• Title/Summary/Keyword: Acid-Base Reaction

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Studies on Oxidation Modification of Polyethylene Wax (폴리에틸렌 왁스의 산화변성에 관한 연구)

  • Choi, Byung-Ryul;Park, Yang-Jun
    • Applied Chemistry for Engineering
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    • v.8 no.5
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    • pp.837-843
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    • 1997
  • In oxidized polyethylene wax preparation, the effects of main parameters such as the property of used wax, oxidation time, oxidation temperature, air feed rates on the change of acid-numbers were investigated. The change in polymer property was also investigated. The results showed under given reaction conditions, the acid numbers with oxidation temperature increased upto $160^{\circ}C$, but at higher temperature, it decreased. The base resin which was lower molecular weight had higher acid number. The result showed molecular weight as a experimental parameter was more effective than density in oxidation experiment. In milder condition, free radical initiator was used for catalyst to get higher acid-numbers, which was successful in comparison to the non-catalyst system. Also the catalyst with longer half-life was efficient, in order of DCPO, HOPO and BPO.

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Synthesis and Characterization of New Polyaza Macrocyclic Nickel(Ⅱ) and Copper(Ⅱ) Complexes Two Nitrile or Imidate Ester Pendant Arms: Metal-Mediated Hydrolysis and Alcoholysis of the Nitrile Groups

  • Kang, Shin-Geol;Song, Jeong-Hoon;Jeong, Jong-Hwa
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.824-829
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    • 2002
  • New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.

Solvolysis of 2-Thiophenesulfonyl Chloride (2-염화티오펜술포닐의 가용매 분해반응)

  • Jin-Chel Choi;Jieun Oh;Dae Ho Kang;In Sun Koo;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.695-701
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    • 1993
  • Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

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Analysis of gibberellic acid from fruits using HPLC/UV-vis (HPLC/UV-vis을 이용한 과일류 중의 지베렐린 산 분석)

  • Ma, Kyung Na;Cho, Hyun-Woo;Myung, Seung-Woon
    • Analytical Science and Technology
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    • v.26 no.1
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    • pp.19-26
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    • 2013
  • Gibberllic acid ($GA_3$) is one of gibberellins (GAs) that are a class of plant growth hormones that exert profound and diverse effects on plant growth and development. $GA_3$ is essentially non-UV absorbing and is difficult to assay by UV-detector. For effective extraction of gibberellic acid from fruits by using liquid-liquid extraction, optimized pH and extraction solvent were established. The selective and sensitive derivative of $GA_3$ for HPLC/UV-vis was derivatized using phenacyl bromide, and the experimental factors, including reaction time, reaction temperature and amount of derivatizing reagent and base were investigated for the effective synthesis. The derivatized $GA_3$ with phenacyl bromide was effectively analyzed by HPLC/UV-vis. The structure of derivatized $GA_3$ was confirmed by HPLC/ESI-MS. For apple, LOD and LOQ were 0.008 mg/kg and 0.027 mg/kg, respectively. For pear, LOD and LOQ were 0.003 mg/kg, 0.012 mg/kg, respectively. The established method can be applied to more effective analysis of $GA_3$ from plant and food.

Procaryotic Expression of Porcine Acid-Labile Subunit of the 150-kDa Insulin-like Growth Factor Complex (미생물에서 돼지 150-kDa Insulin-Like Growth Factor Complex의 Acid-Labile Subunit 발현)

  • Lee, C. Young;Kang, Hye-Kyeong;Moon, Yang-Soo
    • Journal of Animal Science and Technology
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    • v.50 no.2
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    • pp.177-184
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    • 2008
  • Acid-labile subunit(ALS) is a 85-kDa glycosylated plasma protein which forms a 150-kDa ternary complex with 7.5-kDa insulin-like growth factor(IGF) and 40~45-kDa IGF-binding protein-3. In a previous study, the present authors prepared a porcine ALS(pALS) expression construct by inserting a pALS coding sequence into a plasmid vector following synthesis of the sequence by reverse transcription-polymerase chain reaction(RT-PCR). The expression construct, however, was subsequently found to have a mis-sense mutation at two bases of the pALS coding sequence which is presumed to have occurred through a PCR error. In the present study, the correct coding sequence was synthesized by the site-directed mutagenesis and inserted into the pET-28a(+) plasmid expression vector containing the His-tag sequence flanking the last codon of the insert DNA. After induction of the expression construct in E. coli BL21(DE3) cells, the resulting presumptive recombinant peptide was purified by the Ni-affinity chromatography. Upon SDS- PAGE, the affinity-purified peptide was resolved as a single band at a 66-kDa position which is consistent with the expected molecular mass of the presumptive recombinant pALS. Collectively, results indicate that a recombinant pALS peptide was successfully expressed and purified in the present study.

The analysis of products from base-catalyzed depolymerization of kraft lignin (크라프트 리그닌의 염기 촉매 분해(BCD)에 의한 부산물의 조성 분석)

  • Kim, Seok Ju;Kim, Yong Sik
    • Journal of the Korean Wood Science and Technology
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    • v.41 no.6
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    • pp.583-593
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    • 2013
  • The based-catalyzed depolymerization (BCD) of kraft lignin isolated from black liquor which the chemical pulping of a mixture of various Southeast Asia hardwood chips was carried out in a batch reactor in the presence of different NaOH concentrations with supercritical methanol. The S:G ratio of the kraft lignin determined by pyrolysis-GC/MS analysis turned out roughly 1.4:1 and main products were vanillic acid, syringol and 3-methoxy catechol. The diethyl ether extracts as phenolic monomers from BCD reaction were produced similar yield among different NaOH concentrations. The 21 compounds were identified by GC/MS analysis in all experiments and major products were catechol, 3-methoxycatechol, 4-methylcatechol, syringol and isovanillic acid. However, it had been shown to be different monomer contents depending on the dosage of NaOH. Catechol, 4-methylcatechol and 3-methoxycatechol were shown to be the dominant monomer from BCD reaction using 7.5 and 3.25% of NaOH concentration whereas syringol, isovanillic acid, 3-methoxycatechol and 4-methylcatechol were determined to be the most typical products under the condition of 1.63% NaOH.

The Manufacturing Mechanism of Nano-some and Method of Capsulation of Kojic Acid and Kojic Dipalmitate with Hydrogenated Lecithin and Co-emulsifiers (Hydrogenated Lecithin 과 Co-emulsifier를 사용한 Nano-some의 제조 메커니즘과 Kojic Acid 및 Kojic Dipalmitate의 캡슐화 방법)

  • Kim, In-Young;Jae, Koo-Hwan;Lee, Joo-Dong
    • Journal of the Korean Applied Science and Technology
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    • v.17 no.4
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    • pp.248-256
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    • 2000
  • We investigated the property of formation of mono-vesicle(designated nano-some) with using of the combined co-emulsifiers and phospholipid. Nano-some was prepared with hydrogenated lecithin(HL) and diethanolamine cetyl phosphate(DEA-CP) by swelling reaction. Kojic acid and kojic dipalmitate could be made stabilization by nano-some system using microfluidizer(MF). Nano-some has a good affinity to skin by means of this system. The composition was compounded by 2% of hydrogenated lecithin (phosphatidyl choline contained with 75%, 0.5% of DEA-CP and 0.5% of diglyceryl dioleate (DGDO). To make nano-some, several conditions of MF have to be considered as follows. The optimum pH was 6.0. The pressure was 10,000psi and passage temperature was at $306^{\circ}C$. The nano-some base was passed to homogenize continually 3 times through MF. The Particle size distributions of the vesicles were with in $57{\sim}75.7nm$(mean 66nm) by measuring the Zetasizer-3000. Zeta potential of vesicles with 3 times passage through MF was -24.8mV. Formations for nano-some vesicle certificated photograph by scanning electric magnification (SEM). Stability of nano-some was very good for 6months. The turbidity was very good transparency compared nano-some with liposome. It was formed the mono vesicle in the opposite direction to be formed the multi-lamellar vesicle of liposome.

Cloning of An Intron of the Gene Coding for Porcine Acid-Labile Subunit(pALS) of the 150-kDa Insulin-like Growth Factor Complex and the 3' ntranslated Region of pALS Complementary DNA and Confirmation of pALS Gene Expression in Multiple Tissues (돼지 150-kDa Insulin-like Growth Factor Complex의 Acid-labile Subunit(ALS) 유전자의 Intron 및 ALS Complementary DNA의 3' 비해독 부위 Cloning과 생체조직에서의 ALS 유전자 발현 확인)

  • Jin, E.J.;Kim, I.A.;Lee, C.Y.
    • Journal of Animal Science and Technology
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    • v.46 no.4
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    • pp.555-562
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    • 2004
  • 본 연구는 목저은 다음과 같다: 1) 돼지에서 150-kDa temary insulin-like growth faetor(IGF)complex의 한 구성 요소인 acid-labile subunit(ALS) 유전자 intron의 존재 확인. cloning 및 돼지 ALS(porcine ALS; pALS) complementary DNA(cDNA)의 3' 비해독(untranslated) 부위(3' UT) 증폭. cloning, 2) intron-spanning primer pair를 이용한 reverse transcription-polymerase chain reaction(RT-PCR) 방법에 의한 돼지 조직에서의 ALS 유전자 발현 분포 확인 및 3) 돼지 hepatocyte에서의 ALS 유전자 발현 여부 확인. 돼지 genomic DNA를 template로 하여 PCR 방법으로 예상된는 intron 부위를 증폭하고 plasmid vector에 삽입하여 염기서열을 결정한 결과 타 종의 ALS 유전자에서와 같은 위치에 1,371-base pair(bp)의 pALS intron이 존재함을 확인하였다. 역시 본 연구에서 간에서 추출한 RNA를 주형으로 시작하여 3' rapid amplification of cDNA end(3' RACE) 방법으로 147-bp의 3'UT를 합성하고 그 염기성열을 결정하였다. RT-PCR 결과 간은 물론 조사된 모든 돼지의 내장기관(신장, 폐, 비장)과 자성 생식기관(난소, 난관, 자궁) 및 골격근육에서 ALS 유전자가 발현됨이 밝혀졌다. 또한 돼지 간 조직에 대한 in-situ hybridization 결과 hepatocyte에서 ALS 유전자가 발현됨이 확인되었다. 이상의 결과는 ALS가 혈중 IGF의 저정/조절체로서의 주기능 외에 모세혈관 밖에서도 미지의 기능이 있을 기능성을 시사한다.

Molecular Cloning of a Gene Encoding $\alpha$-L-Arabinofuranosidase from Hyperthermophile Thermotoga maritima and Characterization of Its Biochemical Properties

  • Keum, In-Kyung;Lee, Eun-Joo;Kim, Tae-Jip;Kim, Chung-Ho;Han, Nam-Soo
    • Proceedings of the Korean Society for Applied Microbiology Conference
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    • 2004.06a
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    • pp.273-277
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    • 2004
  • $\alpha$-L-Arabinofuranosidase ($\alpha$-L-AFase, EC 3.2.1.55) was isolated from hyperthermophilic microorganism, Thermotoga maritima. The open reading frame (ORF) of $\alpha$-L-AFase gene is 1,455 bp long and encodes 484 amino acid residues with a molecular weight of 55,265 Da. The ORF of $\alpha$-L-AFase gene was introduced into the E. coli expression vector, $_p/RSET-B, and overexpressed in E. coli BL21. The purified recombinant $\alpha$-L-AFase showed the highest activity at 10$0^{\circ}C$ and pH 5.5. The purified enzyme appeared to have no metal cofactor requirement. The Km and specific activity values of the recombinant enzyme were 0.99 mM and 1,200 U/mg on p-nitrophenyl-$\alpha$-L-arabinofuranoside. It released only L-arabinose from sugar beet arabinan, sugar beet debranched arabinan and oat spelts arabinoxylan but had no activity onarabinogalactan and gum arabic. This result suggests that L-arabinose could be produced from natural polysaccharides using this enzyme. Mutant enzymes which Glu26, Glu172 and Glu281 residues were replaced to alanine, aspartic acid or glutamine caused Kcat to decrease by a factor of between 10$^3$ and 10$^4$. Glu172 and Glu281 residues of $\alpha$-L-AFase are seemed to be the acid/base and nucleophile in catalytic reaction, respectively, and Glu26 is supposed to playa key role in substrate binding.ng.

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Effect of ZnCl2 Co-catalyst in the Synthesis of Dimethyl Carbonate from Ethylene Carbonate and Methanol by Using Base Catalysts (염기 촉매를 이용한 디메틸카보네이트 합성에서 ZnCl2 조촉매의 영향)

  • Kim, Dong-Woo;Park, Moon-Seok;Kim, Moon-Il;Park, Dae-Won
    • Korean Chemical Engineering Research
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    • v.50 no.2
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    • pp.217-222
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    • 2012
  • The synthesis of dimethyl carbonate(DMC) is a promising reaction for the use of naturally abundant carbon dioxide. DMC has gained considerable interest owing to its versatile chemical reactivity and unique properties such as high oxygen content, low toxicity, and excellent biodegradability. In this study, the synthesis of DMC through the transesterification of ethylene carbonate(EC) with methanol was investigated by using ionic liquid and metal oxide catalysts. The screening test of different catalysts revealed that choline hydroxide ([Choline][OH]) and 1-n-butyl-3-methyl imidazolium hydroxide([BMIm][OH]) had better catalytic performance than metal salts catalysts such as MgO, ZnO and CaO. The effects of reaction parameters such as reaction temperature, MeOH/EC mole ratio, and carbon dioxide pressure on the reactivity of [Choline][OH] catalyst were discussed. High temperature and high MeOH/EC mole ratio were favorable for high conversion of EC. However, the yield of DMC showed a maximum when carbon dioxide pressure was 1.34 MPa, and then it decreased for higher carbon dioxide pressure. Zinc chloride($ZnCl_2$) was used as co-catalyst with the ionic liquid catalyst. The mixed catalyst showed a synergy effect on the EC conversion and DMC yield probably due to the acid-base properties of the catalysts.