% (w/v) brown macroalgae <i>Ecklonia kurome</i> was used as the sole carbon source for this system, 2.1 g/L of ethanol was produced, along with simultaneous consumption of alginate, mannitol, and glucans.</p

    Influence of the Side Chain Next to C-Terminal Benzimidazole in Opioid Pseudopeptides Containing the Dmt-Tic Pharmacophore

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    To improve the structure−activity studies of the lead δ opioid agonist H-Dmt-Tic-Asp*-Bid, we synthesized and pharmacologically characterized a series of analogues in which the side chain next to 1H-benzimidazole-2-yl (Bid) was substituted by those endowed with different chemical properties. Interesting results were obtained: (1) only Gly, Ala, and Asp resulted in δ agonism, (2) Phe yielded δ antagonism, (3) and all other residues except Glu (devoid of any activity) gave μ agonism

    Nonconjugated Redox-Active Polymer Mediators for Rapid Electrocatalytic Charging of Lithium Metal Oxides

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    For rapid charging of lithium-ion batteries, a series of novel electrode-active materials have been studied. However, those materials suffered from replacing conventional metal oxides, such as LiCoO2 and LiFePO4, because of the strict performance criteria for commercialization. As an alternative approach, we propose the hybridization of the conventional inorganic active materials with organic redox-active polymers which are characterized by fast electrode kinetics. A new robust organic-radical-substituted polyether was synthesized to yield one of the highest charge transportabilities of nonconjugated polymers with a charge diffusion coefficient of 10–7 cm2/s. The hybrid electrode of LiFePO4 and a small amount of the polymer was able to be charged within several minutes by virtue of the electrocatalytic oxidation of the metal oxide with the radical polymer. In addition, several 4 V class organic redox-active polymers were synthesized for the hybrid with LiCoO2. After hybridization, the LiCoO2 electrodes could also be charged within several minutes with the reduced overvoltages

    Small-Angle Neutron Scattering Study on Specific Polymerization Loci Induced by Copolymerization of Polymerizable Surfactant and Styrene during Miniemulsion Polymerization

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    We have investigated the origin of a specific polymerization loci that yielded copolymer particles with a bimodal gel permeation chromatographic profile in the early stage of miniemulsion polymerization of styrene (St) with the polymerizable surfactant <i>N</i>-<i>n</i>-dodecyl-<i>N</i>-2-methacryloyloxyethyl-<i>N</i>,<i>N</i>-dimethylammonium bromide (C<sub>12</sub>DMAEMA). The formation of particles by miniemulsion polymerization using C<sub>12</sub>DMAEMA was investigated as a function of the polymerization time (<i>t</i><sub>p</sub>) and was compared with that using the nonpolymerizable surfactant cetyltrimethylammonium bromide (CTAB). St was miniemulsified with C<sub>12</sub>DMAEMA or CTAB and was polymerized with either a water-soluble initiator, 2,2′-azobis­(2-amidinopropane) dihydrochloride (V50), or an oil-soluble initiator, 2,2′-azobis­(isobutyronitrile) (AIBN), at 60 °C in the presence of polystyrene (PSt) as a hydrophobe. Gel permeation chromatography (GPC) and elemental analysis indirectly predicted two different polymerization loci in the St/C<sub>12</sub>DMAEMA/V50 polymerization system. Time-resolved small-angle neutron scattering (SANS) was used to directly observe and examine the specific polymerization loci in the miniemulsion polymerization solutions. The droplets formed in the St/C<sub>12</sub>DMAEMA/V50/PSt at the initial stage of the polymerization were not fully stabilized by C<sub>12</sub>DMAEMA and poly­(C<sub>12</sub>DMAEMA-<i>ran</i>-St) and were found to build up the large aggregates. The spherical droplets were stabilized later in the polymerization (<i>t</i><sub>p</sub> > 20 min) by forming a homogeneous dispersion in the water phase. In contrast, the droplets stabilized by CTAB in St/CTAB/V50/PSt maintained their size and shape throughout the polymerization. As a result, in both polymerization systems of St/C<sub>12</sub>DMAEMA/V50/PSt and St/CTAB/V50/PSt, the particle size was found to depend strongly on the size of the droplets formed in the early stage of polymerization. Porod analysis of the power law scattering observed by SANS provided direct evidence for the specific polymerization loci, which appeared in the early stage of the polymerization system of St/C<sub>12</sub>DMAEMA/V50/PSt on the surface of the droplet, and was the origin of the bimodal peaks in the GPC chromatogram

    Photonic Crystals Fabricated by Block Copolymerization-Induced Microphase Separation

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    We present a method for fabricating photonic crystals (PCs) by polymerization-induced microphase separation of block copolymers (BCPs). Molecular weight of BCP for PCs is so large that it has been difficult for conventional solution casting and annealing methods to complete the microphase separation to form periodically ordered submicron structures. Our method overcomes the difficulty by inducing the microphase separation and transitions during the polymerization, when the molecular weight of the BCPs is small enough for the microphase separation and transitions. The microphase-separated structure is then enlarged while maintaining the self-similarity. We succeeded in fabricating PCs with reflection wavelength λ<sub>m</sub> ≈ 1000 nm and a full width at half-maximum Δλ = 0.05λ<sub>m</sub> by living-radical bulk block copolymerization of poly­(methyl methacrylate)-<i>block</i>-polystyrene
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