• 제목/요약/키워드: Carbonyl reduction

검색결과 73건 처리시간 0.025초

크로마토그래피용 고정화 8-hydroxyquinoline의 제조 및 특성분석 (Preparation and characterization of immobilized 8-hydroxyquinoline for chromatographic application)

  • 김범수
    • 분석과학
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    • 제13권1호
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    • pp.49-54
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    • 2000
  • 5단계 반응을 통하여 실리카겔의 8-hydroxyquinoline 유도체를 제조하였으며, 각 단계에서 얻은 생성물들을 IR과 NMR을 이용하여 분석하였다. 실리카겔 자체에 관한 IR 스펙트럼으로부터, 자유 hydroxyl기와 수소 결합된 hydroxyl기가 존재하는 것을 확인할 수 있었다. 첫 단계 반응에서는 N-H와 C-H의 IR 밴드와 APTS기에 있는 메틸렌 탄소의 NMR peak을 확인하였다. 둘째 단계에서는 카보닐, nitro, 방향족 탄소의 IR 밴드와 지방족, 방향족, 카보닐 탄소의 NMR peak을 관찰하였으며, 셋째 단계에서 $NO_2$$NH_2$로 환원되는 것을 IR과 NMR로 확인할 수 있었다. 마지막 단계에서는 4번째 단계에서 생성된 $N{\equiv}N$ IR peak이 사라지는 것으로부터 8-quinolinol이 고정화되는 것을 확인할 수 있었다.

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한국산 참깨기름과 중국산 참깨기름의 토코페롤 산화안정성 (Oxidative Stability of Tocopherols on Korean Sesame oil and chinese Sesame oil)

  • 신묘란;주광지
    • 동아시아식생활학회지
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    • 제4권2호
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    • pp.51-57
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    • 1994
  • Six sesame oils prepared from Korean and Chinese sesame were oxidized at 40$^{\circ}C$ for 16 weeks in a dark place. Effects of oxidative stability on tocopherols of those sesame oils were studied in related to chemical changes in the oils. All oil samples showed that the rate of tocopherol reduction was increased by the storage time. The changes of peroxide value, free fatty acid, carbonyl content were not caused in direct relation to the tocopherols oxidation. The amount of total tocopherol in the Korean sesame oil ranged from 48.7-50.3mg/100g and Chinese seseame oil ranged from 42.4-44.7 mg/100g According to the three individual tocopherols remaining content after 16weeks, ${\gamma}$-,${\alpha}$-,${\beta}$- tocopherol showed 70%, 30%, 20% of initial concentrations in the oils respectively. There was no significant difference between Korean and Chinese sesame oil except the higher total amount of the tocopherol in Korean sesame oil than that of Chinese.

The Chemistry of Rhodium in Polysulfone: Reactions with Various Small Gas Molecules

  • Il-Wun Shim;Jin-Si Kim;Seok-Jong Oh;Yong-Sik Yang;Hwan-Kyu Suh;Sang-Kyu Lee
    • Bulletin of the Korean Chemical Society
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    • 제15권2호
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    • pp.126-132
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    • 1994
  • RhCl [P($C_6H_5)_3]_3$ complexes have been incorporated in polysulfone (PS) as a dispersion medium using cosolvent (THF). The interactions between Rh(Ⅰ) complexes and polysulfone polymer molecules are examined by infrared spectroscopy and thermal analysis. The chemical reactivity of Rh in PS films has been investigated by reacting Rh sites with CO, $H_2,\;D_2,\;O_2\;NO,\;C_2H_2\;and\;C_2H_4$ in the temperature range $25-200^{\circ}C$. Various Rh-carbonyl, -hydride and -nitrosyl species formed in PS films are characterized by their infrared spectra. Rh complexes in PS film show interesting catalytic reactivities in the reactions such as hydrogenation of $C_2H_2\;and\;C_2H_4$, oxidation of CO, and reduction of NO by CO or $H_2$ gas under relatively mild conditions.

FT-IR Studies of Molybdena Supported on Titania

  • Kim, Kwan;Lee,, Soon-Bo
    • Bulletin of the Korean Chemical Society
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    • 제12권1호
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    • pp.17-22
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    • 1991
  • Fourier transform infrared spectroscopy has been applied to the characterization of titania supported molybdena. The equilibrium adsorption method seemed to produce molybdena species homogeneously dispersed on the support. Even under an oxidizing environment, molybdena species appeared to be able to possess coordinatively unsaturated $Mo^{5+}$ ions owing to the natures of TiO$_2$, i.e. oxygen deficiency and permeability toward oxygen diffusion. At the initial stage of reduction, the terminal double bond oxygen ( Mo=O ) seemed to be removed, generating presumably $Mo^{4+}$. The carbonyl bands at 2198 and 2190 $cm^{-1}$ observed after CO exposure were attributed to the $Mo^{5+}{\cdots}CO\;and\;Mo^{4+}\;{\cdots}CO$ complexes, respectively, while the band pair at 2136 and 2076 $cm^{-1}$ to $Mo^{4+}(CO)_2$.

Interaction Between Barbiturate and Membrane Components

  • Yu, Byung-Sul;Jo, Seong-Bong;Kim, Chong-Kook;Hwang, Young-Sik
    • Archives of Pharmacal Research
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    • 제13권3호
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    • pp.246-251
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    • 1990
  • Intermolecular interaction between barbiturates and membrane components such as phospholipid and cholesterol were investigated on $^1$H-NMR spectra and infrared spectra. According to previous reports, barbiturates interacted with phospholipid through intermolecular hydrogen bonds. We also investigated thi observation using dipalmitoyl-phosphatidylcholine (DPPC) as phospholipid in deuterochloroform, and characterized quantitatively. Also, the observed drug could interact with cholesterol which is one of the major components of biomembranes through hydrogen bonds. It was the carbonyl groups of barbiturate and the hydroxyl group of cholesterol that formed hydrogen bond complex. In addition to spectroscopic studies, we investigated the direct effect of phenobarbital on lipid multibilayer vesicles, whose compositions were varied, by calorimetric method. Phenobarbital caused a reduction in the temperature of phase transition of vesicles. These studies may provided a basis for interpreting the mode of action of barbiturates.

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Bimetallic Pd@Ni-mesoporous TiO2 nanocatalyst for highly improved and selective hydrogenation of carbonyl compounds under UV light radiation

  • Bathla, Aadil;Pal, Bonamali
    • Journal of Industrial and Engineering Chemistry
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    • 제67권
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    • pp.486-496
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    • 2018
  • Bimetallic Pd@Ni nanostructure exhibited enhanced co-catalytic activity for the selective hydrogenation of benzaldehyde compare to their monometallic counterparts. Impregnation of these mono/bimetallic nanostructures on mesoporous $TiO_2$ leads to several surface modifications. The bimetallic PNT-3 ($Pd_3@Ni_1/mTiO_2$) exhibited large surface area ($212m^2g^{-1}$), and low recombination rate of the charge carriers ($e^--h^+$). The hydrogenation reaction was analyzed under controlled experiments. It was observed that under UV-light irradiations and saturated hydrogen atmosphere the bimetallic PNT-3 photocatalyst display higher rate constant $k=5.31{\times}10^{-1}h^{-1}$ owing to reduction in the barrier height which leads to efficiently transfer of electron at bimetallic/$mTiO_2$ interface.

Genenation of structural diversity in polyketides by combinatorial biosynthesis of polyketides: Part I. Generation of multiple bioactive macrolides by hybrid modular polyketide synthases in Streptomyces venezuelae, Part II. Production of novel rifamycins by combinatorial biosynthesis

  • Yoon, Yeo-Joon
    • 한국미생물생명공학회:학술대회논문집
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    • 한국미생물생명공학회 2002년도 학술발표대회
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    • pp.18-25
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    • 2002
  • The pikromycin biosynthetic system in Streptomyces venezuleae is unique for its ability to produce two groups of antibiotics that include the 12-membered ring macrolides methymycin and neomethymycin, and the 14-membered ring macrolides narbomycin and pikromycin. The metabolic pathway also contains two post polyketide-modification enzymes, a glycosyltransferase and P450 hydroxylase that have unusually broad substrate specificities. In order to explore further the substrate flexibility of these enzymes a series of hybrid polyketide synthases were constructed and their metabolic products characterized. The plasmid-based replacement of the multifunctional protein subunits of the pikromycin PKS in S. venezuelae by the corresponding subunits from heterologous modular PKSs resulted in recombinant strains that produce both 12- and 14-membered ring macrolactones with predicted structural alterations. In all cases, novel macrolactones were produced and further modified by the DesVII glycosyltransferase and PikC hydroxylase leading to biologically active macrolide structures. These results demonstrate that hybrid PKSs in S. venezuelae can produce a multiplicity of new macrolactones that are modified further by the highly flexible DesVII glycosyltransferase and PikC hydroxylase tailoring enzymes. This work demonstrates the unique capacity of the S. venezuelae pikromycin pathway to expand the toolbox of combinatorial biosynthesis and to accelerate the creation of novel biologically active natural products. The polyketide backbone of rifamycin B is assembled through successive condensation and ${\beta}$-carbonyl processing of the extender units by the modular rifamycin PKS. The eighth module, in the RifD protein, contains nonfunctional DH domain and functional KR domain, which specify the reduction of the ${\beta}$-carbonyl group resulting in the C-21 bydroxyl of rifamycin B. A four amino acid substitution and one amino acid deletion were introduced in the putative NADPH binding motif in the proposed KR domain encoded by rifD. This strategy of mutation was based on the amino acid sequences of the corresponding motif of the KR domain of module 3 in the RifA protein, which is believed dysfunctional, so as to introduce a minimum alteration and retain the reading frame intact, yet ensure loss of function. The resulting strain produces linear polyketides, from tetraketide to octaketide, which are also produced by a rifD disrupted mutant as a consequence of premature termination of polyketide assembly. Much of the structural diversity within the polyketide superfamily of natural products is due to the ability of PKSs to vary the reduction level of every other alternate carbon atom in the backbone. Thus, the ability to introduce heterologous reductive segments such as ketoreductase (KR), dehydratase (DH), and enoylreductase (ER) into modules that naturally lack these activities would increase the power of the combinatorial biosynthetic toolbox. The dehydratase domain of module 7 of the rifamycin PKS, which is predicted to be nonfunctional in view of the sequence of the apparent active site, was replaced with its functional homolog from module 7 of rapamycin-producing polyketide synthase. The resulting mutant strain behaved like a rifC disrupted mutant, i.e., it accumulated the heptaketide intermediate and its precursors. This result points out a major difficulty we have encountered with all the Amycolatopsis mediterranei strain containing hybrid polyketide synthases: all the engineered strains prepared so far accumulate a plethora of products derived from the polyketide chain assembly intermediates as major products instead of just analogs of rifamycin B or its ansamycin precursors.

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Effect of Luteolin on the Levels of Glycoproteins During Azoxymethane-induced Colon Carcinogenesis in Mice

  • Pandurangan, Ashok Kumar;Dharmalingam, Prakash;Sadagopan, Suresh Kumar Ananda;Ganapasam, Sudhandiran
    • Asian Pacific Journal of Cancer Prevention
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    • 제13권4호
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    • pp.1569-1573
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    • 2012
  • Luteolin (LUT), a bioflavonoid has been used as a chemopreventive agent world-wide against chemically induced cancer. Hence we designed an experiment to assess chemopreventive action of LUT on lipid peroxidation (LPO) and glycoconjugates in azoxymethane (AOM)-induced colon carcinogenesis. Colon cancer was induced by 15 mg/body kg. body weight of AOM and administration of LUT (at the dose of 1.2 mg/kg. body weight) was till end of the study. Analysis of lipid peroxidative end products such as protein carbonyl (PC), malonadehyde (MDA) and conjucated dienes (CD) demonstrated significant increase in in AOM-induced animals with reduction by LUT (p<0.05). Increased levels of glycoconjugates such as hexose, hexosamine, sialic acid, fucose and mucoprotein were analyzed in serum and colon tissues examined histopathologically by periodic acid Schiff's (PAS) staining were also reversed by LUT l(p<0.05). The secondary marker of colon cancer mucin depleted foci (MDF) was assessed in control and experimental group of animals. A characteristic increase of MDF was observed in AOM-induced colon cancer animals. Treatment with LUT decreased the incidence of MDF. These results suggest that LUT alters the expression of glycoconjugates and suppress colon cancer. Hence, we speculate that LUT can be used as a chemopreventive agent to treat colon cancer.

Norfloxacin Resistance Mechanism of E. coli 11 and E. coli 101-Clinical Isolates of Escherichia coli in Korea

  • Kim, Kyung-Soon;Lee, Soon-Deuk;Lee, Yeon-Hee
    • Archives of Pharmacal Research
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    • 제19권5호
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    • pp.353-358
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    • 1996
  • E. coli 11 and E. coli 101, clinical isolates of Escherichia coli were resistant to various quinolones, especially MICs to norfloxacin of both strains were higher than 100 mg/ml. In the presence of carbonyl cyanide m-chlorophenylhydrazone, a proton gradient uncoupler, norfloxacin uptake in both strains was increased, suggesting that an efflux system play an important role in the norfloxacin resistance. Outer membrane proteins of the susceptible and resistant strains which could affect the route of norfloxacin entry into cells were different. When quinolone resistance determining region(QRDR) of gyrA was amplified using PCR and cut with Hinf I, QRDR in the susceptible strain yielded two fragments while QRDRs in E. coli 11 and E. coli 101 yielded only one uncut fragment. When DNA sequence of QRDR was analyzed, there were two mutations as Ser-83 and Asp-87 in both resistant strains. these residues were changed to Leu-83 and Asn-87, respectively. These results showed that the norfloxacin resistance of E. coli 11 and E. coli 101 was resulted from multiple changes-an altered DNA gyrase A subunit, a change in route of drug entry, and reduction in quinolone concentration inside cells due to an efflux system.

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Thermal-and Bio-degradation of Starch-Polyethylene Films Containing High Molecular Weight Oxidized-Polyethylene

  • Kim, Mee-Ra;Pometto, Anthony-L.
    • Preventive Nutrition and Food Science
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    • 제3권1호
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    • pp.27-35
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    • 1998
  • Starch-polyethylene films containing high molecular weight(NW) oxidized-polyethylene and prooxidant were prepared , and thermal -and bio-degradability of the films were determined. Increased levels of starch resulted in a corresponding reduction in mechanical strength of the films. However, the addition of high MW oxidized-polyethylene did not significantly reduce the percent elongation of the films. Thefilms containing high MW oxidized-polyethylene andproosicant were degreaded faster than those containing no aadditive during the heat treatment. The films lost their measureable mechanical properties when their weight-average MW(Mw) fell below 50,000. Biodegradability of the films was determined by a pure culture assay with either Streptomyces badius 252.S. setonii 75Vi2 or S. viridosporous T7A, and by an extracellulr enzyme assay using S. setonii 75vi2. The results from pure culture assay indicated that biomass accumulation on the film surface inhibited chemical and biological degradation of the films. The extracellular enzyme assay demonstrated decrease of percent elongation and increase of carbonyl index of the films. Therefore, extracellular enzyme assay could be used as a good method to evaluate biodegradability of the films.

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