• Title/Summary/Keyword: ring opening

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Determination of Mercury Ion in Contaminated Soil by Rhodamine B Hydrazide (형광화학센서를 이용한 용출기반 토양 수은 오염조사)

  • Kim, Kyungtae;Park, Junboum
    • Journal of Soil and Groundwater Environment
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    • v.21 no.3
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    • pp.1-5
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    • 2016
  • Rhodamine B Hydrazide as a novel fluorescent and colorimetric probe exhibiting remarkably selective fluorescence enhancement toward Hg2+ ion over other 16 metal ions is herein introduced. The probe reacts with Hg2+ ion followed by its spirolactam ring-opening to give a remarkable enhancement of absorption maximum at 550 nm as well as an enhanced fluorescence intensity at 580 nm in aqueous media. Upon titration with Hg2+ ion in various concentration of 10~200 uM, we found that the probe shows a marked color change from colorless to pink, enabling naked-eye detection toward mercury ion. In addition, in the presence of Hg2+ ion, the probe gave rise to change from non-florescence to strong orange fluorescence (Off-On) with a good linearity of R2=0.97. This preliminary results demonstrate that the fluorescent chemosensor we herein introduced can open a new strategy for marked selective and sensitive detection of mercury ions in contaminated soil containing various metal ions.

Structure Determination of Sucrose by Acetylation and Acid Hydrolysis

  • Min, Hee-Jeong;Lee, Tae-Seong;Bae, Young-Soo
    • Journal of the Korean Wood Science and Technology
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    • v.42 no.2
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    • pp.183-192
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    • 2014
  • For the structure determination of D-(+)-sucrose, which consists of ${\alpha}$-D-(+)-glucose and ${\beta}$-D-(+)-fructose, it was acetylated with acetic anhydride and triethyl amine, pyridine, zinc chloride, and sodium acetate as catalysts. The acetylated D-(+)-sucrose was acid-hydrolyzed using sulfuric acid and sodium chloride in methanolic solution. The structures of the reaction products were determined by $^1H$-NMR and $^{13}C$-NMR spectra. The yield of the acetylation indicated the high value in zinc chloride as 70% in zinc chloride catalyst. The acid-hydrolyzed product of the acetylated D-(+)-sucrose, 2,3,4,6,1',3',4',6'-octa-O-acetyl-D-(+)-sucrose, gave 2,3,4,6-tetra-O-acetyl-${\beta}$-D-(+)-glucose and it suggests that the acetylated D-(+)-sucrose was rearranged through the formation of oxonium ion by mutarotation in the 2,3,4,6-tetra-O-acetyl-${\alpha}$-D-(+)-glucose moiety and through the ring opening in the 1',3',4',6'-tetra-O-acetyl-${\beta}$-D-(+)-fructose moiety.

Cor Triatriatum with Coronary Artery Disease in an Old Man -A case report- (고령환자에서 관상동맥 질환을 동반한 삼심방심의 수술치험 -1예 보고-)

  • 천종록;이응배;조용근;장봉현;이종태;김규태
    • Journal of Chest Surgery
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    • v.32 no.1
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    • pp.58-61
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    • 1999
  • Cor triatriatum is a rare anomaly in old age. This is a case report of a 66 year-old man who had been preoperatively diagnosed as coronary artery disease and cor triatriatum. The operative findings revealed that the left atrium had an intra-atrial septum with one small opening 10mm in diameter, the upper compartment received both pulmonary veins, and there were no other anomalies like anormalous pulmonary venous connection or atrial septal defect. The patient successfully underwent open heart surgery ; the anomalous septum was resected, the mitral valve was reconstructed using French technique with Carpentier-Edwards ring, and coronary artery bypass grafting was performed.

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Enantioselective Phenolic Kinetic Resolution of Epoxides Catalyzed by New Chiral Salen Complexes (새로운 구조의 키랄 살렌 촉매상에서 페놀유도체에 의한 에폭사이드의 광학선택적 개환반응)

  • Rahul, B. Kawthekar;Lee, Kwang-Yeon;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.18 no.6
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    • pp.630-635
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    • 2007
  • New chiral Co-salen complexes with one $C_3-^tBu$ group in the structure have been synthesized and applied as a chiral catalyst. A dimeric chiral salen having aluminum group metal salts such as $AlCl_3$ displayed very high catalytic reactivity and enantioselectivity for the asymmetric ring opening of epoxides to synthesize optically pure ${\alpha}$-aryloxy alcohols via phenolic kinetic resolution. The salen complexes immobilized on the inorganic support were also used as effective catalysts in that reaction. The identity of metal salts in the new chiral salen complex has proved to be important in the enantioselective reactions.

Synthesis and pH-Dependent Micellization of Sulfonamide-Modified Diblock Copolymer

  • Pal Ravindra R.;Kim Min Sang;Lee Doo Sung
    • Macromolecular Research
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    • v.13 no.6
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    • pp.467-476
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    • 2005
  • The main objective of this study was to develop and characterize pH-sensitive biodegradable polymeric materials. For pH-sensitivity, we employed three kinds of moieties: 2-amino-3-(lH-imidazol-4-yl)-propionic acid (H), N-[4-( 4,6-dimethyl-pyrimidin-2ylsulfamoyl)-phenyl]succinamic acid (SM), and 2- {3-[ 4-( 4,6-dimethyl-pyrim­idin- 2-ylsulfamoyl)-phenylcarbamoyl]-propionylamino} -3-(3 H - imidazol-4-yl)-propionic acid (SH). The pH -sensitive diblock copolymers were synthesized by ring opening polymerization and coupling reaction from poly(ethylene glycol) (MPEG), $\varepsilon$-caprolactone (CL), D,L-lactide (LA) and pH-sensitive moieties. The pH-sensitive SH molecule was synthesized in a two-step reaction. The first step involved the synthesis of SHM, a methyl ester derivative of SH, by coupling reaction of SM and L-histidine methyl ester dihydrochloride, whereas the second step involved the hydrolysis of the same. The synthesized SM, SHM and SH molecules were characterized by FTIR, $^{1}H$-NMR and $^{13}C$-NMR spectroscopy, whereas diblock copolymers and pH-sensitive diblock copolymer were characterized by $^{1}H$-NMR and GPC analysis. The critical micelle concentrations were determined at various pH conditions by fluorescence technique using pyrene as a probe. The micellization and demicellization studies of pH-sensitive diblock copolymers were also done at different pH conditions. The pH-sensitivity was further established by acid-based titration and DLS analysis.

Synthesis of the Polysaccharide, (1 $\longrightarrow$ 5)-$\alpha$-D-Ribofuranan and Its Catalytic Activities for the Hydrolysis of Phosphates and the Cleavage of Nucleic Acids

  • Han, Man-Jung;Yoo, Kyung-Soo;Kim, Young-Heui;Kim, Hong-Youb;Shin, Hyun-Joon;Chang, Ji-Young
    • Macromolecular Research
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    • v.12 no.4
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    • pp.359-366
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    • 2004
  • The polysaccharide, (1\longrightarrow5)-$\alpha$-D-ribofuranan, was synthesized by a cationic ring-opening polymerization of 1,4-anhydro-2,3-di-O-benzyl-$\alpha$-D-ribopyranose with the aid of boron trifluoride etherate and subsequent debenzylation. This polysaccharide catalyzed the hydrolysis of ethyl p-nitrophenyl phosphate, uridylyl(3'\longrightarrow5')uridine ammonium salt, and 4-tert-butylcatechol cyclic phosphate N-methyl pyridinium. The polymer also catalyzed the cleavage of nucleic acids (DNA and RNA). The hydrolysis of ethyl p-nitrophenyl phosphate in the presence of the polymer was accelerated by 1.5 ${\times}$ 10$^3$ times relative to the uncatalyzed reaction. The catalytic activity was attributable to the vic-cis-diols of the riboses being located inside the active center that is formed by polymer chain folding; these diols form hydrogen bonds with two phosphoryl oxygen atoms of the phosphates so as to activate the phosphorus atoms to be attacked by nucleophile ($H_2O$).

Development of Hybrid Sol-Gel Coating to Prevent Corrosion of Magnesium Alloys (마그네슘 합금의 방청을 위한 하이브리드 졸-겔 코팅제의 개발)

  • Lee, Dong Uk;Kim, Young Hoon;Moon, Myung Jun
    • Corrosion Science and Technology
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    • v.17 no.1
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    • pp.30-36
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    • 2018
  • The high rate of corrosion of magnesium alloys makes it limited for industrial applications. Therefore, surface treatment is required to enhance their corrosion resistance. In our study, a chemical conversion coating for protecting the corrosion of the magnesium alloy, AZ31B, was prepared by using a phosphate-permanganate solution. The chemical conversion coating had a limited protection ability due to defects arising from cracks and pores in the coating layer. The sol-gel coating was prepared by using trimethoxymethylsilane (MTMS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) as precursors, and aluminum acetyl acetonate as a ring opening agent. The corrosion protection properties of sol-gel and conversion coatings in 0.35wt% NaCl solution were measured by the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization test. The EIS results indicated that the resistance of the chemical conversion coating with the sol-gel coating was significantly improved through the sol-gel sealed phosphate-permanganate conversion coating. The results of the potentiodynamic polarization test revealed that the sol-gel coating decreased the corrosion current density ($I_{corr}$). The SEM image showed that the sol-gel coating sealed conversion coating and improved corrosion protection.

Drug Release Behavior of Poly($\varepsilon$-caprolactone )-b-Poly( acrylic acid) Shell Crosslinked Micelles below the Critical Micelle Concentration

  • Hong Sung Woo;Kim Keon Hyeong;Huh June;Ahn Cheol-Hee;Jo Won Ho
    • Macromolecular Research
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    • v.13 no.5
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    • pp.397-402
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    • 2005
  • To explore the potential of shell crosslinked micelle (SCM) as a drug carrier, the drug release behavior of poly($\varepsilon$-caprolactone)-b-poly(acrylic acid) (PCL-b-PAA) SCMs was investigated. PCL-b-PAA was synthesized by ring opening polymerization of $\varepsilon$-caprolactone and atom transfer radical polymerization of tert-butyl acrylate, followed by selective hydrolysis of tert-butyl ester groups to acrylic acid groups. The resulting amphiphilic polymer was used to prepare SCMs by crosslinking of PAA corona via amidation chemistry. The drug release behavior of the SCMs was studied, using pyrene as a model drug, and was compared with that of non-crosslinked micelles, especially below the critical micelle concentration (CMC). When the shell layers were crosslinked, the drug release behavior of the SCMs was successfully modulated at a controlled rate compared with that of the non-crosslinked micelles, which showed a burst release of drug within a short time.

Formation of Poly(ethylene glycol)-Poly($\varepsilon$-caprolactone) Nanoparticles via Nanoprecipitation

  • Lee, Jae-Sung;Hwang, Su-Jong;Lee, Doo-Sung;Kim, Sung-Chul;Kim, Duk-Joon
    • Macromolecular Research
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    • v.17 no.2
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    • pp.72-78
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    • 2009
  • Size control of therapeutic carriers in drug delivery systems has become important due to its relevance to biodistribution in the human body and therapeutic efficacy. To understand the dependence of particle size on the formation condition during nanoprecipitation method, we prepared nanoparticles from biodegradable, amphiphilic block copolymers and investigated the particle size and structure of the resultant nanoparticles according to various process parameters. We synthesized monomethoxy poly(ethylene glycol)-poly($\varepsilon$-caprolactone) block copolymer, MPEG-PCL, with different MPEG/PCL ratios via ring opening polymerization initiated from the hydroxyl end group of MPEG. Using various formulations with systematic change of the block ratio of MPEG and PCL, solvent choice, and concentration of organic phase, MPEG-PCL nanoparticles were prepared through nanoprecipitation technique. The results indicated that (i) the nanoparticles have a dual structure with an MPEG shell and a PCL core, originating from self-assembly of MPEG-PCL copolymer in aqueous condition, and (ii) the size of nanoparticles is dependent upon two sequential processes: diffusion between the organic and aqueous phases and solidification of the polymer.

Kinetic Studies on the Reaction of Thiocyanate with Di-$\mu$-oxobis-(aquaoxalatooxomolybdate (V)) in Acid Media (산성수용매에서 이-$\mu$-옥소비스-(아쿠아옥살라토옥소몰리브덴 (V)) 산이온과 티오시안산이온의 반응)

  • Chang-Su Kim;Chang-Yong Kwon;Moon-Pyoung Yi;Chann-Woo Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.623-628
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    • 1985
  • Rate constants for complexing with thiocyanate after ring opening of molybdenum-oxalate in acid media were obtained spectrophotometrically at 460nm. The acid-assisted dissociation of molybdenum-oxalate and the reaction of thiocyanate with oxalatooxomolybdenum (V) complex in acid media were investigated with thiocyanate and hydrogen ion concentration. The kinetic data indicate that molybdenum-oxalate is protonated to a limited extent in acid media and the protonated complex is responsible for an increase in rate for the reaction of thiocyanate with oxalatooxomolybdenum (V) complex. Replacement of an oxalate ligand in acid media has been interpreted in terms of dissociative mechanism involving bond-breaking of the oxygen trans to the yl oxygen.

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