• Title/Summary/Keyword: Ring opening

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Accelerating Effects of Ultrasonic Irradiation on Reaction Rates for the Asymmetric Ring Opening Reaction of Epoxides (초음파 조사에 의한 에폭사이드 비대칭 고리열림 반응의 속도 증진 효과)

  • Lee, Yae Won;Park, Geun Woo;Kim, Geon Joong
    • Applied Chemistry for Engineering
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    • v.30 no.3
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    • pp.365-370
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    • 2019
  • In this study, effects of the ultrasonic irradiation during the reaction process were investigated for the enantioselective kinetic resolution (EKR) reaction of racemic epoxides in the presence of chiral cobalt salen catalysts, as compared to that of using the conventional mechanical stirring. In order to compare catalytic activities, the chiral cobalt salen complexes having $AlCl_3-$, $BF_3-$ and nitrobenzenesulfonic acid (NBSA) were synthesized and used as catalysts, and then three kinds of the racemic epoxides such as ephichlorohydrine (ECH), epoxy phenoxypropane (EPP) and propylene oxide (PO) were used as reactants. In addition, EKR reactions have been performed using the water and methanol as nucleophiles, respectively. The unique contribution of ultrasonic irradiation as a powerful mixing medium was evaluated in this study to improve the kinetics in comparison to the conventional mechanical agitation during EKR reactions. The reaction time to obtain the highest 99 ee% became shorten more than that of above 60%, when the ultrasonic irradiation was used. This result may be interpreted by the cavitation effect of ultrasound in the solution, generating a powerful shear force for the very violent mixing.

From L-Ascorbic Acid to Protease Inhibitors: Practical Synthesis of Key Chiral Epoxide Intermediates for Aspartyl Proteases

  • Chang, Sun-Ki;So, Soon-Mog;Lee, Sang-Min;Kim, Min-Kyu;Seol, Kyoung-Mee;Kim, Sung-Min;Kang, Jae-Sung;Choo, Dong-Joon;Lee, Jae-Yeol;Kim, B.-Moon
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2213-2218
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    • 2012
  • Efficient synthetic routes were developed to prepare a sizable amount (4-15 grams) of the chiral epoxides 4-6 as versatile intermediates for the synthesis of aspartyl protease inhibitors of therapeutic interest such as HIV protease and ${\beta}$-secretase. Oxidative cleavage of the C(2)-C(3) double bond of L-ascorbic acid followed by functional group manipulation led to the preparation of the epoxide 10, which was opened with an azide to yield a common aziridine intermediate 12. Through opening of the aziridine ring of 12 with either a carbon or a sulfur nucleophile, chiral epoxide precursors 4-6 could be prepared for various HIV protease inhibitors. Except for the final low melting epoxides 5 and 6, all intermediates were obtained as crystalline solids, thus the synthetic pathway can be easily applied to a large-scale synthesis of the chiral epoxides.

Attachment of Silver Nanoparticles to the Wool Fiber Using Glycidyltrimethylammonium Chloride(GTAC) (Glycidyltrimethylammonium Chloride(GTAC)를 이용한 양모 섬유 표면의 Silver Nanoparticle 부착)

  • Lee, Seungyoung;Sul, In Hwan;Lee, Jaewoong
    • Textile Coloration and Finishing
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    • v.28 no.2
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    • pp.70-76
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    • 2016
  • Silver nanoparticles(AgNPs) were attached to wool fibers using glycidyltrimethylammonium chloride(GTAC), which is a type of quaternary ammonium salt. GTAC, which contains an epoxy functional group that, under high temperatures, generates a ring-opening reaction with wool fibers, which contain the amine group. Then, the AgNPs are attached to the surface of the GTAC-treated wool fibers by treatment with a silver colloidal solution. The process involves the following procedures: (1) The wool fibers are immersed in the GTAC solution, followed by pre-drying at $80^{\circ}C$ and curing at $180^{\circ}C$ to induce an alteration in the chemical structure; and (2) The wool fibers treated with GTAC are immersed in the silver colloid at $40^{\circ}C$ for 120 min to chemically induce a strong attachment of the AgNPs to the wool fibers. Scanning electron microscopy was used to analyze the influence of the concentrations of GTAC and the silver colloid, as well as the influence of the applied temperature of the silver colloid on the wool fibers, and the influence of the morphological changes in the wool fiber surfaces. As a result, the enhanced concentrations of GTAC and the silver colloid together with an elevated applied temperature of silver colloid have a tendency to increase in Ag atomic%.

Composition of Cotton Textile Dyeing Process Wastewater and its Treatment Characteristics by Ionized Gas (면섬유염색폐수의 공정별 폐수성상과 이온화가스에 의한 처리특성)

  • Lim, Gyeong-Eun;Chung, Paul-gene;Kwon, Ji-Young;Lee, Eun-Ju
    • Journal of Korean Society on Water Environment
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    • v.23 no.3
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    • pp.303-308
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    • 2007
  • Three types dyeing wastewater (dark, medium, light color) discharged from cotton textile dyeing with reactive dye was collected at each step of process. Each process dying wastewater was analyzed and treated by ionized gas. The analysis focused on $COD_{Cr}$, SS and color. Bleaching & scouring process wastewater has the highest $COD_{Cr}$ value in the three type dyeing wastewater. SS shows the highest value at dyeing process wastewater in dark and medium color but light color has at finishing process wastewater. The result of process wastewater treatment by ionized gas was that the ionized gas was effective in $COD_{Cr}$ removing of bleaching & scouring process and finishing process wastewater but was not good at dyeing process wastewater. From that result it is estimated that the ionized gas could not work in opening the aromatic ring and react only in aliphatic component of the molecule. Because the surfactants contained in bleaching & scouring process and finishing process wastewater have only one aromatic ring in its molecular structure, in contrast with the reactive dye compounds consist of aromatic rings great part of its molecular structure. The color almost removed in 1.5 hrs reaction time but $COD_{Cr}$ removal effiency was only 30.7% through 3hrs in 1500 mL of total dyeing wastewater treated by 10 L/min ionized gas.

Molecular Cloning and Enzymatic Characterization of Cyclomaltodextrinase from Hyperthermophilic Archaeon Thermococcus sp. CL1

  • Lee, Jae-Eun;Kim, In-Hwan;Jung, Jong-Hyun;Seo, Dong-Ho;Kang, Sung-Gyun;Holden, James F.;Cha, Jaeho;Park, Cheon-Seok
    • Journal of Microbiology and Biotechnology
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    • v.23 no.8
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    • pp.1060-1069
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    • 2013
  • Genome organization near cyclomaltodextrinases (CDases) was analyzed and compared for four different hyperthermophilic archaea: Thermococcus, Pyrococcus, Staphylothermus, and Thermofilum. A gene (CL1_0884) encoding a putative CDase from Thermococcus sp. CL1 (tccd) was cloned and expressed in Escherichia coli. TcCD was confirmed to be highly thermostable, with optimal activity at $85^{\circ}C$. The melting temperature of TcCD was determined to be $93^{\circ}C$ by both differential scanning calorimetry and differential scanning fluorimetry. A size-exclusion chromatography experiment showed that TcCD exists as a monomer. TcCD preferentially hydrolyzed ${\alpha}$-cyclodextrin (${\alpha}$-CD), and at the initial stage catalyzed a ring-opening reaction by cleaving one ${\alpha}$-1,4-glycosidic linkage of the CD ring to produce the corresponding single maltooligosaccharide. Furthermore, TcCD could hydrolyze branched CDs (G1-${\alpha}$-CD, G1-${\beta}$-CD, and G2-${\beta}$-CD) to yield significant amounts (45%, 40%, and 46%) of isomaltooligosaccharides (panose and $6^2$-${\alpha}$-maltosylmaltose) in addition to glucose and maltose. This enzyme is one of the most thermostable maltogenic amylases reported, and might be of potential value in the production of isomaltooligosaccharides in the food industry.

Development of Degassing Valves for Food Packaging using Ring Type Rubber Disk (링타입 고무막을 이용한 식품 포장용 가스배출 밸브(Degassing Valve) 개발)

  • Yu, Ha Kyoung;Lee, Kyungo Ho;Oh, Jae Young
    • KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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    • v.20 no.2
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    • pp.35-39
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    • 2014
  • One-way degassing valves are designed to allow pressure to be released from an air-tight package while preventing air from getting back into the package. Air, especially the oxygen ($O_2$) portion of air, can have negative effects on the package contents and its freshness. The most common application of the one-way degassing valve is for fresh roasted coffee. Demands of one-way degassing valves have been increasing with the high growth of global coffee market. In this study, we have developed one-way degassing valves for coffee and food packaging using ring type rubber disk, named SP valve. Its quality and performance was verified with test results to be equal with that of global top maker's product, Goglio valve. SP valves showed 820~1200 Pa of opening pressure, 10~50 Pa of closing pressure, 1.2~1.6 L/ min of flow rate. And, the SP valve applicable to ferment food packaging is expected to contribute to globalize Korean traditional food.

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Determination of Stereochemistry of Acetoxy 1,3-Oxathiolane (아세톡시 1,3-옥사티올란의 입체화학의 결정)

  • Hahn, Hoh Gyu;Chang, Kee Hyuk;Lee, Wha Suk;Ma, He Duck
    • Journal of the Korean Chemical Society
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    • v.40 no.5
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    • pp.357-364
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    • 1996
  • Stereochemistries of acetoxy 1,3-oxathiolane 1 were determined by two methods. First, the structures of $\alpha$ isomer 7 and $\beta$ isomer 9 were confirmed by the difference of their conversion rates to dihydrooxathiin 2 under acid catalysis. When the acetoxy leaving group is located in trans relationship to sulfur, a isomer in which carboxanilide is less hindered sterically against the 1,3-oxathiolane ring is $\beta$ isomer 7, and the other isomer of which the reaction rate is slower than 7 is $\beta$ isomer 9. Second, in the deuterium reactions of diastereomeric sulfoxides, the isomers of which methine hydrogen is substituted to deuterium were cis isomers 15 and 17, and another isomers of which methyl hydrogen is substituted to deuterium were trans isomers 16 and 18. Substitution of either methine or methyl hydrogen to deuterium resulted from stereospecific ring opening followed by recyclization by [2,3] sigmatropic rearrangement.

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Preparation and Characterization of Water-Dispersible Silver Nanoparticles Stabilized by PEO-Conjugated Pro-Drugs

  • Kim, Tae-Hwan;Kim, Keun-Suk;Park, Geon-Hee;Choi, Jin-Hee;Lee, Sang-Mi;Kang, Ho-Jung;Lee, Jae-Yeol;Kim, Jung-Ahn
    • Macromolecular Research
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    • v.17 no.10
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    • pp.770-775
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    • 2009
  • $\omega$-Anhydride-functionalized poly(ethylene oxide) (PEO) obtained from chain-end functionalization and anionic ring-opening polymerization of ethylene oxide using n-butyllithium with potassium t-butoxide in the presence of dimethylsulfoxide (DMSO) was found to be an efficient material for the preparation of water-soluble, polymeric pro-drugs. The reaction of $\omega$-anhydride-functionalized PEO with sulfonamide or with vancomycin provided an efficient method to produce corresponding, water-soluble, PEO-conjugated sulfonamide or PEO-conjugated, vancomycin pro-drugs. These were used successfully to prepare water-dispersible, silver nanoparticles. In this study, the particle sizes were in the range of $5{\sim}40$ nm. The resulting products were characterized by $^1H$ NMR spectroscopy, transmission electron microscopy, electron and X-ray diffraction, size exclusion chromatography, and UV/Visible spectroscopy.

Preparation and Properties of Novel Biodegradable Hydrogel based on Cationic Polyaspartamide Derivative

  • Moon, Jong-Rok;Kim, Bong-Seop;Kim, Ji-Heung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.7
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    • pp.981-985
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    • 2006
  • Novel copolymers consisting of poly(2-hydroxyethyl aspartamide-co-N,N'-dimethyl-1,3-propane aspartamide) (PHEA-DPA) were prepared from polysuccinimide (PSI), which is the thermal polycondensation product of aspartic acid, via a ring-opening reaction with N,N'-dimethyl-1,3-propane diamine (DPA) and ethanolamine. The prepared water-soluble copolymer was then crosslinked by reacting it with hexamethylene diisocyanate to provide the corresponding gel. The swelling behavior and morphology of the crosslinked hydrogels were investigated. The degree of swelling decreased with increasing crosslinking reagent due to the higher crosslinking density. It was also confirmed that the swelling property is affected by pH. At low pH (< pH 4), swelling is increased due to the ionization of DPA with a tertiary amine moiety. In addition, a reversible swelling and de-swelling behavior was demonstrated by adjusting the pH of the solution. The prepared hydrogels showed a well-interconnected microporous structure with regular 5-20 $\mu$m sized pores.

Synthesis and Physicochemical Characterization of Biodegradable PLGA-based Magnetic Nanoparticles Containing Amoxicilin

  • Alimohammadi, Somayeh;Salehi, Roya;Amini, Niloofar;Davaran, Soodabeh
    • Bulletin of the Korean Chemical Society
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    • v.33 no.10
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    • pp.3225-3232
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    • 2012
  • The purposes of this research were to synthesize amoxicillin-carrying magnetic nanoparticles. Magnetic nanoparticles were prepared by a chemical precipitation of ferric and ferrous chloride salts in the presence of a strong basic solution. PLGA and PLGA-PEG copolymers were prepared by ring opening polymerization of lactide (LA) and glycolide (GA) (mole ratio of LA: GA 3:1) with or without polyethylene glycol (PEG). Amoxicillin loaded magnetic PLGA and PLGA-PEG nanoparticles were prepared by an emulsion-evaporation process (o/w). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) photomicrographs showed that the magnetic nanoparticles have the mean diameter within the range of 65-260 nm also they were almost spherical in shape. Magnetic nanoparticles prepared with PLGA showed more efficient entrapment (90%) as compared with PLGA-PEG (48-52%) nanoparticles. In-vitro release of amoxicillin from magnetic PLGA nanoparticles showed that 78% of drug was released over 24 hours. The amount of amoxicillin released from PLGA-PEG s was higher than PLGA.