• Title/Summary/Keyword: reductive reaction

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Formation of Methyl 2${\beta},\;3{\beta}$-Epoxy-23-hydroxyurs-12-en-28-oate from Asiaticoside and Its Reductive Epoxide Ring Opening Reaction (아시아티코사이드로부터 메칠 2${\beta},\;3{\beta}$-에폭시-23- 히드록시우르스-12-엔-28-오애이트의 합성 및 이의 환원적 에폭시환 개열반응)

  • Jew, Sang-Sup;Lim, Doo-Yeon;Seo, Sung-Ki;Nam, Tae-Gyu;Park, Hyeung-Geun;Kim, Hee-Doo;Kim, Chang-Min;Lee, Min-Hee;Paik, Hyeung-Geun;Lee, Min-Jung;Jung, Young-Hoon
    • YAKHAK HOEJI
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    • v.42 no.5
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    • pp.500-506
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    • 1998
  • Steroidal 2${\beta},\;3{\beta}$--epoxy compound was prepared from asiaticoside via six steps and reduced regioselectively with lithium aluminum hydride. Epoxide ring opening furnished 9 as a sole product at reflux condition through axial hydride attack at C-3.

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Synthesis and Spectroscopic Investigations of Some New rganotelluronium alts Based on Dicyclohexyl Telluride (디시클로헥실 텔루르염에 기반한 유기텔루로늄염의 성과 분광학적 분석)

  • Al-Rubaie, Ali Z.;Al-Mudhaffar, Dhafir M. H.;Al-Mowali, Ali H.;Asker, Kahtan A.
    • Journal of the Korean Chemical Society
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    • v.53 no.5
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    • pp.530-535
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    • 2009
  • Dicyclohexyl telluride was obtained in a high yield by the reaction of cyclohexyl bromide with NaTeH(prepared in situ) in an aqueous ethanolic solution. A series of new organotelluronium salts of the general formula ${(cyclo-C_6H_11)}_2Te(R)X$ (where R = $CH_3$, X = I (1); R = $C_2H_5$, X = Br(2); R = $C_2H_5$, X = I (3); R = C_3H_5$, X = Br (4)) were prepared by the reaction of ${(cyclo-C_6H_11)}_2Te$ with the corresponding alkyl halide. Reaction of 1 with NaBPh4 gave compound 5 ( i.e. R = CH3, X = BPh4 ‒) in 78% yield. Reaction of ${(cyclo-C_6H_11)}_2Te$ with benzyl bromide and 4-bromophenacyl bromide gave unexpectedly dibenzylcyclohexyltelluronium bromide (6) and bis(4-bromophenacyl)cyclohexyltelluronium bromide (7), respectively. Reaction of 6 with NaBPh4 gave the corresponding tetraphenylborate derivative (8) in high yield. $^1H$ NMR studies revealed that in $CDCl_3$solution compound 1 eliminated alkyl halide. Conductivity, IR, $^1H\;and\;^{13}C$ NMR and thermal data for the new compounds are presented and discussed.

Selective Electrochemical Reduction on the Imino Group of ${\alpha},{\beta}$-Dibenzyl N-Benzylidene L-Aspartate (${\alpha},{\beta}$-Dibenzyl N-Benzylidene L-Aspartate 의 Imino 기에 대한 선택적 전해환원반응)

  • Kim, Il-Kwang;Kim, Youn-Geun;Lee, Young-Haeng;Chai, Kyu-Yun
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.614-622
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    • 1989
  • The electrochemical reduction of ${\alpha},{\beta}$-dibenzyl N-benzylidene L-aspartate in 0.1M LiCl ethanol solution was investigated by direct current (DC), differential pulse (DP) polarography, cyclic voltammetry and controlled potential coulometry(CPC). The irreversible reductive amination of imino group proceeded to form ${\alpha},{\beta}$-dibenyl N-benzyl L-aspartate by CEC or CE electrochemical reaction mechanism at the first reduction step (-0.92 volts vs. Ag-AgCl). The polarographic reduction wave was slightly suppressed due to inhibitory effect of micelle, while the irreversibility was increased according to the increase of Triton X-100 concentration. Upon the basis of product analysis and polarogram interpretation with pH change, possible CE electrode reaction mechanism was suggested.

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Microbial Community in the TPH-Contaminated Aquifer for Hot Air Sparging using Terminal-Restriction Fragment Length Polymorphism (유류오염대수층 고온공기분사공정시 제한효소다형성 미생물 군집)

  • Lee, Junho;Park, Kapsong
    • Journal of Korean Society on Water Environment
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    • v.24 no.1
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    • pp.19-29
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    • 2008
  • Hot air sparging is a groundwater remediation technique, in which organic contaminants volatilized into hot air from the saturated to vadose zone. In the laboratory diesel (10,000 mg TPH/kg) was spiked in contaminated saturated aquifer soil. The hot air ($34.9{\pm}2.7^{\circ}C$) was injected in intermittent (Q=1,500 mL/min, 10 minute injection and 10 minute idle) modes. We performed microcosm tests using the groundwater samples to assess TPH reductive remediation activity. For Terminal-Restriction Fragment Length Polymorphism (T-RFLP) analysis of eubacterial communities in sludge of wastewater treatment plants and soil of experiment site, the 16S rDNA was amplified by Polymerase Chain Reaction (PCR) from the sludge and the soil. The obtained 16S rDNA fragments were digested with Msp I and separated by electrophoresis gel. We found various sequence types for hot air sparging experiment with sludge soil samples that were closely related to Bacillus (149 bp, Firmicutes), Methlobacterium (149 bp, Euryarchaeotes), Pseudomonas (492 bp, ${\gamma}$-Proteobacteria), etc., in the clone library. In this study we find that TPH-water was reduced to 78.9% of the initial value in this experiment aquifer. The results of the present study suggests that T-RFLP method may be applied as a useful tool for the monitoring in the TPH contaminated soil fate of microorganisms in natural microbial community.

Reduction of Nitrate-nigrogen by Zero-valent Iron Adhered in Mesoporous Silicas (메조기공 실리카에 부착된 영가철을 이용한 질산성 질소의 환원)

  • Yeon, Kyeong-Ho;Lee, Seunghak;Lee, Kwanyong;Park, Yong-Min;Kang, Sang-Yoon;Lee, Jae-Won;Choi, Yong-Su;Lee, Sang-Hyup
    • Journal of Korean Society of Water and Wastewater
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    • v.21 no.1
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    • pp.139-147
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    • 2007
  • For environmental remediation of a contaminated groundwater plume, the use of zero-valent metal represents one of the latest innovative technologies. In this study, the effects of denitrification by zero-valent iron adsorbed in mesoporous silicas have been studied for groundwater contaminant degradation. The mesoporous silica was functionalized with 3-mercaptopropyltrimethoxysilane (MPTS) ligands and the zero-valent iron precipitated in the mesopore of granular silica was made by $FeCl_2$ and $NaBH_4$. Hydrogen was exchanged with $Fe^{2+}$ ions in the granular silicas. And then the ions were reduced by sodium borohydride in the mesoporous silicas. The surface area of the silica determined via the BET method ranged from 858 to $1275m^2/g$. The reductive reaction of nitrate-nitrogen indicated that the degradation of nitrate-nitrogen appeared to be pseudo first-order with the observed reaction rate constant kobs ($0.1619h^{-1}$) and to be directly proportional to the specific surface area. Therefore, the mesoporous silica with nano zero-valent iron proposed as a novel treatment strategy for contaminated groundwater was successfully implemented herein for the removal of nitrate-nitrogen.

Reduction Leaching of Manganese Dioxide Ore Using Black Locust as Reductant in Sulfuric Acid Solution

  • Xue, Jianrong;Zhong, Hong;Wang, Shuai;Li, Changxin;Li, Jinzhong;Wu, Fangfang
    • Korean Chemical Engineering Research
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    • v.53 no.4
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    • pp.509-516
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    • 2015
  • We investigated the reduction leaching process of manganese dioxide ore using black locust as reductant in sulfuric acid solution. The effect of parameters on the leaching efficiency of manganese was the primary focus. Experimental results indicate that manganese leaching efficiency of 97.57% was achieved under the optimal conditions: weight ratio of black locust to manganese dioxide ore (WT) of 4:10, ore particle size of $63{\mu}m$, $1.7mol{\cdot}L^{-1}\;H_2SO_4$, liquid to solid ratio (L/S) of 5:1, leaching time of 8 h, leaching temperature of 368 K and agitation rate of $400r{\cdot}min^{-1}$. The leaching rate of manganese, based on the shrinking core model, was found to be controlled by inner diffusion through the ash/inert layer composed of associated minerals. The activation energy of reductive leaching is $17.81kJ{\cdot}mol^{-1}$. To conclude the reaction mechanism, XRD analysis of leached ore residue indicates manganese compounds disappear; FTIR characterization of leached residue of black locust sawdust shows hemicellulose and cellulose disappear after the leaching process.

The Biochemical Characterization of D-Hydroxyisovalerate Dehydrogenase, a Key Enzyme in the Biosynthesis of Enniatins

  • Lee, Chan; Zocher, Rainer
    • BMB Reports
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    • v.29 no.6
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    • pp.493-499
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    • 1996
  • The biochemical properties of purified D-hydruxyisovalerate dehydrogenase from Fusarium sambucinum was elucidated. D-Hydroxyisovalerate dehydrogenase produced solely D-hydroxyisovalerate from 2-ketoisovalerate. The isoelectric point of the purified enzyme was 7.0. The enzyme was highly specific with 2-ketoisovalerate ($K_{m}=0.188$ mM, $V_{max}=8.814$ mmol/min mg) and 2-keto-3-methyl-n-valerate ($K_{m}=0.4$ mM, $V_{max}=1.851$ mmol/min mg) for the reductive reaction. This was also seen by comparing D-hydroxyisovalerate ($K_{m}=1.667$ mM, $V_{max}=0.407$ mmol/min mg) and D-hydroxy-3-methyl-n-valerate ($K_{m}=6.7$ mM, $V_{max}=0.648$ mmol/min mg) for the oxidative reaction. Thiol blocking reagents, such as iodoacetamide, N-ethylmaleimide and p-chloromecuribenzoate inhibited about 80% of enzyme activity at 0.02 mM, 50 mM and 50 mM, respectively. The enzyme activity was also inhibited by the addition of 0.1 mM of various metal ions, such as $Fe^{2+}$ (67%), $Cu^{2+}$ (88%), $Zn^{2+}$ t (76%) and $Mg^{2+}$ (9%). The enzyme was stable over three months in 50 mM potassium phosphate buffer (pH 5~7) at $-80^{\circ}C$. However the purified enzyme lost 30% of its activity in the same buffer after 24 h at $4^{\circ}C$. The studies about thermal inactivation of D-hydroxyisovalerate dehydrogenase exhibit 209.2 kJ/M of activation enthalpy and 0.35 kJ/mol K of activation entropy.

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Synthesis of 1-Benzyl-4-Iodomethyl-2-Azetidinone and Electrochemical Reduction on the Iodo Group (1-Benzyl-4-Iodomethyl-2-Azetidinone의 합성과 Iodo기에 대한 전기화학적 환원반응)

  • Kim Il Kwang;Lee Young Haeng;Lee Chai Ho;Chai Kyu Yun;Kim Yoon Geun
    • Journal of the Korean Chemical Society
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    • v.35 no.1
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    • pp.70-77
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    • 1991
  • 1-Benzyl-4-iodomethyl-2-azetidinone(BIMA) was synthesized and its electrochemical reduction was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The irreversible two electron transfer on reductive dehalogenation of iodo group proceeded to form 1-benzyl-4-methyl-2-azetidinone by EEC electrode reaction mechanism at the first reduction step(-1.35 volts vs. Ag-AgCl). The polarographic reduction waves separated into two reduction steps due to anionic surfactant (sodium lauryl sulfate) effects, while the waves were shifted to the positive potential as the concentration of cationic surfactant (cetyltrimethylammonium bromide) increased. Upon the basis of results on the product analysis and interpretation of polarogram with pH variable, EEC electrochemical reaction mechanism was suggested.

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Removal Characteristics of Dissolved Uranium by Shewanella p. and Application to Radioactive Waste Disposal (스와넬라균(Shewanella p.)에 의한 용존우라늄 제거 특성 및 방사성폐기물 처분에의 응용)

  • Lee, Seung-Yeop;Baik, Min-Hoon;Song, Jun-Kyu
    • Economic and Environmental Geology
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    • v.42 no.5
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    • pp.471-477
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    • 2009
  • An experimental removal of dissolved uranium (U) exsiting as uranyl ion (${UO_2}^{2+}$) was carried out using Shewanella p., iron-reducing bacterium. By the microbial reductive reaction, initial U concentration ($50{\mu}M$) was constantly decreased, and most U were removed from solution after 2 weeks. Major mechanism that U was removed from the solution was adsorption, precipitation and mineralization on the microbe surface. Under the transmission electron microscopy, the U adsorbed on the microbe was observed as being crystallized and eventually enlarged to several ${\mu}m$ sizes of minerals by combining with individual microbes and organic exudates. It seems that such U growth and mineralization on the microbial surface could affect the U behavior in a radioactive waste disposal site. Thus, the biogechemical reaction of metal-reducing bacteria observed in this experiment could give an affirmative measure that the microbial activity may retard U movement in subsurface environment.

Recovery of Lithium and Leaching Behavior of NCM Powder by Carbon Reductive Treatment from Li(NCM)O2 System Secondary Battery Scraps (Li(NCM)O2계(係) 이차전지(二次電池) 공정(工程)스크랩의 탄소환원처리(炭素還元處理)에 의한 리튬회수(回收) 및 NCM 분말(粉末)의 침출거동(浸出擧動))

  • Kim, Dae Weon;Jang, Seong Tae
    • Resources Recycling
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    • v.22 no.4
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    • pp.62-69
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    • 2013
  • A study on the recovery of lithium and leaching behavior of NCM powder by carbon reduction for NCM-system Li-ion battery scraps was conducted. First of all, the oxide powders of NCM-system with layer structure were decomposed by carbon, lithium was converted to lithium carbonate by carbon reaction at above $600^{\circ}C$. The lithium carbonate powders with 99% purity were manufactured by washing method with water and concentration process for NCM powder after carbon reduction. The reaction yield was approximately 88% at $800^{\circ}C$ by carbon reduction. At this time, leaching efficiency at 2M sulfuric acid concentration was over 99% for cobalt, nickel and manganese.