• Title/Summary/Keyword: Michael reactions

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Kinetic Studies on the Nucleophilic Addition of Thioglycolic Acid to S-Phenyl-S-vinyl-N-p-tosylsulfilimine Derivatives (S-Phenyl-S-vinyl-N-p-tosylsulfilimine 유도체에 대한 Thioglycolic Acid의 친핵성 첨가반응에 관한 반응속도론적 연구)

  • Kim, Tae Rin;Han, Man So;Pyun, Sang Yong
    • Journal of the Korean Chemical Society
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    • v.40 no.10
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    • pp.663-669
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    • 1996
  • The rate constants for the nucleophilic addition reactions of thioglycolic acid to vinylsulfilimine(VSI) derivatives(p-OCH3, H, p-Cl and p-Br) were determined by an ultraviolet spectrophotometric method, and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base catalysis and substituent effect, a plausible addition reaction mechanism was proposed: Below pH 3.0, the reaction was proceeded via the addition of neutral molecule to carbon-carbon double bond after protonation at the nitrogen atom of the sulfilimine, and in the pH range of 3.0 to 9.0, the neutral molecule and its anion attacked to carbon-carbon double bond competitively. Above pH 9.0, sulfide anion added to the double bond (Michael type addition).

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Kinetic Studies on the Nucleophilic Addition of Thiourea to ${\beta}$-Nitrostyrene Derivatives (${\beta}$-Nitrostyrene 유도체에 대한 Thiourea의 친핵성 첨가반응에 관한 반응속도론적 연구)

  • Tae-Rin Kim;Yeun-Soo Chung;Myung-Sook Chung
    • Journal of the Korean Chemical Society
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    • v.35 no.3
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    • pp.268-274
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    • 1991
  • The rate constants for the nucleophilic addition reactions of thiourea to ${\beta}$-nitrostyrene derivatives(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$) were determined by UV spectrophotometer and rate equations which can be applied over a wide pH ranges were obtained. On the basis of substituent effect, general base catalysis and rate equations, a reaction mechanism was proposed and revealed quantitively. Above pH 9.00, sulfide anion adds to the double bond(Michael type addition) and between pH 7.00 and 9.00, the neutral molecules and its anions add to the double bond competitively. Below pH 7.00, the addition reaction to double bond is initiated by the addition of neutral thiourea molecule.

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Spectroscopic Analysis on Michael Addition Reaction of Secondary Amino Groups on Silica Surface with 3-(Acryloyloxy)-2-hydroxypropyl Methacrylate (2차 아미노기가 결합된 실리카 나노 입자 표면에 3-(Acryloyloxy)-2-hydroxypropyl Methacrylate의 마이클 부가 반응에 대한 분광학적 분석)

  • Lee, Sangmi;Ha, Ki Ryong
    • Polymer(Korea)
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    • v.38 no.2
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    • pp.257-264
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    • 2014
  • In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]ethylenediamine (BTPED) silane coupling agent, which has two secondary amino groups in a molecule, to introduce amino groups on the silica surface. After modification of silica, we used acrylate group containing 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce polymerizable methacrylate groups by Michael addition reaction. We used Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and liquid and solid state cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand the reactions between N-H groups of BTPED modified silica surface and acrylate groups of AHM monomer. We confirmed Michael addition reaction between BTPED modified silica and AHM completed in 2 hr reaction time. We also found increased methacrylate group introduction with increase of mol ratio of the acrylate group of AHM to N-H group of BTPED modified silica by increase of C=O peak area of measured FTIR spectra. These results were also supported by EA and solid state $^{13}C$ and $^{29}Si$ NMR results.

Biguanide-Functionalized Fe3O4/SiO2 Magnetic Nanoparticles: An Efficient Heterogeneous Organosuperbase Catalyst for Various Organic Transformations in Aqueous Media

  • Alizadeh, Abdolhamid;Khodaei, Mohammad M.;Beygzadeh, Mojtaba;Kordestani, Davood;Feyzi, Mostafa
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2546-2552
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    • 2012
  • A novel biguanide-functionalized $Fe_3O_4/SiO_2$ magnetite nanoparticle with a core-shell structure was developed for utilization as a heterogeneous organosuperbase in chemical transformations. The structural, surface, and magnetic characteristics of the nanosized catalyst were investigated by various techniques such as transmission electron microscopy (TEM), powder X-ray diffraction (XRD), vibrating sample magnetometry (VSM), elemental analyzer (EA), thermogravimetric analysis (TGA), $N_2$ adsorption-desorption (BET and BJH) and FT-IR. The biguanide-functionalized $Fe_3O_4/SiO_2$ nanoparticles showed a superpara-magnetic property with a saturation magnetization value of 46.7 emu/g, indicating great potential for application in magnetically separation technologies. In application point of view, the prepared catalyst was found to act as an efficient recoverable nanocatalyst in nitroaldol and domino Knoevenagel condensation/Michael addition/cyclization reactions in aqueous media under mild condition. Additionally, the catalyst was reused six times without significant degradation in catalytic activity and performance.

New Hyperbranched Polyimides and Polyamides: Synthesis, Chain-End Functionalizations, Curing Studies, and Some Physical Properties (새로운 Hyperbranchedpolyimidesandpolyamides: 합성, 말단기 변형, 경화 연구, 그리고 물리적 성질)

  • Baek, Jong-Beom;Chris B. Lyon;Tan, Loon-Seng
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2003.10a
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    • pp.1-2
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    • 2003
  • While aromatic polyimides and polyamides have found widespread use as high performance polymers, the present work addressed the need for organosoluble materials through the use of a hyperbranching scheme. The $AB_2$ monomers were prepared. The $AB_2$ monomers were then polymerized via aromatic fluoride-displacement and Yamazaki reactions to afford the corresponding hydroxyl-terminated hyperbranched polyimides (HT-PAEKI) and amine-terminated hyperbranched polyamides, respectively. HT-FAEKI was then functionalized with allyl and propargyl bromides as well as epichlorohydrin to afford allyl-terminated AT-PAEKI, propargyl-terminated PT-PAEKI, and epoxy (glycidyl)-terminated ET-PAEKI, in that order. All hyperbranched poly(ether-ketone-imide)s were soluble in common organic solvents. AT-PAEKI was blended with a bisphenol-A-based bismaleimide (BFA-BMI) in various weight ratios. Thermal, rheological, and mechanical properties of these blend systems were evaluated. Two characteristic hyperbranched polyamides, which the one has para-electron donating groups to the surface amine groups and the other has para-electron withdrawing groups to the surface amine groups, were selected to compare BMI curing behaviors. The electron rich polymer displayed ordinary Michael addition type exothermic reaction, while electron deficient polymer did display unusual curing behaviors. Based on analytical data, the later system provided the strong evidences to support room temperature curing of BMI by reactive intermediates instead of reactive primary amine groups on the macromolecule surface.

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A comparison of photosynthesis measurements by O2 evolution, 14C assimilation, and variable chlorophyll fluorescence during light acclimatization of the diatom Coscinodiscus granii

  • Trampe, Erik;Hansen, Per Juel;Kuhl, Michael
    • ALGAE
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    • v.30 no.2
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    • pp.103-119
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    • 2015
  • Photosynthetic rates of the large centric diatom Coscinodiscus granii were measured by means of multicolor variable chlorophyll fluorescence imaging, single cell $^{14}C$ assimilation, and optical $O_2$ sensor measurements during light acclimatization of cultures grown at five different irradiances: 50, 150, 235, 332, and $450{\mu}mol$ photons $m^{-2}\;s^{-1}$. Photo-acclimatization was evident from changes of cellular chlorophyll a content, growth rates, and light response curves. Each of the applied methods evaluates different parts and reactions in the photosynthetic apparatus, which makes a direct quantitative comparison of rates difficult, although a different degree of correlation were found between all three methods. However, when used in combination, they provide information about the internal relationship of photosynthetic pathways as well as the variation in photosynthetic capacity between individual cells within a single algal culture.

Detection of Avian Influenza-DNA Hybridization Using Wavelength-scanning Surface Plasmon Resonance Biosensor

  • Kim, Shin-Ae;Kim, Sung-June;Lee, Sang-Hun;Park, Tai-Hyun;Byun, Kyung-Min;Kim, Sung-Guk;Shuler, Michael L.
    • Journal of the Optical Society of Korea
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    • v.13 no.3
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    • pp.392-397
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    • 2009
  • We designed a wavelength interrogation-based surface plasmon resonance (SPR) biosensor to detect avian influenza DNA (AI-DNA). Hybridization reactions between target AI-DNA probes and capture probes immobilized on a gold surface were monitored quantitatively by measuring the resonance wavelength in the visible waveband. The experimental results were consistent with numerical calculations. Although the SPR detection technique does not require the DNA to be labeled, we also evaluated fluorescently-labeled targets to verify the hybridization behavior of the AI-DNA. Changes in resonance were found to be linearly proportional to the amount of bound analyte. A wavelength interrogation-type SPR biosensor can be used for rapid measurement and high-throughput detection of highly pathogenic AI viruses.

Silk Fibroin/Chitosan Conjugate Crosslinked by Tyrosinase

  • Kang, Gyung-Don;Lee, Ki-Hoon;Ki, Chang-Seok;Nahm, Joong-Hee;Park, Young-Hwan
    • Macromolecular Research
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    • v.12 no.5
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    • pp.534-539
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    • 2004
  • Two biopolymers, silk fibroin (SF) and chitosan, were conjugated by tyrosinase (EC 1.14.18.1), a polyphenolic oxidase, to improve their physicochemical properties, such as their thermal properties and morphological stabilities in organic solvents. The crosslinking between SF and chitosan took place mainly through Michael addition reactions. A main reaction between the amino groups in chitosan and o-quinone, the oxidation product of the tyrosyl residue in SF, was confirmed by UV spectroscopy. Measurements of viscosity and light scattering indicated that the crosslinked SF/chitosan conjugate was compact: it had a smaller particle size because of tight bonding forces between the SF and chitosan molecular chains. Thermal decomposition of SF/chitosan conjugates crosslinked by tyrosinase occurred at higher temperatures. The adhesiveness of the SF/chitosan conjugates decreased steadily as the crosslinking reaction progressed. We propose that this new crosslinking method be used for the preparation of silk fibroin/chitosan conjugates using tyrosinase. We expect that SF/chitosan conjugates crosslinked by tyrosinase can be used preferentially in biomedical applications because of its unique properties and non-toxicity.

Controlled Conversion of Sodium Metal From Nuclear Systems to Sodium Chloride

  • Herrmann, Steven;Zhao, Haiyan;Shi, Meng;Patterson, Michael
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.19 no.2
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    • pp.233-241
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    • 2021
  • A series of three bench-scale experiments was performed to investigate the conversion of sodium metal to sodium chloride via reactions with non-metal and metal chlorides. Specifically, batches of molten sodium metal were separately contacted with ammonium chloride and ferrous chloride to form sodium chloride in both cases along with iron in the latter case. Additional ferrous chloride was added to two of the three batches to form low melting point consolidated mixtures of sodium chloride and ferrous chloride, whereas consolidation of a sodium-chloride product was performed in a separate batch. Samples of the products were characterized via X-ray diffraction to identify attendant compounds. The reaction of sodium metal with metered ammonium chloride particulate feeds proceeded without reaction excursions and produced pure colorless sodium chloride. The reaction of sodium metal with ferrous chloride yielded occasional reaction excursions as evidenced by temperature spikes and fuming ferrous chloride, producing a dark salt-metal mixture. This investigation into a method for controlled conversion of sodium metal to sodium chloride is particularly applicable to sodium containing elevated levels of radioactivity-including bond sodium from nuclear fuels-in remote-handled inert-atmosphere environments.

Assessment on Recovery of Cesium, Strontium, and Barium From Eutectic LiCl-KCl Salt With Liquid Bismuth System

  • Woods, Michael E.;Phongikaroon, Supathorn
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.18 no.4
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    • pp.421-437
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    • 2020
  • This study provides an assessment on a proposed method for separation of cesium, strontium, and barium using electrochemical reduction at a liquid bismuth cathode in LiCl-KCl eutectic salt, investigated via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS). CV studies were performed at temperatures of 723-823 K and concentrations of the target species up to 4.0wt%. Redox reactions occurring during potential sweeps were observed. Concentration of BaCl2 in the salt did not seem to influence the diffusivity in the studied concentration range up to 4.0wt%. The presence of strontium in the system affected the redox reaction of lithium; however, there were no distinguishable redox peaks that could be measured. Impedance spectra obtained from EIS methods were used to calculate the exchange current densities of the electroactive active redox couple at the bismuth cathode. Results show the rate-controlling step in deposition to be the mass transport of Cs+ ions from the bulk salt to the cathode surface layer. Results from SEM-EDS suggest that Cs-Bi and Sr-Bi intermetallics from LiCl-KCl salt are not thermodynamically favorable.