• Title/Summary/Keyword: C-H amination

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A Study on the Photoreaction between Organic Halides and Amines (有機 Halides 와 Amines 間의 光反應에 關한 硏究)

  • Kim, You-Sun;Park, Yong-Ja
    • Journal of the Korean Chemical Society
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    • v.6 no.2
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    • pp.148-154
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    • 1962
  • The reactions between organic halides$(CCl_4,\;C_6H_5Br,\;C_6H_5Cl,\;C_6H_5I)$ and amines $(C_6H_5NH_2,\;R_2NH,\;R_3N,\;(CH_2)_5NH,\;pyridine)$ were studied under mixed u.v. irradiation. The modes of reactions were examined by means of gas chromatography and product-reactant ratio determination. The reaction of $CCl_4$ with amines give chloroform and hexachloroethanes, and the reaction of aromatic halides with amines gave biphenyl and benzene. In each series of reaction there obtained mainly corresponding amine hydrohalides, but no amination products. The reactivity was in the order of the basicity of amines and of the reactivity of organic hahides, except in the case of cyclic tertiary amine. The result was interpreted as a non-chain photodecomposition process. A competitive proton abstraction reaction path via the formation of a change transfer complex was proposed as the reaction mechanism.

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The Kinetic Parameters of Hafnia alvei Aspartase from pH Studies

  • Kim, Sung-Kun;Choi, Jung-Hoon;Yoon, Moon-Young
    • BMB Reports
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    • v.28 no.3
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    • pp.204-209
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    • 1995
  • The pH dependence of kinetic parameters in the amination direction of the aspartase from Hafnia alvei has been determined. The V/K for fumarate is bell shaped with pK values of 6.4 and 8.7. The maximum velocity for fumarate is also bell shaped with pK values of 7.2 and 9.1. The pH dependence of 1/K, for potassium (competitive inhibitor of ammonia) decreases at low pH with pK 7.6. Together with data [Yoon and Cook (1994) Korean J. Biochem. 27, 1-5] on the deamination direction of the aspartase, these results are consistent with two enzyme groups which are necessary for catalysis. An enzymatic group that must be deprotonated has been identified. Another enzyme group must be protonated for substrate binding. Both the general base and general acid group are in a protonation state opposite that in which they started when aspartate was bound. A proton is abstracted from C-3 of the monoanionic form of L-aspartate by an enzyme general base with, a pK of 6.3~6.6 in the absence and presence of $Mg^{2+}$ Ammonia is then expelled with the assistance of a general acid group giving $NH_{4+}$ as the product.

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Optimized Conditions for In Situ Immobilization of Lipase in Aldehyde-silica Packed Columns

  • Seo Woo Yong;Lee Kisay
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.9 no.6
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    • pp.465-470
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    • 2004
  • Optimal conditions for the in situ immobilization of lipase in aldehyde-silica packed columns, via reductive amination, were investigated. A reactant mixture, containing lipase and sodium borohydride (NaCBH), was recirculated through an aldehyde-silica packed column, such that the covalent bonding of the lipase, via amination between the amine group of the enzyme and the aldehyde terminal of the silica, and the reduction of the resulting imine group by NaCBH, could occur inside the bed, in situ. Mobile phase conditions in the ranges of pH $7.0{\~}7.8$, temperatures between $22{\~}28^{circ}C$ and flow rates from $0.8{\~}1.5\;BV/min$ were found to be optimal for the in situ immobilization, which routinely resulted in an immobilization of more than 70 mg­lipase/g-silica. Also, the optimal ratio and concentration for feed reactants in the in situ immobilization: mass ratio [NaCBH]/[lipase] of 0.3, at NaCBH and lipase concentrations of 0.75 and 2.5 g/L, respectively, were found to display the best immobilization characteristics for concentrations of up to 80 mg-lipase/g-silica, which was more than a 2-fold increase in immobilization compared to that obtained by batch immobilization. For tributyrin hydrolysis, the in situ immobilized lipase displayed lower activity per unit mass of enzyme than the batch-immobilized or free lipase, while allowing more than a $45\%$ increase in lipase activity per unit mass of silica compared to batch immobilization, because the quantity of the immobilization on silica was aug­mented by the in situ immobilization methodology used in this study.

Synthesis of p-Phenylenediamine (PPD) using Supercritical Ammonia (초임계 암모니아를 이용한 p-Phenylenediamine(PPD) 합성 및 특성연구)

  • Cho, Hang-Kyu;Lim, Jong Sung
    • Korean Chemical Engineering Research
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    • v.53 no.1
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    • pp.53-56
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    • 2015
  • In this study, investigated the synthesis method of p-Phenylenediamine (PPD) by amination of p-Diiodobenzene (PDIB) under supercritical ammonia and CuI catalyst conditions. We examined the effects of various process variables (e.g., reaction temperature, pressure, amount of ammonia inserted, amount of catalyst inserted, and reaction time) on the production yield of PPD by analyzing the Gas Chromatography (GC). The experimental results demonstrated that PPD was not produced under non-catalyst conditions, and PPD production yield increased with increasing temperature, pressure, amount of catalyst inserted, and reaction time. However, for the reaction temperature case, it was found that $200^{\circ}C$ was the optimal temperature, because thermal degradation of PPD occurred above $250^{\circ}C$. In addition, we confirmed the structure of PPD and the bonding characteristics of the amine group via FT-IR and H-NMR analysis.

Synthesis of Alginate-derived Polymeric Surfactants (알지네이트계 고분자 계면활성제의 합성)

  • 강현아
    • KSBB Journal
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    • v.15 no.4
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    • pp.375-379
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    • 2000
  • Alginate derivatives possessing various lengths of alkyl amine (C8, C12, C16) chain were prepared by oxidation followed by reductive amination of alginate and the products were characterized by spectral analysis. The surface tension critical micelle concentration (c. m. c) and solubility of a hydrophobic compound azobenzene were examined. Series of synthesized alginate-derived polymeric surfactants(APSs) reduced the surface tension. The dissolving capacity of APSs toward azobenzene was about half that of SDS. In order to investigate the capacity of metal adsorption Co and Pb were selected as a representative metal. The overall removal efficiency of APSs were high compared with that of alginate at pH 3.5 and 7 respectively. Major mechanism of the heavy metal removal is the complex of metal with carboxyl group.

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Purification and Biochemical Characterization of Recombinant Alanine Dehydrogenase fvom Thermus caldophilux GK24

  • Bae, Jung-Don;Cho, Youn-Jeung;Kim, Doo-Il;Lee, Dae-Sil;Shin, Hyun-Jae
    • Journal of Microbiology and Biotechnology
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    • v.13 no.4
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    • pp.628-631
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    • 2003
  • The recombinant alanine dehydrogenase (ADH) from E. coli containing Thermus caldophilus ADH was purified to homogeneity from a cell-free extract. The enzyme was purified 38-fold with a yield of 68% from the starting cell-free extract. The purified enzyme gave a single band in polyacrylamide gel electrophoresis, and its molecular weight was estimated to be 45 kDa. The pH optimum was 8.0 for reductive amination of pyruvate and 12.0 for oxidative deamination of L-alanine. The enzyme was stable up to $70^{\circ}C$. The activity of the enzyme was inhibited by 1 mM $Zn^{2+}$, 20% hexane, and 20% $CHCl_3$. However, 10 mM $Mg^{2+}$ and 40% propanol had no effect on the enzyme activity. The Michaelis constants ($K_m$) for the substrates were $50\;\mu\textrm{M}$ for NADH, 0.2 mM for pyruvate, 39.4 mM for $NH_4+$, 2.6 mM for L-alanine, and 1.8 mM for $NAD^+$.

Studies on the Synthesis of Aminated PP-g-GMA Fibrous ion Exchanger by E-beam Pre-irradiation and Their Properties of Selective Adsorption for $NO_{3} ^{-}$ (E-beam 전조사에 의한 $NO_{3} ^{-}$ 선택 흡착용 아민화 PP-g-GMA 섬유 이온교환체의 합성과 그 특성에 관한 연구)

  • 황택성;이선아;이면주
    • Polymer(Korea)
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    • v.26 no.2
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    • pp.153-159
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    • 2002
  • In order to remove $NO_3;^-$ ion from ground-water, fibrous ion -exchangers, APP-g-GMA, were synthesized by GMA grafting onto PP trunk polymer with E-beam accelerator for pre-irradiation. Their degrees of grafting and amination yield increased up to $60^{\circ}C$ and showed maximum values as 133%, 88%, respectively. And their swelling ratio and ion exchange capacity at the maximum values are 86%, 2.5 meq/g, respectively which was higher than commercial ion-exchangers such as IMAC HP555 and Amberlite IRA 400. Optimum adsorption condition of $NO_3;^-$ ion was measured at pH 5~6 and -Cl form of APP-g-GMA containing trimethylammonium group showed the highest adsorption capacity.