• 제목/요약/키워드: $K^+$ ion catalysis

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Furfurylidene acetophenone유도체의 합성과 가수분해 반응 (Synthesis and Hydrolysis of Furfurylidene acetophenone Derivatives)

  • 이기창;이광일;윤철훈;황성규;오세영
    • 한국응용과학기술학회지
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    • 제13권1호
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    • pp.99-105
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    • 1996
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that hydrolysis made use of UV at a wide pH $1.0{\sim}13.0$ range in 30% $dioxane-H_2O$ solution, $25{\pm}1^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of hydrolysis products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It maybe concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion : Above pH 10.0, It was in proportion to concentration of hydroxide ion, a part having no concern with pH was added to the neutral $H_2O$ molecule. From the result of measurement the reaction rate, hydrolysis of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect, It found that reaction rate was accelerated by electron attracting group. Also, From the result of final product, There were furfural and acetophenone. On the basis of these findings, Hydrolysis for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

Furfurylidene acetophenone유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구 (The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Furfurylidene Acetophenone derivatives)

  • 이기창;목갑영;오세영;류정욱
    • 한국응용과학기술학회지
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    • 제14권1호
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    • pp.27-32
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    • 1997
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

Styryldiphenylphosphine Oxide의 가수분해 반응 메카니즘에 관한 반응속도론적 연구 (Kinetic Studies on the Mechanism of Hydrolysis of Styryldiphenylphosphine Oxide)

  • 김태린;신갑철;편상용;이석희
    • 대한화학회지
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    • 제44권5호
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    • pp.429-434
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    • 2000
  • Styryldiphenylphosphine(SDPO)의 가수분해 속도상수를 자외선 분광법으로 측정하여 넓은 pH에서 잘 맞는 반응속도식을 구하였다. pH에 따르는 속도상수의 변화, 가수분해 생성물의 확인, 일반염기 및 치환기 효과 등으로부터 실험 결과에 잘 맞는 반응 메커니즘을 제안하였다. 즉 pH 4.5 이하에서는 phosphine oxide기의 산소에 양성자가 첨가된 다음 탄소 이중결합에 물의 첨가가 일어나 가수분해가 진행되며, pH 4.5-8.0 사이에서는 물분자와 수산와 음이온의 첨가가 경쟁적으로 일어나 반응이 진행되었고, pH 8.0 이상에서는 반응속도 상수가 수산화 음이온의 농도에만 비례함을 알았다.

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Leuconostoc mesenteroides NRRL B-1149의 Glucosyltransferase와 Fructosyltransferase의 분리와 특성 연구 (Purification and Characterization of Glucosyltransferase and Fructosyltransferase in Leuconostoc mesenteroides NRRL B-1149)

  • 이진하;박준성;이희선;김도만
    • KSBB Journal
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    • 제19권5호
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    • pp.368-373
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    • 2004
  • The optimal condition for the production of a glucan and a fructan synthesizing enzymes from Leuconostoc mesenteroides NRRL B-1149 were studied based on the different medium compositions. Response surface methodology was applied to find the optimistic condition showing the relationship between the fermentation response (enzyme activities) and the fermentation variable concentrations of yeast extract, peptone concentration, K2HP04 concentration and sucrose. Optimum medium composition for both enzymes production was $0.75\%$ yeast extract, $0.72\%$ peptone, $1\%$ K2HP04 and $2.17\%$ sucrose. Using this medium, the activities produced in culture was 0.90 U/m~ for glucosyltransferase (GTase) and 0.96 U/ml for fructosyltransferase (FTase). After purification of 1149FTase by consecutive chromatographies using Sephadex G-150 and DEAE-Sepharose, a 1149FTase of 210 kDa on $7\%$ polyacrylamide gel was isolated and it synthesized soluble fructan. The 1149GTase showed a band of 180 kDa on $8\%$ polyacrylamide gel after purification using Bio-Gel P-100 gel chromatography and DEAE-Sepharose ion exchange chromatography and it synthesized insoluble glucan. The linkages of polymers were determined by methylation using Hakomori reagent and following NMR analysis. The glucan was composed of a(1~6) and a(1~3) linkages and the fructan was levan.

Purification and Characterization of Novel Bifunctional Xylanase, XynIII, Isolated from Aspergillus niger A-25

  • Chen Hong-Ge;Yan Xin;Liu Xin-Yu;Wang Ming-Dao;Huang Hui-Min;Jia Xin-Cheng;Wang Jin-An
    • Journal of Microbiology and Biotechnology
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    • 제16권7호
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    • pp.1132-1138
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    • 2006
  • Three types of xylanases (EC 3.2.1.8) were detected in the strain Aspergillus niger A-25, one of which, designated as XynIII, also displayed ${\beta}-(l,3-1,4)-glucanase$ (EC 3.2.1.73) activity, as determined by a zymogram analysis. XynIII was purified by ultrafiltration and ion-exchange chromatography methods. Its apparent molecular weight was about 27.9 kDa, as estimated by SDS-PAGE. The purified XynIII could hydrolyze birchwood xylan, oat spelt xylan, lichenin, and barley ${\beta}-glucan$, but not CMC, avicel cellulose, or soluble starch under the assay conditions in this study. The xylanase and ${\beta}-(l,3-1,4)-glucanase$ activities of XynIII both had a similar optimal pH and pH stability, as well as a similar optimal temperature and temperature stability. Moreover, the effects of metal ions on the two enzymatic activities were also similar. The overall hydrolytic rates of XynIII in different mixtures of xylan and lichenin coincided with those calculated using the Michaelis-Menten model when assuming the two substrates were competing for the same active site in the enzyme. Accordingly, the results indicated that XynIII is a novel bifunctional enzyme and its xylanase and ${\beta}-(l,3-1,4)-glucanase$ activities are catalyzed by the same active center.

Role of the Amino Acid Residues in the Catalysis of Catechol 2,3-dioxygenase from Pseudomonas putida SU10 as Probed by Chemical Modification and Random Mutagenesis

  • Park, Sun-Jung;Park, Jin-Mo;Lee, Byeong-Jae;Min, Kyung-Hee
    • Journal of Microbiology
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    • 제35권4호
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    • pp.300-308
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    • 1997
  • The catechol 2,3-dioxygenase (C23O) encoded by the Pseudomonas putida xylE gene was over-produced in Escherichia coli and purified to homogeneity. The activity of the C23O required the reduced form of the Fe(II) ion since the enzyme was highly susceptible to inactivation with hydrogen perocide but reactivated with the addition of ferrous sulfate in conjunction with ascorbic acid. The C23O activity was abolished by treatment with the chemical reagents, diethyl-pyrocarbonate (DEPC), tetranitromethane (TNM), and 1-cyclohexy1-3-(2-morpholinoethyl) car-bodiimidemetho-ρ-toluenesulfontate (CMC), which are modifying reagents of histidine, tyrosine and glutamic acid, respectively. These results suggest that histidine, tyrosine and glutamic acid residues may be good active sites for the enzyme activity. These amino acid residues are conserved residues may be good active sites for the enzyme activity. These amino acid residues are conserved residues among several extradion dioxygenases and have the chemical potential to serveas ligands for Fe(II) coordination. Analysis of random point mutants in the C23O gene derived by PCR technique revealed that the mutated positions of two mutants, T179S and S211R, were located near the conserved His165 amd Hos217 residues, respectively. This finding indicates that these two positions, along with the conserved histidine residues, are specially effective regions for the enzyme function.

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Sol-gel법을 이용한 백색도가 높은 가시광 응답형 N-doped TiO2 제조 및 특성 평가 연구 (Preparation and Characterization of Visible Light-Sensitive N-doped TiO2 Using a Sol-gel Method)

  • 이나리;유리;김태관;피재환;김유진
    • 한국분말재료학회지
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    • 제24권6호
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    • pp.477-482
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    • 2017
  • Nitrogen-doped titanium dioxide (N-doped $TiO_2$) is attracting continuously increasing attention as a material for environmental photocatalysis. The N-atoms can occupy both interstitial and substitutional positions in the solid, with some evidence of a preference for interstitial sites. In this study, N-doped $TiO_2$ is prepared by the sol-gel method using $NH_4OH$ and $NH_4Cl$ as N ion doping agents, and the physical and photocatalytic properties with changes in the synthesis temperature and amount of agent are analyzed. The photocatalytic activities of the N-doped $TiO_2$ samples are evaluated based on the decomposition of methylene blue (MB) under visible-light irradiation. The addition of 5 wt% $NH_4Cl$ produces the best physical properties. As per the UV-vis analysis results, the N-doped $TiO_2$ exhibits a higher visible-light activity than the undoped $TiO_2$. The wavelength of the N-doped $TiO_2$ shifts to the visible-light region up to 412 nm. In addition, this sample shows MB removal of approximately 81%, with the whiteness increasing to +97 when the synthesis temperature is $600^{\circ}C$. The coloration and phase structure of the N-doped $TiO_2$ are characterized in detail using UV-vis, CIE Lab color parameter measurements, and powder X-ray diffraction (XRD).

금속유기구조체를 이용한 이산화탄소 흡착 연구 (CO2 Adsorption in Metal-organic Frameworks)

  • 김준;김희영;안화승
    • Korean Chemical Engineering Research
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    • 제51권2호
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    • pp.171-180
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    • 2013
  • 금속유기구조체(metal-organic frameworks, MOF)는 넓은 비표면적, 규칙적인 구조 및 높게 분산된 금속 성분 등 뛰어난 물리화학적 특성으로 인해 활발한 연구가 이뤄지고 있는 다공성 물질이며, 특히 가스의 흡착, 분리 매체로서 뛰어난 성능이 보고되고 있다. MOF를 이용한 온실가스 이산화탄소의 흡착 연구는 상온 고압 영역에서 이산화탄소 저장 공정과 상온 저압 영역에서 이산화탄소 흡착 공정의 두 범주로 나눌 수 있으며, MOF의 넓은 비표면적 외에도 (1) MOF의 빈 배위결합 자리, (2) MOF의 기능화, (3) MOF의 상호 침투 효과, 및 (4) 이온 교환 효과를 이용한 연구 결과가 보고되고 있다. MOF 물질들은 비교적 낮은 수분 및 열에 대한 안정성이 문제로 제기되고 있으며, 제올라이트 유사 구조체(zeolitic imidazolate frameworks, ZIF) 또는 유기 골격 구조체(covalent organic frameworks, COF) 물질의 이산화탄소 흡착 특성이 거론되고 있다. 본 소고에서는 MOF를 이용한 이산화탄소 흡착에 대한 최근의 연구 결과를 본 연구실의 실험 결과를 중심으로 간략히 소개하고자 한다.

Aliphatic Ketone과 Alicyclic Ketone의 Semicarbazone 생성반응에 관한 연구 (Studies on the Semicarbazone Formation of Aliphatic and Alicyclic Ketones.)

  • 임락빈;오양환;김용인
    • 한국응용과학기술학회지
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    • 제8권1호
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    • pp.59-67
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    • 1991
  • The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.

${\beta}$-Nitrostyrene 유도체에 대한 Thiourea의 친핵성 첨가반응에 관한 반응속도론적 연구 (Kinetic Studies on the Nucleophilic Addition of Thiourea to ${\beta}$-Nitrostyrene Derivatives)

  • 김태린;정연수;정명숙
    • 대한화학회지
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    • 제35권3호
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    • pp.268-274
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    • 1991
  • ${\beta}$-nitrostyrene 유도체(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$)에 대한 thiourea의 친핵성 첨가반응속도를 자외선 분광분석법으로 측정하여 pH에 따르는 반응속도 상수의 변화, general base 및 치환기 효과등으로부터 넓은 pH 범위에서 실험치와 잘 일치하는 반응속도식을 구하였고, 실험사실에 잘 맞는 반응 메카니즘을 제안하였다. 즉, pH 9.00 이상에서의 반응속도는 hydroxide ion의 농도에 비례하는 sulfide anion이 첨가되는 전형적인 Michael type의 반응이 일어나며, pH 9.00 ~ 7.00에서는 thiourea의 중성분자와 그의 anion들이 경쟁적으로 첨가되며 pH 7.00 이하에서는 thiourea의 중성분자만이 첨가됨을 알았다.

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