• Title/Summary/Keyword: Ring-opening reaction

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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.

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 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 ($H_2O$).

Strength Properties of Bisphenol A-Type Epoxy-Modified Mortars under Various Curing Conditions (각종 양생조건에 따른 비스페놀 A형 에폭시수지 혼입 모르타르의 강도성상)

  • Kim, Wan-Ki
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2009.11a
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    • pp.55-59
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    • 2009
  • The epoxy resin without hardener can harden by a ring-opening reaction in the presence of the alkalies produced by the hydration of cement in epoxy-modified mortars and concretes. This paper investigates the effect of curing conditions on the strength improvement of polymer-modified mortars using bisphenol A-type epoxy resin without hardener. The polymer-modified mortars using epoxy resin are prepared with various polymer-cement ratios, and subjected to ideal, water, dry and heat cures. In the heat cure, the epoxy-modified mortars are sealed or unsealed with a PVDC (polyvinylidene chloride) film. The epoxy-modified mortars are tested for flexural and compressive strengths at desired curing methods. The microstructures of the epoxy-modified mortars are also observed by scanning electron microscope. The effects of curing conditions on the strength development of the epoxy-modified mortars are examined. From the test results, the marked effectiveness of the heat cure under the PVDC film sealing against the development of the strength of the epoxy-modified mortar without the hardener is recognized. The flexural and compressive strengths of 7-day-90℃ heat-cured, PVDC film-sealed epoxy-modified mortars without hardener reach 7 to 17MPa and 24 to 44MPa respectively, and are two to three times of Unmodified mortar. Such high strength development of the epoxy-modified mortars may be achieved by the dense microstructure formation by cement hydrates and the hardening of the epoxy resin in the mortars.

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Stereoselective Synthesis of Diverse α-Hydroxy-β-amino Acids and It's Application for Synthesis of Dipeptide Expecting as a Protease Inhibitor

  • Jang, Sang-Hun;Kim, Ju-Young;Kim, Min-Kyu;Han, Jeong-Woo;Park, Ki-Hun;Yoon, Yong-Jin;Lee, Sang-Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.30 no.1
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    • pp.163-171
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    • 2009
  • Few $\alpha$-Hydroxy-$\beta$-amino acids were synthesized via various nucleophilic addition of the epoxide and followed by stereoselective nucleophilic substitution reaction and eliminative cleavage of the acetal selectively in diacetal compound. One of the synthesized $\alpha$-Hydroxy-$\beta$-amino acid reacted with L-leucine methylester to give corresponding dipeptide in good yields.

Turn-On Type Fluorogenic and Chromogenic Probe for the Detection of Trace Amount of Nitrite Ion in Water

  • Saleem, Muhammad;Abdullah, Razack;Hong, In Seok;Lee, Ki-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.389-393
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    • 2013
  • A rhodamine B-based fluorescent probe for nitrite ion ($NO{_2}^-$) has been designed, synthesized, characterized and its properties for recognition of $NO{_2}^-$ were studied. Nearly non fluorescent probe upon reaction with nitrite ion significantly triggered the fluorescence. Fluorescence response is based on ring opening of the spirolactam of rhodamine B phenyl hydrazide showing maximum absorbance at 552 nm and maximum emission at 584 nm. Probe 3 exhibited high sensitivity and extreme selectivity for nitrite ion over other common ions and oxidants ($Cl^-$, $ClO^-$, $ClO{_2}^-$, $ClO{_3}^-$, $ClO{_4}^-$, $SO{_4}^{2-}$, $SiO{_3}^{2-}$, $NO{_3}^{2-}$, $CO{_3}^{2-}$) examined in methanol water (1:1, v/v) at pH 7.0. The probe might be a new efficient tool for detection of nitrite ion in natural water and biological system.

Manufacturing and Numerical Analysis of Glass Fiber Chopped Strand Mat Reinforced p-DCPD Composites Processed by S-RIM (S-RIM을 이용한 Glass Fiber Chopped Strand Mat 강화 p-DCPD 복합재료 제작 및 수치해석을 통한 공정 시간 예측)

  • YOO, HYEONGMIN;UM, MOONKWANG;CHOI, SUNGWOONG
    • Journal of Hydrogen and New Energy
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    • v.30 no.6
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    • pp.629-634
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    • 2019
  • Dicyclopentadiene is a low viscosity resin which forms a poly-dicyclopentadiene rapidly through ring opening metathesis polymerization (ROMP). This poly-dicyclopentadiene has outstanding properties of low-temperature, water and impact resistances. Due to these advantages, military and offshore structures try to apply the DCPD composites by using liquid composite molding process. In this study, 14%, 38% volume fraction fiber glass strand mat reinforced p-DCPD composites processed by structural reaction injection molding (S-RIM) which has resin-catalsyt mixing head and glass fiber preform in the mold. Additionally, S-RIM numerical analysis was conducted to predict the process time depending on fiber volume fraction and mold temperature. The process time is shorter when it has the lower fiber volume fraction or the higher mold temperature. At higher mold temperature, it is necessary to set the maximum mold temperature considering the resin curing time.

Acid-Base Bifunctional Metal-Organic Frameworks: Green Synthesis and Application in One-Pot Glucose to 5-HMF Conversion

  • Zhang, Yunlei;Jin, Pei;Meng, Minjia;Gao, Lin;Liu, Meng;Yan, Yongsheng
    • Nano
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    • v.13 no.11
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    • pp.1850132.1-1850132.14
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    • 2018
  • The direct synthesis of metal-organic frameworks (MOFs) with acidic and basic active sites is challenging due to the introduction of functional groups by post-functionalization method often jeopardize the framework integrity. Herein, we report the direct synthesis of acid-base bifunctional MOFs with tuning acid-base strength. Employing modulated hydrothermal (MHT) approach, microporous MOFs named $UiO-66-NH_2$ was prepared. Through the ring-opening reaction of 1,3-propanesultone with amino group, $UiO-66-NH_2-SO_3H-type$ catalysts can be obtained. The synthesized catalysts were well characterized and their catalytic performances were evaluated in one-pot glucose to 5-HMF conversion. Results revealed the acid-base bi-functional catalyst possessed high activity and excellent stability. This work provides a general and economically viable approach for the large-scale synthesis of acid-base bi-functional MOFs for their potential use in catalysis field.

A Kinetic Study of the Fe(Ⅲ)-Catalyzed Aquation of Bis(malonato)Diaquochromate(Ⅲ) Ion

  • Shim, Jeong-Ae;Moon, Jung-Dae;Park, Heung-Jae;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.318-323
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    • 1990
  • The bis(malonato)diaquochromate(III) ion, $Cr(C_3H_2O_4)_2^-$ in acidic solution hydrolyzes to give $Cr(C_3H_2O_4)^{+}.$ This reaction is catalyzed by ferric ion and the rate law for this cation catalyzed-aquation in a $HClO_4/NaClO_4$ medium, $I = 1.00 M, is-d[Cr(C_3H_2O_4)_2^-]/dt = ({\kappa}_1[Fe^{3+}] + {\kappa}_2[H^+])[Cr(C_3H_2O_4)_2^-]$ where ${\kappa}_1(25^{\circ}C) = 4.72×10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 22.5 Kcal/mol, {\Delta}S^{\neq} = - 2.58 eu) and {\kappa}_2(25^{\circ}C) = 4.75{\times}10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 21.2 Kcal/mol, {\Delta}S^{\neq} = - 7.13 eu).$ Rapid preequilibrium association of basic Cr-bound oxygen with $Fe^{3+},$ followed by rate-determining ring opening, is proposed to account for the ${\kappa}_1,$ hydrolysis pathway.

Bidirectional Interactions between Green Tea (GT) Polyphenols and Human Gut Bacteria

  • Se Rin Choi;Hyunji Lee;Digar Singh;Donghyun Cho;Jin-Oh Chung;Jong-Hwa Roh;Wan-Gi Kim;Choong Hwan Lee
    • Journal of Microbiology and Biotechnology
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    • v.33 no.10
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    • pp.1317-1328
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    • 2023
  • Green tea (GT) polyphenols undergo extensive metabolism within gastrointestinal tract (GIT), where their derivatives compounds potentially modulate the gut microbiome. This biotransformation process involves a cascade of exclusive gut microbial enzymes which chemically modify the GT polyphenols influencing both their bioactivity and bioavailability in host. Herein, we examined the in vitro interactions between 37 different human gut microbiota and the GT polyphenols. UHPLC-LTQ-Orbitrap-MS/MS analysis of the culture broth extracts unravel that genera Adlercreutzia, Eggerthella and Lactiplantibacillus plantarum KACC11451 promoted C-ring opening reaction in GT catechins. In addition, L. plantarum also hydrolyzed catechin galloyl esters to produce gallic acid and pyrogallol, and also converted flavonoid glycosides to their aglycone derivatives. Biotransformation of GT polyphenols into derivative compounds enhanced their antioxidant bioactivities in culture broth extracts. Considering the effects of GT polyphenols on specific growth rates of gut bacteria, we noted that GT polyphenols and their derivate compounds inhibited most species in phylum Actinobacteria, Bacteroides, and Firmicutes except genus Lactobacillus. The present study delineates the likely mechanisms involved in the metabolism and bioavailability of GT polyphenols upon exposure to gut microbiota. Further, widening this workflow to understand the metabolism of various other dietary polyphenols can unravel their biotransformation mechanisms and associated functions in human GIT.