• Title/Summary/Keyword: Substitution reaction

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Modification of Starch using Dextransucrase and Characterization of the Modified Starch. (덱스트란수크라제를 이용한 전분의 변형 및 특성 조사)

  • ;;;;;John E. Robyt
    • Microbiology and Biotechnology Letters
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    • v.26 no.2
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    • pp.143-150
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    • 1998
  • Many enzymes catalyze a primary reaction and/or secondary reaction. Dextransucrase usually synthesize dextran from sucrose as a primary reaction. The secondary reaction of dextransucrase is the transfer of glucose from sucrose to carbohydrate accepters. We have reacted dextransucrase from Leuconostoc mesenteroides B-742CB with sucrose and starches; granule or gelatinized starches, and Small or Potato starches. The yield of modified starch was ranged from 46% to 72%(s.d.<${pm}$5%) of theoretical depends on various reaction conditions. Modified products were more resistant against the hydrolysis of ${alpha}$-amylase, isoamylase, pullulanase and endo-dextranase than those of native starch. Based on the reactions from enzyme hydrolysis and methylation followed by acid hydrolysis modification of granule starch was more efficient than the modification of gelatinized starch. After modification of granule starch with dextransucrase, there produced a soluble modified starch. After modification the starch granules were fractionated to small size. The positions of glucose substitution of the modified products were determined by methylation followed by acid hydrolysis and analyzed by TLC. The products were modified by the addition of glucose to the position of C3, C4 and C6 free hydroxyl group of glucose residues in the starch.

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Synthesis of Characterization of Poly(alkylene oxide) Copolyols by Catioinc Ring Opening Polymerization and Their Azide Functionalized Copolyols (양이온 개환중합에 의한 폴리알킬렌 옥사이드 코폴리올의 합성과 아지드화 코폴리올의 특성 연구)

  • Lee, Jae-Myung;Seol, Yang-Ho;Kwon, Jung-Ok;Jin, Yong-Hyun;Noh, Si-Tae
    • Applied Chemistry for Engineering
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    • v.31 no.3
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    • pp.267-276
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    • 2020
  • Poly(epichlorohydrin) copolyol series (PECH copolyols) were synthesized via cationic ring-opening copolymerization (ROCP) of oxirane-based monomers and effects of reaction temperature, solvent type, and initiator were studied. As a comonomer, two types of alkylene oxides were used, and polymerization conditions were conducted both with diethylene glycol (DEG) as an initiator in methylene chloride (MC) solvent and tripropylene glycol (TPG) in toluene solvent. In order to induce the active monomer (AM) mechanism in the ring-opening copolymerization reaction, the monomer was injected by an incremental monomer addition (IMA) method using a syringe pump, and the polymerization was performed at -5 ℃. PECH copolyol, a synthesized ephichorohydrin (ECH)-based copolyol, was converted to glycidyl azide-based energy-containing copolyol (GAP copolyol) by azadizing the ECH unit through a substitution reaction. It was confirmed that the synthesized azide copolyol had little effects on changes of the solvent and the initiator. Also, the molecular weight increased 500 after the azide reaction, thereby the GAP copolyol was polymerized as designed. As the content of the comonomer increased, both the Tg and viscosity tended to decrease due to the influence of the alkyl chain length. It is possible to fundamentally prevent CH3N3 amount produced in the azide reaction process, and it is expected that a large-scale process could be achievable.

An Application of Optoacoustic Technique for the CO Oxidation Reaction Catalyzed by $Gd_{1-x}Sr_xCoO_{3-y}$ (광음향분광법을 이용한 CO 산화반응에서의 $Gd_{1-x}Sr_xCoO_{3-y}$ 촉매효과 연구)

  • Kang Hee-Seok;Oum Ka-Won;Hwang Jin-Soo;Yo Chul-Hyun;Choi Joong-Gill
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.55-61
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    • 1993
  • An application of the optoacoustic detection method to investigate the catalytic effect of a perovskite, $Gd_{1-x}Sr_xCoO_{3-y}$ (x = 0.00, 0.25, 0.50, 0.75) system, in the oxidation reaction of CO is described. The optoacoustic signals Of $CO_2$ produced from the oxidation reaction were measured for differing x values in $Gd_{1-x}Sr_xCoO_{3-y}$. By monitoring optoacoustic signals with respect to the time, the concentration ratios of CO and $O_2$, and the temperature, the kinetic information on the catalytic properties of the perovskite for CO oxidation reaction can be obtained. The effect of Sr substitution in $Gd_{1-x}Sr_xCoO_{3-y}$ has been found to show the maximum catalytic effect at x = 0.25 and the substantial increase in catalytic activity at temperatures above 200$^{\circ}C$. It demonstrates that the optoacoustic detection method allows the investigation of the integrated catalytic effect not only for the oxidation reaction of CO, but also for many reactions, in general, by continuously and directly detecting the species associated with the reactions.

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Occurrence and Chemical Composition of Carbonate Mineral from Wallrock Alteration Zone of Janggun Pb-Zn Deposit (장군 연-아연 광상의 모암변질대내 탄산염 광물의 산상 및 화학조성)

  • Bong Chul Yoo
    • Korean Journal of Mineralogy and Petrology
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    • v.36 no.3
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    • pp.167-183
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    • 2023
  • The Janggun Pb-Zn deposit consists of Mn orebody, Pb-Zn orebody and Fe orebody. The Mn orebody composed of manganese carbonate orebody and manganese oxide orebody on the basis of their mineralogy and genesis. The geology of this deposit consists of Precambrian Weonnam formation, Yulri group, Paleozoic Jangsan formation, Dueumri formation, Janggum limestone formation, Dongsugok formation, Jaesan formation and Mesozoic Dongwhachi formation and Chungyang granite. This manganese carbonate orebody is hydrothermal replacement orebody formed by reaction of lead and zinc-bearing hydrothermal fluid and Paleozoic Janggum limestone formation. The wallrock alteration that is remarkably recognized with Pb-Zn mineralization at this hydrothermal replacement orebody consists of mainly rhodochrositization with minor of dolomitization, pyritization, sericitization and chloritization. Carbonates formed during wallrock alteration on the basis of paragenetic sequence are as followed : Ca-dolomite (Co type, wallrock) → ankerite and Ferroan ankerite (C1 type, early stage) → ankerite (C2 type) → sideroplesite (C3 type) → sideroplesite and pistomesite (C4 type, late stage). This means that Fe and Mn elements were enriched during evolution of hydrothermal fluid. Therefore, The substitution of elements during wallrock alteration beween dolomitic marble (Mg, Ca) and lead and zinc-bearing hydrothermal fluid (Fe, Mn) with paragenetic sequence is as followed : 1)Fe ↔ Mn and Mn ↔ Mg, Ca, Fe elements substitution (ankerite and Ferroan ankerite, C1 type, early stage), 2)Fe ↔ Mn, Mn ↔ Mg, Ca and Mg ↔ Ca elements substitution (ankerite, C2 type), 3)Fe ↔ Mn, Fe ↔ Ca and Mn ↔ Mg, Ca elements substitution (sideroplesite, C3 type), and 4)Fe ↔ Mg, Fe ↔ Mn and Mn ↔ Mg, Ca elements substitution (sideroplesite and pistomesite, C4 type, late stage)

O-Methylation of Flavonoids Using DnrK Based on Molecular Docking

  • Kim, Na-Yeon;Kim, Jeong-Ho;Lee, Youn-Ho;Lee, Eun-Jung;Kim, Jin-Young;Lim, Yoong-Ho;Chong, You-Hoon;Ahn, Joong-Hoon
    • Journal of Microbiology and Biotechnology
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    • v.17 no.12
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    • pp.1991-1995
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    • 2007
  • O-Methylation is a common substitution reaction found in microbes as well as in mammalians. Some of the O-methyltransferases (OMTs) have broad substrate specificity and could be used to methylate various compounds. DnrK from Streptomyces peucetius encodes an anthracycline 4-O-methyltransferase, which uses carminomycin as a substrate, and its crystal structure has been determined. Molecular docking experiments with DnrK using various flavonoids were successfully conducted, and some of the flavonoids such as apigenin and genistein were predicted to serve as substrates. Based on these results, O-methylations of various flavonoids with the DnrK were successfully carried out. The methylation position was determined to be at the hydroxyl group of C7. Important amino acid residues for the enzymatic reaction of DnrK with apigenin could be identified using site-directed mutagenesis. Molecular docking could be useful to predict the substrate specificity ranges of other OMTs.

Crystallographic Site Dependent $^{16}\textrm{O}^{18}\textrm{O}$ Exchange Reaction in Bi-2212 High $\textrm{T}_{\textrm{c}}$ Oxide Superconductors (Bi-2212산화물 고온초전도체의 결정학적 위치에 의존하는 $^{16}\textrm{O}^{18}\textrm{O}$ 교환반응)

  • Kim, Byeong-Guk
    • Korean Journal of Materials Research
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    • v.7 no.2
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    • pp.157-161
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    • 1997
  • The crystallographic site dependent substitution of $^{18}O$ for $^{16}O$ in $Bi_{2}Sr_{2}Ca_{0.8}Y_{0.2}Cu_{2}^{16}O_{8+\delta}$ has heen investigated. In the Kaman spectra of $Bi_{2}Sr_{2}Ca_{0.8}Y_{0.2}Cu_{2}^{16}O_{8+\delta}$ three prominent Raman bands are observed at 297. 464, and $623cm^{-1}$. As the $^{16}O$ arc replaced hy $^{18}O$, all the three bands shift to lower wavewnumbers. The rate of this isotopic shift is similar for the hands at 397 and $464cm^{-1}$. whereas it is quite slower for the hand at $623cm^{-1}$ '['his implys that the $^{16}O-^{18}O$ exchange reaction is crystallographic sites dependent. .Assuming a tetragonal symmetry, we assign the bands at 623. 464, and $297cm^{-1}$ to the vibrations of $O_{pl}(A_{g}),\;O_{ap}\;and\;O_{Bi}$ respectively.

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Mechanism of the Hydrolysis of Phenyl N-(p-chlorobenzoyl)Chloroformimidate Derivatives in Acid Media (산성용액 중에서 Phenyl N-(p-chlorobenzoyl)chloroformimidate 유도체의 가수분해 반응 메카니즘)

  • Nack-Do Sung;Young-Gu Cheun;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.4
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    • pp.352-358
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    • 1987
  • Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

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Leaving-Group Substituent Controls Reactivity and Reaction Mechanism in Aminolysis of Phenyl Y-Substituted-Phenyl Carbonates

  • Kang, Ji-Sun;Song, Yoon-Ju;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2023-2028
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    • 2013
  • A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

Alteration of Recognition Sequence by Restriction Endonuclease -Effect of pH and Hydrophobicity on BamHI- (제한효소의 인식자리 변화 -BamHI 특이성에 미치는 산도와 소수성의 영향-)

  • 이강민
    • KSBB Journal
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    • v.11 no.2
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    • pp.193-200
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    • 1996
  • In molecular biology, type-II restriction endonuclease, which specifically recognize and cleave DNA at a limited number of sites, have been exploited as a means of characterizing DNA fragments, DNA mapping for genetic engineering. Type-II restriction endonucleases have been found to modulate their substrate specificity under modified conditions such as extreme pH, ionic strength, high enzyme concentration, substitution of metallic cofactors or addition of organic solvents. This study was initiated to investigate the modification of recognition specificity of BamHI according to the different pH and organic solvent under the given buffer condition. The specificity of BamHI is highly depends on the presence of hydrophobicity (LogP: partition coefficient) and pH of reaction solution. The specificity of BamHI is changed in range of LogP -1.03∼-1.35(at pH 7.5), -1.03∼-2.5 (at pH 8.0), -0.75∼-0.25(at pH 8.5), 0.32∼-2.5(at pH 8.9), respectively. Alteration of specificity appears in lower concentration of organic solvent when the reaction occurs in more alkali pH. For example, in DMSO solution, alteration of specificity appears in 20% concentration at pH 7.5 but in 4% concentration at pH 8.9.

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Kinetic Properties of Wild-type and C117D Mutant UDP-N-Acetylglucosamine Enolpyruvyl Transferase (MurA) from Haemophilus influenzae

  • Han, Seong-Gu;Jin, Bong-Suk;Lee, Won-Kyu;Yu, Yeon-Gyu
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2549-2552
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    • 2011
  • In this study, the kinetic properties of wild-type and C117D mutant H. influenzae MurA (Hi MurA), which catalyzes the first reaction in the biosynthetic pathway of the cell wall, were characterized. Purified recombinant Hi MurA was active at pH values ranging from pH 5.5 to pH 10, and its $K_m$ (UNAG), $K_m$ (PEP), and $k_{cat}$ values were measured to be 31 ${\mu}M$, 24 ${\mu}M$, and 210 $min^{-1}$, respectively. Hi MurA activity was effectively inhibited by fosfomycin with an $IC_{50}$ value of 60 ${\mu}M$. Hi MurA contains a cysteine residue (C117) at the loop region near the PEP binding, whereas MurA from fosfomycin resistant Mycobaterium tuberculosis or Chlamydia trachomatis contain an aspartate residue instead of the cysteine at the corresponding site. Aspartate substitution of Cys117 in Hi MurA shifted its optimum pH from 7.8 to 6.0. In addition, the $K_m$ values for UNAG and PEP were increased to 160 ${\mu}M$ and 150 ${\mu}M$, respectively, and the $k_{cat}$ value was significantly reduced to 41 $min^{-1}$. Furthermore, the C117D mutant form of Hi MurA was not inhibited by 1 mM fosfomycin. These results indicate that the Cys117 of Hi MurA is the binding site of fosfomycin and plays an important role in the fast turnover of the catalytic reaction.