• 제목/요약/키워드: Michael-type addition

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Kinetics and Thermodynamic Studies on the Reaction of Cysteine with Cinnamaldehyde

  • Kim, Tae-Rin;Yun, Se-Joon;Park, Byung-Bin
    • Bulletin of the Korean Chemical Society
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    • 제7권1호
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    • pp.25-29
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    • 1986
  • The reaction of cysteine with cinnamaldehyde have been studied kinetically and thermodynamically. It was found that the reaction proceeds in two steps; formation of the monoadduct by a Michael type addition followed by the nucleophilic attack of the second cysteine to the carbonyl carbon of the monoadduct to afford the thiazolidine derivative. A reaction profile for the reaction of cysteine with cinnamaldehyde was constructed based on the thermodynamic parameters analyzed for the forward and the reverse reactions. It was assumed that the second step of this reaction accompanies an intermediate, a Schiff base.

2-Phenyl-4H,5H-3-methyl-3-thiazolinium Perchlorate 유도체의 가수분해 반응 메카니즘에 관한 반응속도론적 연구 (Kinetic Studies on the Mechanism of Hydrolysis of 2-Phenyl-4H,5H-3-methyl-3-thiazolinium Perchlorate Derivatives)

  • 김태린;이소영;한만소;변상용;이석희
    • 대한화학회지
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    • 제44권2호
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    • pp.120-126
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    • 2000
  • 2-PhenyI-4H,5H-3-methyl-3-thiazolinium perchlorate(PTP)유도체들의 가수분해속도상수를 수용액에서 자외선 분광법으로 측정하여 넓은 pH 범위에서 적용될 수 있는 속도식을 구하였다. pH에 따른 속도상수의 변화, 가수분해 생성물의 확인, 일반염기 및 치환기 효과 등을 바탕으로 반응 메카니즘을 제안하였다. 즉 pH 4.0 이하에서는 물분자의 첨가가 일어나 가수분해가 진행되며, pH 9.0 이상에서는 전형적인 Michael type의 반응이 일어나며, pH $4.5{\sim}8.0$ 사이에서는 이들 두 반응이 경쟁적으로 일어남을 알았다.

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Furfurylidene acetophenone유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구 (The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Furfurylidene Acetophenone derivatives)

  • 이기창;목갑영;오세영;류정욱
    • 한국응용과학기술학회지
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    • 제14권1호
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    • pp.27-32
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    • 1997
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

광경화형 자가광개시 아크릴레이트의 경화특성 및 도막물성 (Curing and Coating Properties of Photo-Curable Self-Photoinitiating Acrylate)

  • 한아람;홍진후;김현경
    • 접착 및 계면
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    • 제15권1호
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    • pp.22-30
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    • 2014
  • 본 연구는 자가광개시형 아크릴레이트를 Michael addition 반응을 이용하여 합성하고 자유라디칼, 양이온 및 하이브리드 시스템을 통해 배합-경화-물성 상관관계를 유도하여 이들의 경화물성, 표면 물성을 Photo-DSC, 진자경도, 연필경도 및 내오염성 측정을 이용하여 평가하였다. 그 결과, 자유라디칼 반응형 모노머 첨가를 통해 경화 특성의 향상을 유도할 수 있었으나, 일정량 이상의 모노머 첨가 시 반응성 저하로 인해 경화성이 오히려 저하되었으며, 이는 자유라디칼 반응형 모노머에 의한 이동성의 향상이 SPIA의 경화 향상에는 한계가 있음을 확인하였다. 자유 라디칼 광개시제에 의한 자유 라디칼의 생성과 자가광개시 반응에 의한 자유라디칼이 동시에 연속적으로 반응에 참여되어 우수한 경화 특성을 보였으며, 양이온 시스템을 접목한 하이브리드 시스템의 경우 양이온계 광개시제와 양이온계 모노머가 라디칼 생성과 확산까지 촉진 시켜 우수한 경화특성을 보이며, 라디칼 중합에 비해 산소에 의한 영향이 적은 양이온 중합의 영향으로 표면물성을 비롯한 도막 물성 또한 가장 우수하였다.

Facile Regiocontrolled Three-Step Synthesis of Poly-Substituted Furans, Pyrroles, and Thiophenes: Consecutive Michael Addition of Methyl Cyanoacetate to α,β-Enone, CuI-Mediated Aerobic Oxidation, and Acid-Catalyzed Paal-Knorr Synthesis

  • Kim, Se-Hee;Lim, Jin-Woo;Lim, Cheol-Hee;Kim, Jae-Nyoung
    • Bulletin of the Korean Chemical Society
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    • 제33권2호
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    • pp.620-624
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    • 2012
  • An efficient synthesis of poly-substituted furans, pyrroles, and thiophenes was carried out in a regiocontrolled manner via a three-step process; (i) conjugate addition of methyl cyanoacetate derivatives to ${\alpha}$,${\beta}$-enones, (ii) CuI-mediated aerobic oxidation, and (iii) Paal-Knorr type synthesis of five-membered heterocycles.

The Kinetics and Mechanism of Nucleophilic Addition of Thioglycolic Acid to ${\beta}$-Nitrostyrene Derivatives

  • Kim, Tae-Rin;Huh, Tae-Sung;Han, In-Sup
    • Bulletin of the Korean Chemical Society
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    • 제3권4호
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    • pp.162-165
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    • 1982
  • The rate constants of the nucleophilic addition of thioglycolic acid to the derivatives $(H,\;p-CH_3,\;p-CH_3O,\;p-Cl,\;p-NO_2)$ of ${\beta}$-nitrostyrene were determined by ultraviolet spectrophotometry. The rate equations which can be applied over a wide pH range were obtained. Therefrom a reaction mechanism was proposed. Above pH 8.5 sulfide anion adds to the double bond (Michael type addtion). However, below pH 8.5, the neutral molecule and $HSCH_2COO^{\theta}$ add to the double bond.

Surface-modified Nanoparticle Additives for Wear Resistant Water-based Coatings for Galvanized Steel Plates

  • Becker-Willinger, Carsten;Heppe, Gisela;Opsoelder, Michael;Veith, H.C. Michael;Cho, Jae-Dong;Lee, Jae-Ryung
    • Corrosion Science and Technology
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    • 제9권4호
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    • pp.147-152
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    • 2010
  • Conventional paints for conversion coating applications in steel production derived mainly from water-based polymer dispersions containing several additives actually show good general performance, but suffer from poor scratch and abrasion resistance during use. The reason for this is because the relatively soft organic binder matrix dominates the mechanical surface properties. In order to maintain the high quality and decorative function of coated steel sheets, the mechanical performance of the surface needs to be improved significantly. In fact the wear resistance should be enhanced without affecting the optical appearance of the coatings by using appropriate nanoparticulate additives. In this direction, nanocomposite coating compositions (Nanomer$^{(R)}$) have been derived from water-based polymer dispersions with an increasing amount of surface-modified nanoparticles in aqueous dispersion in order to monitor the effect of degree of filling with rigid nanoparticles. The surface of nanoparticles has been modified for optimum compatibility with the polymer matrix in order to achieve homogeneous nanoparticle dispersion over the matrix. This approach has been extended in such a way that a more expanded hybrid network has been condensed on the nanoparticle surface by a hydrolytic condensation reaction in addition to the quasi-monolayer type small molecular surface modification. It was expected that this additional modification will lead to more intensive cross-linking in coating systems resulting in further improved scratch-resistance compared to simple addition of nanoparticles with quasi-monolayer surface modification. The resulting compositions have been coated on zinc-galvanized steel and cured. The wear resistance and the corrosion protection of the modified coating systems have been tested in dependence on the compositional change, the type of surface modification as well as the mixing conditions with different shear forces. It has been found out that for loading levels up to 50 wt.-% nanoparticles, the mechanical wear resistance remains almost unaffected compared to the unmodified resin. In addition, the corrosion resistance remained unaffected even after $180^{\circ}$ bending test showing that the flexibility of coating was not decreased by nanoparticle addition. Electron microscopy showed that the inorganic nanoparticles do not penetrate into the organic resin droplets during the mixing process but rather formed agglomerates outside the polymer droplet phase resulting in quite moderate cross linking while curing, because of viscosity. The proposed mechanisms of composite formation and cross linking could explain the poor effect regarding improvement of mechanical wear resistance and help to set up new synthesis strategies for improved nanocomposite morphologies, which should provide increased wear resistance.

Combined Isotropic-Kinematic 경화규칙에 기초한 자동차용 알루미늄합금-및 Dual-Phase 강 판재의 스프링백 예측 (Spring-back Evaluation of Automotive Sheets Based on Combined Isotropic-Kinematic Hardening Rule)

  • 이명규;김대용;정관수
    • 한국소성가공학회:학술대회논문집
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    • 한국소성가공학회 2003년도 추계학술대회논문집
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    • pp.144-147
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    • 2003
  • In order to evaluate spring-back behavior in automotive sheet forming processes, a panel shape idealized as a SS-rail has been investigated. After spring-back kas been predicted fer SS-rails using the finite element analysis, results has been compared with experimental measurements for three automotive sheets. To account for hardening behavior such as the Bauschinger and transient effects in addition to anisotropic behavior, the combined isotropic-kinematic hardening law based on the Chaboche type single-surface model and a recently developed non-quadratic anisotropic yield function have been utilized, respectively.

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The Role of Thymic Stromal Lymphopoietin (TSLP) in Glomerulonephritis

  • Lee, Keum Hwa;Yang, Jae Won;Cho, Jin Young;Lee, Joo Yup;Lim, Eun Kyung;Eisenhut, Michael;Jeong, Dong Yeon;Steingroever, Johanna;Shin, Jae Il
    • Childhood Kidney Diseases
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    • 제22권1호
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    • pp.17-21
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    • 2018
  • Thymic stromal lymphopoietin (TSLP) is an interleukin-7-like cytokine that is an important trigger and initiator of many allergic diseases. TSLP promotes a T-helper type 2 (Th2) cytokine response that can be pathological. A relationship is formed both at the induction phase of the Th2 response through polarization of dendritic cells to drive Th2 cell differentiation and at the effector phase of the response, by promoting the expansion of activated T cells and their secretion of Th2 cytokines and TSLP. In transgenic mice with TSLP overexpression, it has been reported that TSLP leads to the development of mixed cryoglobulinemic membranoproliferative glomerulonephritis. In addition, TSLP can play an important role in the pathogenesis of IgA nephropathy and systemic lupus erythematosus-related nephritis. From our knowledge of the role of TSLP in the kidney, further studies including the discovery of new therapies need to be considered based on the relationship between TSLP and glomerulonephritis.

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

  • Baek, Jong-Beom;Chris B. Lyon;Tan, Loon-Seng
    • 한국복합재료학회:학술대회논문집
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    • 한국복합재료학회 2003년도 추계학술발표대회 논문집
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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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