15 research outputs found

    Micropatterning of Multiple Photonic Colloidal Crystal Gels for Flexible Structural Color Films

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    We herein report the micropatterning of flexible multiple photonic colloidal crystal gels (PCCGs) using single-layered microchannels. These patterned PCCGs exhibit structural colors that can be tuned by adjustment of the diameter and concentration of the colloidal particles in precursor solutions of <i>N</i>-isopropylacrylamide (NIPAM) or polyethylene glycol diacrylate (PEGDA). The precursor solutions containing dispersed colloidal particles were selectively injected into single-layered microchannels where they polymerized rapidly. The shape, density, and height of the patterned PCCG pixels were determined by the microchannels, which in turn determined the optical properties of the PCCG arrays. Furthermore, the preparation of three different types of PCCGs exhibiting three different structural colors at a high pixel density was demonstrated successfully using the single-layered polydimethylsiloxane (PDMS) microchannels. Finally, the optical reflective properties and the mechanical flexibility of the patterned multiple PCCG arrays were evaluated. We expect that our method for the preparation of such patterned PCCG arrays will contribute to the development of flexible optical devices

    Enantioselective Formal Synthesis of (−)-Podophyllotoxin from (2<i>S</i>,3<i>R</i>)‑3-Arylaziridine-2-carboxylate

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    Meyers’ 4-aryl-1-tetralone-lactone and <i>ent</i>-Zhang’s 2-diarylmethyl-4-oxobutanoate were synthesized in the formal synthesis of (−)-podophyllotoxin from (2<i>S</i>,3<i>R</i>)-3-arylaziridine-2-carboxylate, via 3,3-diarylpropanoate as a common intermediate, in an overall 42% yield through 10 steps and 31% yield through 6 steps, respectively. The key steps in the synthesis were regio- and diastereoselective ring opening with an aromatic nucleophile, samarium iodide promoted reductive C–N bond cleavage, and Stille coupling for introducing the vinyl functionality. The starting aziridine was enantioselectively prepared from 3,4,5-trimethoxybenzaldehyde by guanidinium ylide mediated asymmetric aziridination. All nitrogen components used in the reaction sequence are reusable as the starting guanidinium source

    Estimation of long-term dietary exposure to acrylamide of the Japanese people

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    <p>Acrylamide is a probable human carcinogen and known human neurotoxin. This study estimated hypothetical long-term dietary exposure to acrylamide of the Japanese people using probabilistic and deterministic approaches by combining the concentration of acrylamide in foods with the amount and frequency of food consumption in the population. Data included acrylamide concentrations in more than 2400 individual food samples from a national survey and the literature from 2004 to 2013. Food consumption amounts were derived from the data of 24,293 Japanese citizens aged 1 year and older in the 2012 National Health and Nutrition Survey. Median lifetime average dietary exposure to acrylamide was estimated as 147–154 ng/kg body weight (bw)/day (95th percentile, 226–261 ng/kg bw/day). The deterministic estimate of lifetime exposure was 158 ng/kg bw/day and ranged from 119 ng/kg bw/day for the period of life after 60 years old to 409 ng/kg bw/day for the period between 1 and 6 years old. This study found that vegetables cooked at a high temperature, coffee and cooked potato were the major food groups contributing to long-term dietary acrylamide exposure of the Japanese people.</p

    Enantioselective Construction of a Polyhydroxylated Pyrrolidine Skeleton from 3‑Vinylaziridine-2-carboxylates: Synthesis of (+)-DMDP and a Potential Common Intermediate for (+)-Hyacinthacine A<sub>1</sub> and (+)-1-<i>epi</i>-Australine

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    We report an enantioselective synthesis of the polyhydroxylated pyrrolidine alkaloid (+)-DMDP. The key steps in the synthesis were guanidinium ylide mediated asymmetric aziridination, stereospecific ring opening of <i>trans</i>-3-vinylaziridine-2-carboxylate with an oxygen nucleophile, iodine-mediated 5<i>-endo-trig</i> amino cyclization, and Prévost displacement. In addition, a potential common intermediate for the polyhydroxylated pyrrolizidine alkaloids (+)-hyacinthacine A<sub>1</sub> and (+)-1-<i>epi</i>-australine was synthesized from a diastereoisomeric <i>cis</i>-aziridine coformed in the asymmetric aziridination using the same strategy. A rationale for the diastereoselectivity observed for the iodine-mediated amino cyclization reactions is proposed on the basis of the heats of formation of the products

    Enantioselective Construction of a Polyhydroxylated Pyrrolidine Skeleton from 3‑Vinylaziridine-2-carboxylates: Synthesis of (+)-DMDP and a Potential Common Intermediate for (+)-Hyacinthacine A<sub>1</sub> and (+)-1-<i>epi</i>-Australine

    No full text
    We report an enantioselective synthesis of the polyhydroxylated pyrrolidine alkaloid (+)-DMDP. The key steps in the synthesis were guanidinium ylide mediated asymmetric aziridination, stereospecific ring opening of <i>trans</i>-3-vinylaziridine-2-carboxylate with an oxygen nucleophile, iodine-mediated 5<i>-endo-trig</i> amino cyclization, and Prévost displacement. In addition, a potential common intermediate for the polyhydroxylated pyrrolizidine alkaloids (+)-hyacinthacine A<sub>1</sub> and (+)-1-<i>epi</i>-australine was synthesized from a diastereoisomeric <i>cis</i>-aziridine coformed in the asymmetric aziridination using the same strategy. A rationale for the diastereoselectivity observed for the iodine-mediated amino cyclization reactions is proposed on the basis of the heats of formation of the products

    Typical appearance of the periocular swelling and chemosis.

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    <p>Moderate chemosis, lid swelling, and subcutaneous bleeding were observed dominantly in the superior part or the periocular tissues. (10 min after release of the head-down position).</p

    Intraocular pressure of at each time point.

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    <p>P1: Day before RALP (conscious).P2: 5 min after systemic anesthesia induction.P3: 10 min after maintaining head-down position.P4: 1 hour after maintaining head-down position.P5: 2.5 hours after maintaining head-down position.P6: 4 hours after maintaining head-down position.P7: 10 min after release of head-down position.P8: Day after RALP (conscious).All: 50 eyes of all 25 subjects.VF defect +: 7 eyes with postoperative visual field defects.Error bars represent standard deviations of IOP of all subjects’ eyes.**: P<0.01, compared with the value at P1, after Bonferroni’s correction.</p

    High-Resolution Inventory of Japanese Anthropogenic Mercury Emissions

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    Heavy metals like mercury that are emitted into the environment remain there indefinitely, posing a long-term threat to both the environment and human health. Elemental mercury is volatile and is in gaseous form, and because of the long residence time, transported over long distances. Comprehensive control of mercury emissions therefore remains an important international issue. The crucial steps for designing effective approaches for such control include the quantification of mercury emissions by sources and the identification of geographical characteristics of the emissions. In this study a detailed, high-resolution inventory of Japanese mercury emissions in 2005 was developed to improve understanding of their geographical distribution. Proceeding from a national emissions inventory per source category, emissions were spatially allocated with increasing geographical resolution in a stepwise procedure using statistics from geographic information resources, yielding mercury emissions per prefecture, per municipality and per grid cell of approximately 1 × 1 km. The five prefectures with the highest emissions were Fukuoka, Yamaguchi, Hyogo, Oita, and Hokkaido, accounting for 35.2% of all emissions. In each prefecture a small number of municipalities account for a major share of emissions. Distribution by grid cell is characterized by a concentration of 50% of all emissions in a mere 32 of the 255 954 grid cells over which emissions are distributed in this study. It was also quantitatively confirmed that use of larger grid cells leads to greater uncertainty in emissions distribution. Problems with data collection are clarified and measures to improve the accuracy of future estimation are proposed

    Time points of intraocular pressure measurements and condition of the subjects.

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    <p>RALP: Robot-assisted laparoscopic radical prostatectomy.</p><p>Time points of intraocular pressure measurements and condition of the subjects.</p
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