• Title/Summary/Keyword: Anionic pathway

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Synthesis of N-Alkylated 4-Fluoro-5-phenylpyrrole-2-carboxylate via Isolable Pyrroline Ionic Intermediates

  • Kim, Sung-Kwan;Jun, Chang-Soo;Kwak, Kyung-Chell;Park, Kwang-Yong;Chai, Kyu-Yun
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2324-2328
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    • 2007
  • Organic fluorine chemistry produces many useful products. This paper elucidates the reaction of ethyl-4,4- difluoro-2-iodo-5-oxo-5-phenylpentanoate (2) with primary amines in a one-pot scheme. The reaction produced a series of β-fluoropyrrole derivatives at ambient temperatures. In this reaction, the less bulky the primary amine the higher was the resultant yield. When (2) and aqueous methylamine (40%) were allowed to react below 0 oC, 5-(ethoxycarboxyl)-1-methyl-3,3-difluoro-2-hydroxy-2-phenylpyrrolidine, an intermediate molecule for 2-ethyl-4-flouro-1-methyl-5-phenylpyrrole-2-carboxylate (5), was isolated first. Then, (5) reacted with hydroperchloric acid and acetic anhydride to form 5-(ethoxycarboxyl)-1-methyl-3,3-difluoro-2- phenylpyrrolinium perchlorate (6), which was converted to 2-ethyl-4-flouro-1-methyl-5-phenylpyrrole-2- carboxylate gradually in the presence of a base. Our experiments demonstrate that the formation of 2-ethyl-4- flouro-1-methyl-5-phenylpyrrole-2-carboxylate occurs via both one-pot schemes and stepwise pathways, depending on the reaction conditions. The isolation and characterization of the isolated intermediate (6) suggest an anionic pathway for this reaction.

Poly(3,4-ethylenedioxythiophene) Electrodes Doped with Anionic Metalloporphyrins

  • 송의환;여인형;백운기
    • Bulletin of the Korean Chemical Society
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    • v.20 no.11
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    • pp.1303-1308
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    • 1999
  • Conducting poly(3,4-ethylenedioxythiophene) (PEDT) films with metalloporphyrins incorporated as the counter ions were prepared by electropolymerization of the monomer in the presence of metal-tetra(sulfonatophenyl) porphyrin anions. Cathodic reduction of oxygen on the resulting conducting polymer films was studied. The overpotential for O2 reduction on electrodes with cobalt-porphyrin complex was significantly smaller in acidic solutions than on gold. In basic solutions, the overpotential at low current densities was close to those on platinum and gold. Polymer electrode with Co-complex yielded higher limiting currents than with Fe-complex, although the Co-complex polymer electrode was a poorer electrocatalyst for O2 reduction in the activation range of potential than the Fe counterpart. From the rotating ring-disk electrode experiments, oxygen reduction was shown to proceed through either a 4-electron pathway or a 2-electron pathway. In contrast to the polypyr-role-based electrodes, the PEDT-based metalloporphyrin electrodes were stable with wider potential windows, including the oxygen reduction potential. Their electrocatalytic properties were maintained at temperatures up to 80℃ in KOH solutions.

The Reaction between Organothioenamine Phosphonate and Styrene Oxide (유기 티오엔아민 포스포네이트와 산화스티렌과의 반응)

  • Keun Jae Kim;Chi Sun Han
    • Journal of the Korean Chemical Society
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    • v.20 no.4
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    • pp.295-298
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    • 1976
  • The fact that a reaction between organothioenamine phosphonate and styrene oxide produces a derivative of cyclopropane has been proved by structural identification. This suggests that an anionic oxygen atom from the ring opening of the styrene oxide by nucleophilic attack of thioenamine phosphonate links to the phosphorous atom to from a betaine as an intermediate which is followed by cleavage of the weak P-C bond. The dextrorotatory optical activity of the product showed that the reaction was under the control of steric stability of the benzyl carbon in styrene which leads to the product through a sterically stable pathway.

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Theoretical Studies on Gas-Phase Reactions of Negative Ions with Alkyl Nitrites

  • Park, Hyeong Yeon;Kim, Chan Gyeong;Lee, Bon Su;Lee, Hae Hwang;Lee, Ik Chun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.8
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    • pp.823-827
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    • 2000
  • Gas-Phase reactions of methyl and ethyl nitrites with anionic nucleophiles of SH-, F- and OH- are investigated theoretically at the MP2/6-311+G* level. The SN2 processes are all highly exothermic and proceed with a typ-icaI double-weIl reaction coordinate profile. The elimination reactions of methyl nitrite with SH- and F- are double-well energy surface processes,with stabilizedproduct complexes of NO-...H2S and NO-...HF, pro-ceeding by an E1 cb-like E2 mechanism. The $\beta-elimination$ of ethyl nitrite is an E2 type process. The $\alpha-elimi-nation$ reactions of methyl and ethyl nitrites with OH- have triple-well energy profiles of Elcb pathway with an $\alpha-carbanion$ intermediate which is stabilized bythe vicinal $nc\alpha-{\sigma}*o-N$ charge transfer interactions. CompIex-ation ofmethyl carbanion with HF seems to provide a stable intermediate within a triple-well energy profile of El cb channel in the reaction of F- with methyl nitrite.

Effects of Homolactic Bacterial Inoculant Alone or Combined with an Anionic Surfactant on Fermentation, Aerobic Stability and In situ Ruminal Degradability of Barley Silage

  • Baah, J.;Addah, W.;Okine, E.K.;McAllister, T.A.
    • Asian-Australasian Journal of Animal Sciences
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    • v.24 no.3
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    • pp.369-378
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    • 2011
  • The effect of a homolactic inoculant containing a blend of Lactobacillus plantarum, Pediococcus acidilactici and Enterococcus faecium or, the anionic surfactant, sodium dodecyl sulphate (SDS), alone or in combination on fermentation characteristics, aerobic stability and in situ DM, OM and NDF degradability of barley silage was investigated. Barley (Hordeum vulgare, L.) was harvested (45% DM), chopped and treated with water at 24 ml/kg forage (Control), inoculant at $1.09{\times}10^5$ cfu/g forage (I), SDS at 0.125% (wt/wt) of forage (S) or with the inoculant ($1.09{\times}10^5$ cfu/g) plus SDS (0.125% wt/wt; I+S). The treated forages were ensiled in triplicate mini silos and opened for chemical and microbiological analyses on d 1, 2, 3, 7, 14, 42 and 77. Silage samples from d 77 were opened and aerobically exposed for 7 d. The in situ rumen degradability characteristics of silage DM, OM and NDF were also determined. The terminal concentration of NDF in S and I+S was lower (p<0.001) than in other treatments. Lactate concentration was higher (p<0.001) and the rate and extent of pH decline were greater (p<0.001) in I and I+S than S and Control silages. A homolactic pathway of fermentation in I and I+S was evidenced by reduced (p<0.001) water-soluble carbohydrates concentration, higher lactate (p<0.01), lower acetate (p<0.01) and lower pH values (p<0.001) than in S and Control silages. All silages remained stable over 7 d of exposure to air as indicated by lower temperatures and moulds, and by non-detectable yeast populations. The treated silages had lower DM and OM degradability than in the Control but NDF degradation characteristics of I+S were improved compared to other treatments. It is concluded that the inoculant alone improved the fermentation characteristics whereas the combination of the inoculant with SDS improved both fermentation and NDF degradability of barley silage.

Quantum Yield of Photoinduced Electron Transfer Across Microemulsion Interfaces (마이크로 에멀젼 계면을 통과하는 광유발전자의 양자수득률)

  • Yong-Tae Park
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.213-217
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    • 1983
  • Devices that mimic the natural photosynthetic pathway are of considerable interest as fuel sources. Quantum yield of viologen radical formation in several water-in-oil microemulsion system were measured. The yield of hexadecylviologen radical formation in microemulsion system using EDTA as an electron donor, ruthenium bipyridinium complex as photosensitizer, and hexadecylviologen as an electron acceptor was 12%. When benzylnicotinamide was inserted in the interface of the microemulsion and azo compound was dissolved in oil face, the quantum yield of hydroazo compound was 0.16. Organic dye (Rose bengal) was used as photosensitizer for the photoinduced electron transfer reaction. In anionic microemulsion no electrontransfer was observed.

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[ $^{99m}Tc-DISIDA$ ] Scintigraphic Findings of Hepatocellular Carcinoma (간세포암의 $^{99m}Tc-DISIDA$ 신티그램 소견)

  • Kim, Sung-Hoon;Chung, Soo-Kyo;Bahk, Yong-Whee
    • The Korean Journal of Nuclear Medicine
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    • v.20 no.1
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    • pp.33-37
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    • 1986
  • It is well known that $^{99m}Tc-sulfur$ colloid or phytate hepatic scintigraphy is highly sensitive but not specific. Both $^{99m}Tc-DISIDA$ and bilirubin have been shown to share the same anionic transport pathway in the liver. Hepatocellular carcinoma(HCC) retains the ability to produce bile but has marked limitation to excreting it resulting in accumulation of bile within the tumor cells. Based upon such a fact, $^{99m}Tc-DISIDA$ hepatobiliary scintigraphy is used for the diagnosis of HCC. The present communication deals with our experience of DISIDA scintigraphic exploration of 9 cases of HCC in a retrospective way. We have made an observation on intensity of positive radio nuclide accumulation in the cold area of HCC as it is demonstrated by phytate scintigraphy. In addition we have semi quantitatively analyzed time-activity pattern and the following results were obtained. (1) All of 9 cases showed an increased uptake of $^{99m}Tc-DISIDA$ in delayed scintigrams. Of these 5 cases showed accumulation less than, 3 equal to, 1 more than the surrounding liver tissue. (2) The mean of the first appearing time of $^{99m}Tc-DISIDA$ activity in tumoral region was 2 hours and 20 minutes. (3) DISIDA scintigraphy provides us with positive informations of diagnostic value.

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Diffusion Characteristics of Iodide in a Domestic Bentonite of Korea (국산벤토나이트에서의 요오드이온의 확산특성)

  • Lee, J.O.;Cho, W.J.;Hahn, P.S.;Park, H.H.
    • Nuclear Engineering and Technology
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    • v.26 no.2
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    • pp.285-293
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    • 1994
  • The transport of radionuclides in a compacted bentonite is dominated by diffusion. Through-diffusion tests for iodide were performed to investigate the diffusion characteristics of anionic radionuclides in a domestic bentonite. The bentonite used was sampled from the southeastern area of Korea and the solution was synthetic groundwater spiked with a tracer of I -125(as Na$^{125}$ I). The dry densities of compacted bentonite were 1.2, 1.4, and 1.7 Mg/㎥. The apparent diffusion coefficients and the effective diffusion coefficients of the iodide decrease with increasing dry density. The values were from 3.80 to 7.12$\times$10$^{-11}$ $m^2$/s for the apparent diffusion coefficients and from 1.25 to 7.97$\times$10$^{-12}$ $m^2$/s for the effective diffusion coefficient, respectively. The experimental results also showed that the apparent diffusion coefficients depended on the pore structure of compacted bentonite and the effective diffusion coefficients were attributed to the pore structure and the effective porosity that represents the available pathway for the diffusional transport of iodide. The results obtained will be used as basic data for the safety assessment of a repository.

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Role of ghrelin in the pancreatic exocrine secretion via mitogen-activated protein kinase signaling in rats

  • Lee, Kyung-Hoon;Lee, Jae-Sung;Wang, Tao;Oh, Jin-Ju;Roh, Sanggun;Lee, Hong-Gu
    • Journal of Animal Science and Technology
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    • v.59 no.7
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    • pp.16.1-16.6
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    • 2017
  • Background: This study was performed to investigate the impact of exogenous ghrelin on the pancreatic ${\alpha}$-amylase outputs and responses of pancreatic proteins to ghrelin that may relate to pancreatic exocrine. Methods: Sprague-Dawley male rats (9 weeks old, $300{\pm}10g$) were injected with ghrelin via intraperitoneal (i.p.) infusion at dosage of 0, 0.1, 1.0 and $10.0{\mu}g/kg$ body weight (BW), respectively. The plasma ghrelin and cholecystokinin (CCK) level were determined using enzyme immunoassay kit; the mRNA expression of ghrelin receptor ($GHSR-1{\alpha}$) and growth hormone (GH) receptor were assessed by reverse transcription PCR; the expressions of pancreatic ${\alpha}$-amylase activity, extracellular-signal-regulated kinases (ERK), phosphorylated extracellular-signal-regulated kinases (pERK) and c-Jun N-terminal kinase (JNK) were evaluated by western blotting; moreover the responses of pancreatic proteins to ghrelin were analyzed using the two-dimensional gel electrophoresis system. Results: The exogenous ghrelin (1.0 and $10.0{\mu}g/kg\;BW$) elevated the level of plasma ghrelin (p < 0.05), and suppressed the expression of pancreatic ${\alpha}$-amylase at a dose of $10.0{\mu}g/kg\;BW$ (p < 0.05). No difference in the level of plasma CCK was observed, even though rats were exposed to any dose of exogenous ghrelin. In addition, a combination of western blot and proteomic analysis revealed exogenous ghrelin ($10.0{\mu}g/kg\;BW$) induced increasing the JNK and ERK expressions (p < 0.05) and four proteins such as Destrin, Anionic trypsin-1, Trypsinogen, and especially eukaryotic translation initiation factor 3 in rat pancreas. Conclusions: Taken together, exogenous ghrelin by i.p. infusion plays a role in the pancreatic exocrine secretion via mitogen-activated protein kinase signaling pathway.