• Title/Summary/Keyword: epoxidation

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Stereoselective Synthesis of L-Deoxyaltronojirimycin from L-Serine

  • Rengasamy, Rajesh;Curtis-Long, Marcus J.;Ryu, Hyung-Won;Oh, Kyeong-Yeol;Park, Ki-Hun
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1531-1534
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    • 2009
  • (2S,3R)-3-Hydroxy-2-(hydroxymethyl)-3,6-dihydro-2H-pyridine 8, an important precursor for the synthesis of polyhydroxylated piperidine azasugars, has been prepared from L-serine. Highly stereoselective nucleophilic addition to amino aldehyde 5 gave the corresponding allylic alcohol 6 which proceeded to give dihydro-2H-piridine 7a via a Grubbs II catalyzed RCM. Stereoselective H-bond directed epoxidation of allylic alcohol led to the oxiranyl alcohol 9 which was easily converted to L-deoxyaltronojirimycin by regioselective ring opening.

Synthesis of Glucuronic Acid Conjugates of Linoleic Acid Metabolites (리놀레산 대사체들의 글루쿠론산 결합화합물 합성)

  • Kang, Dong Wook
    • Journal of the Korean Chemical Society
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    • v.57 no.6
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    • pp.738-743
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    • 2013
  • Linoleic acid and its metabolites have various medicinal effects with carboxylic acid functional group. General carboxylic acid compounds are discovered as glucuronide metabolites by UGT glucuronosyl transferase at liver. Consequently, glucuronides of linoleic acid metabolites are expected as potent conjugated metabolite. A previous study reported two epoxide metabolites and two dihydroxy metabolites of linoleic acid. There are prepared their glucuronic acid conjugated compounds as potent linoleic acid metabolites.

Biocatalysis and Biotransformation for the Production of Chiral Epoxides (바이오촉매 및 생물전환을 이용한 광학활성 에폭사이드 제조)

  • Kim, Hee-Sook;Lee, Ok-Kyung;Lee, Eun-Yeol
    • Journal of Life Science
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    • v.15 no.5 s.72
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    • pp.772-778
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    • 2005
  • Chiral epoxides are important chiral synthons in organic synthesis for the production of chiral pharmaceuticals and functional food additives. Chiral epoxides can be synthesized by enantioselective introduction of oxygen to double bond of substrate by monooxygenase. Peroxidase also carry out asymmetric epoxidation of alkene in the presence of hydrogen peroxide. Kinetic resolution of racemic epoxides via enantioselective hydrolysis reaction by epoxide hydrolase (EH) is a very promising method since chiral epoxides with a high optical purity can be obtained from cheap and readily available racemic epoxides. In this review, various biocatalytic approaches for the production of chiral epoxides with several examples are presented and their commercial potential is discussed.

A Spectrophotometric Assay for Cytochrome P450 Monooxygenase Activity

  • Lee, Sung-Eun;Choi, Won-Sik;Park, Byeoung-Soo;Lee, Byung-Ho
    • Applied Biological Chemistry
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    • v.41 no.4
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    • pp.213-217
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    • 1998
  • An assay for cytochrome P450 monooxygenase activity by determination of the products of organophosphate oxidation via inhibition of acetylcholinesterase was described. Extracts from strains of Oryzaephilus surinamensis selected for resistance to chlorpyrifos-methyl (QVOS 102), fenitrothion (VOS F) and malathion (VOS 3), and a standard susceptible strain VOS 48, were incubated with an organophosphate in the presence of a NADPH-generating system and acetylcholinesterase. The degree of inhibition of the acetylchoinesterase activity was converted to manooxygenase activity using standard curves for the inhibition of acetylcholiesterase by chlorpyrifos-methyl-oxon, fenitrooxon and malaoxan. Activity was detectable in VOS 48 and was present at different increased levels with the different organophosphates in the three resistant strains, suggesting that different forms of P450 might be involved in organophosphate oxidation in these insects. The assays were carried out using crude insect homogenates and much smaller samples of insect material than the standard aldrin to dieldrin assay. It should be possible to use the method for determination of monooxygenase activity in single insert.

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Photochemical Response in 0-Year-Old and 1-Year-Old Needles of Picea glehnii during Cold Acclimation and Low Temperature

  • Bae, Jeong-Jin;Hara, Toshihiko;Choo, Yeon-Sik
    • Journal of Ecology and Environment
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    • v.31 no.4
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    • pp.317-325
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    • 2008
  • P. glehnii, an evergreen conifer found in northern areas, is known as a cold-resistant species. In this experiment, we measured the water content, PSⅡ efficiency, chlorophyll fluorescence, pigments of the xanthophyll-cycle and activity of enzymes of the ascorbate-glutathione cycle during cold acclimation and at subsequent low-temperature conditions to examine the importance of acclimation to cold tolerance. P. glehnii showed a decrease in PSⅡ efficiency (especially in Fv) during cold acclimation and at subsequent low temperatures. However, cold-acclimated needles showed higher PSⅡ efficiency at low temperatures than nonacclimated needles. In addition, 0-YON (first-year needles) showed an increase in $\beta$-carotene and lutein, while 1-YON (one-year-old needles) immediately developed an antioxidant mechanism in the ascorbate-gluthathione cycle as soon as they were exposed to low temperature and both 0-YON and 1-YON showed increased zeaxanthin and de-epoxidation ratios at continuous low temperature. Based on our results, we suggest that P. glehnii maintain PSⅡ efficiency at low temperature by effectively protecting the photosynthetic apparatus from photo-damage by rapid induction of an antioxidant mechanism in 1-YON and dissipation of excess energy by $\beta$-carotene and lutein in 0-YON.

Microwave Synthesis of Titanium Silicalite-1 Using Solid Phase Precursors

  • Kim, K.Y.;Ahn, W.S.;Park, D.W.;Oh, J.H.;Lee, C.M.;Tai, W.P.
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.634-638
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    • 2004
  • Titanium silicalite-1 (TS-1) molecular sieve was produced by microwave heating of amorphous titanium-containing solid precursors after impregnation with aqueous TPAOH solution. $SiO_2-TiO_2$ xerogel, sub-micron sized $SiO_2-TiO_2$ prepared by thermal plasma process, and Ti-containing mesoporous silica, Ti-HMS, were tested as the solid phase substrates. Highly crystalline product was obtained within 30 min. after microwave irradiation with yields over 90% using $SiO_2-TiO_2$ xerogel, which showed essentially identical physicochemical properties to TS-1 prepared by conventional hydrothermal method. Excellent catalytic activity was also obtained for 1-hexene epoxidation using $H_2O_2.\;SiO_2-TiO_2$ particles prepared by thermal plasma and Ti-HMS were found inferior as a substrate for TS-1, probably due to difficulties in wetting the surface uniformly with TPAOH.

Acclimation of maximum quantum yield of PSII and photosynthetic pigments of Panax quinquefolius L. to understory light

  • Fournier, Anick R.;T.A., John;Khanizadeh, Shahrokh;Gosselin, Andre;Dorais, Martine
    • Journal of Ginseng Research
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    • v.32 no.4
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    • pp.347-356
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    • 2008
  • Forest-grown American ginseng (Panax quinquefolius L.) is exposed to daily and seasonal light variations. Our goal was to determine the effect of understory light changes on the maximum quantum yield of photosystem II, expressed as $F_v/F_m$, and photosynthetic pigment composition of two-year-old plants. Understory light photon flux density and sunfleck durations were characterized using hemispherical canopy photography. Our results showed that understory light significantly affected the $F_v/F_m$ of American ginseng, especially during the initial development of the plants when light levels were the highest, averaging 28 mol $m^{-2}d^{-1}$. Associated with low $F_v/F_m$ during its initial development, American ginseng had the lowest levels of epoxidation state of the xanthophyll cycle of the season, suggesting an active dissipation of excess light energy absorbed by the chlorophyll pigments. As photon flux density decreased after the deployment of the forest canopy to less than 10 mol $m^{-2}d^{-1}$, chlorophyll a/b decreased suggesting a greater investment in light harvesting pigments to reaction centers in order to absorb the fleeting light energy.

Growth, Structure, and Stability of Ag on Ordered ZrO2(111) Films

  • Han, Yong;Zhu, Junfa;Kim, Ki-jeong;Kim, Bongsoo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.204.2-204.2
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    • 2014
  • Among various metal oxides, ZrO2 is of particular interests and has received widespread attention thanks to its ideal mechanical and chemical stability. As a cheap metal, Ag nanoparticles are also widely used as catalysts in ethylene epoxidation and methanol oxidation. However, the nature of Ag-ZrO2 interfaces is still unknown. In this work, the growth, interfacial interaction and thermal stability of Ag nanoparticles on ZrO2(111) film surfaces were studied by low-energy electron diffraction (LEED), synchrotron radiation photoemission spectroscopy (SRPES), and X-ray photoelectron spectroscopy (XPS). The ZrO2(111) films were epitaxially grown on Pt(111). Three-dimensional (3D) growth model of Ag on the ZrO2(111) surface at 300 K was observed with a density of ${\sim}2.0{\times}1012particles/cm2$. The binding energy of Ag 3d shifts to low BE from very low to high Ag coverages by 0.5 eV. The Auger parameters shows the primary contribution to the Ag core level BE shift is final state effect, indicating a very weak interaction between Ag clusters and ZrO2(111) film. Thermal stability experiments demonstrate that Ag particles underwent serious sintering before they desorb from the zirconia film surface. In addition, large Ag particles have stronger ability of inhibiting sintering.

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Preparation of Fullerene Oxides by Fullerenes[$C_{60},C_{70}$] with Several Oxidants under Ultrasonic Condition (초음파 조건에서 산화제를 이용한 풀러렌 산화물의 제조)

  • Kown, Sock-Chan;Jeong, Hong-Seok;Ko, Weon-Bae
    • Elastomers and Composites
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    • v.38 no.2
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    • pp.147-156
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    • 2003
  • Synthesis of fullerene oxides by fullerenes [$C_{60},\;C_{70}$] and several oxidants such as benzoylperoxide, trichloroisocyanuric acid, methyltrioxorhenium(VII), iodosobenzene, phosphorous pentoxide take place under ultrasonic condition at room temperature. The MALDI-TOF MS,UV-visible spectra and HPLC analysis confirmed that the products of fullerenes oxidation are [$C_{60}(O)_n$], ($n=1{\sim}3$ or n=1) and [$C_{70}(O)_n$], ($n=1{\sim}2$ or n=1). As compared with the reactivity of epoxidation of fullerenes [$C_{60},\;C_{70}$], the reaction rate of $C_{70}$ was lower than that of $C_{60}$ under same reaction condition.

Microwave Synthesis of a Porous Metal-Organic Framework, Nickel(II) Dihydroxyterephthalate and its Catalytic Properties in Oxidation of Cyclohexene

  • Lee, Ji-Sun;Halligudi, Shiva B.;Jang, Nak-Han;Hwang, Dong-Won;Chang, Jong-San;Hwang, Young-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1489-1495
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    • 2010
  • A porous coordination solid of nickel(II) dihydroxyterephthalate has been synthesized by the microwave-assisted (MW) method. The synthesized nickel(II) dihyroxylterephthalate was designated by the general formula of [$Ni_2$(dhtp) $(H_2O)_2]{\cdot}8H_2O$ (where, dhtp = 2,5-dihydroxyterephthalate, denoted by Ni-DHTP). The effect of microwave-irradiation temperature and time of irradiation on the porosity and morphological changes in the solids have also been investigated. The catalytic performance of Ni-DHTP synthesized by MW method has been studied in the oxidation of cyclohexene with aqueous $H_2O_2$, which gave cyclohexene oxide as the primary product and 2-cyclohexene-1-ol as a major product.