• Title/Summary/Keyword: C-C bond formation

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A Novel Method to Fabricate Tough Cylindrical Ti2AlC/Graphite Layered Composite with Improved Deformation Capacity

  • Li, Aijun;Chen, Lin;Zhou, Yanchun
    • Journal of the Korean Ceramic Society
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    • v.49 no.4
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    • pp.369-374
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    • 2012
  • Based on the structure feature of a tree, a cylindrical $Ti_2AlC$/graphite layered composite has been fabricated through heat treating a graphite column and six close-matched thin wall $Ti_2AlC$ cylinders bonded with the $Ti_2AlC$ powders at $1300^{\circ}C$ and low oxygen partial pressure. SEM examination reveals that the bond interlayers between cylinders or that between cylinder and column are not fully dense without any crack formation. During the compressive test, the strain of the $Ti_2AlC$/graphite layered composite is about twice higher than that of the monolithic $Ti_2AlC$ ceramic, and the compressive strength of the layered composite is 348 MPa. The layered composite show the noncatastrophic fracture behaviors due to the debonding and shelling off of the layers, which are different from the monolithic $Ti_2AlC$ ceramic. The mechanism of the improved deformation capacity and noncatastrophic failure modes are attributed to the presence of the central soft graphite column and cracks deflection by the bond interlayers.

Density Functional Theory Studies on the Electrophilic versus Electron Transfer Mechanisms of Aryl Vinyl Ethers

  • 김왕기;손창국;임선희;이순기;김창곤;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.20 no.10
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    • pp.1177-1180
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    • 1999
  • The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

Baylis-Hillman Reaction and Chemical Transformations of Baylis-Hillman Adducts

  • Lee, Ka-Young;Gowrisankar, Saravanan;Kim, Jae-Nyoung
    • Bulletin of the Korean Chemical Society
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    • v.26 no.10
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    • pp.1481-1490
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    • 2005
  • Carbon-carbon single bond-forming reaction is the most useful and fundamental reaction in organic synthesis. Most of the basic carbon-carbon single bond-forming reactions, thus, developed in the past. In these respects, conceptually new C-C bond formation reaction can be highlighted. The Baylis-Hillman reaction was found at the early 1970’s. However, extensive studies on this highly potential reaction were started only before 15 years. This review has been written to shed more lights to the importance of Baylis-Hillman reaction. We have focused mainly on the reaction mechanism, conceptually related reactions, and chemical transformations of the Baylis-Hillman adducts.

Role of class-C fly Ash in the Development of Strength & Microstructure of Fly Ash-GGBS Geopolymer

  • Sasui, Sasui;Kim, Gyu Yong;Lee, Sang Kyu;Son, Min jae;Hwang, Eui Chul;Nam, Jeong Soo
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2020.06a
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    • pp.79-80
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    • 2020
  • The class-C fly ash (FA) and ground granulated blast-furnace slag (GGBS) based geopolymer activated in NaOH (4M) was studied regarding compressive strength, porosity, microstructure and formation of crystalline phases. The class-C FA and GGBS blends resulted in reduced strength and increased porosity of the matrix with the increase in FA content. The unreactivity of calcium in blends was observed with increasing FA content leading to strength loss. it is evident from XRD patterns that calcium in FA did not contribute in forming CSH bond, but formation of crystalline calcite was observed. Furthermore, XRD analyses revealed that reduction in FA leads to the reduction in crystallinity and SEM micrographs showed the unreactive FA particles which hinder the formation of denser matrix.

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Role of cysteine at positions 67, 161 and 241 of a Bacillus sphaericus binary toxin BinB

  • Boonyos, Patcharaporn;Soonsanga, Sumarin;Boonserm, Panadda;Promdonkoy, Boonhiang
    • BMB Reports
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    • v.43 no.1
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    • pp.23-28
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    • 2010
  • Binary toxin consisting of BinA and BinB from Bacillus sphaericus is toxic to mosquito larvae. BinB is responsible for specific binding to the larval gut cell membrane while BinA is crucial for toxicity. To investigate functional role of cysteine in BinB, three cysteine residues at positions 67, 161, and 241 were replaced by alanine or serine. Mutations at these positions did not affect protein production and overall structure of BinB. These cysteine residues are not involved in disulfide bond formation between BinB molecules. Mosquito-larvicidal assays revealed that C67 and C161 are essential for toxicity, whereas C241 is not. Mutations at C67 and C161 resulted in weaker BinA-BinB interaction. The loss of toxicity may be due to the reduction of interactions between BinA and BinB or BinB and its receptor. C67 and C161 could also play a part during conformational changes or internalization of the binary toxin into the target cell.

Necleophilic Substitution Reaction of Dansyl, Bansyl, Dabsyl Chloride (Dansyl, Bansyl, Dsbsyl Chloride의 친핵성 치환반응)

  • 김문식;채기수
    • The Korean Journal of Food And Nutrition
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    • v.5 no.1
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    • pp.23-32
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    • 1992
  • Kinetic studies of nucleophilic substitution reactions of dansyl, bansyl, dabsyl chlorides with pyridines have been investigated at $0^{\circ}C$ in a range of methanol-acetonitrile binary solvent mixtures. The order of magnitude for reactivity of substrates with pyridines in the same reaction condition is dabsyl chloride>dansyl chloride> bansyl chloride. The value of $\rho$n(-2.29~ -4.66) and $\beta$(0.537~0.901) associated with a change substituent in the nucleophile are large and indicate a relatively advanced bond formation in the transition state. Solvatochromic correlations were predicted the increase of bond formation transition state according to the increasing MeCN contents, showing the greater contribution of polarity polarizability ($\pi$*) than hydro-gen bond donar acidity($\alpha$). We conclude that the reactions of dansyl, bansyl, dabsyl chlorides with pyridines proceed via associative Sn2 type reaction mechanism.

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Association of Riboflavin and Drug Molecules (Riboflavin과 약품 분자와의 회합)

  • 유병설
    • YAKHAK HOEJI
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    • v.28 no.2
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    • pp.101-127
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    • 1984
  • The study of interaction between riboflavin derivatives and biologically active substances was reviewed. With combination of spectroscopic methods such as NMR, UV, Fluorescence and IR, informations about interaction mechanism including hydrogen bond formation, conformation of association complex, and association constant were obtained. 1. Riboflavin associated with adenine but not with other bases found in the nucleic acids. -CONHCO- group was included in the formation of hydrogen bond with adenine. 2. Riboflavin interacted with alcohol to make a 1 : 1 association complex through the 3N-imino and 2C-carbonyl group of the isoalloxazine ring and the hydroxyl group of the alcohols. 3. Riboflavin associated with salicylates to produce the cyclic hydrogen-bonded dimer. The strongest complex was formed with salicylic acid, a weaker one with aspirin, and an even weaker one with salicylamide. 4. Other bio-active substances, orotic acid and inhibitors such as phenol, trichloroacetic acid and indol also formed hydrogen bond with riboflavin. 5. Reduced riboflavin showed strong self-association to produce the cyclic hydrogen-bonded complex and it associated with adenine and with cytosine to form 1 : 3 complex.

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Adhesion improvement between metals and fluoropolymers by ion assisted reaction (이온보조반응에 의한 금속과 불소계 고분자의 접착력 증진)

  • Han, Sung;Cho, Jun-Sik;Choi, Sung-Chang;Yoon, Ki-Hyun;Koh, Seok-Keun
    • Journal of the Korean Vacuum Society
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    • v.10 no.1
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    • pp.37-43
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    • 2001
  • Polyvinylidenefluoride and Polytetrafluoroethylene have been irradiated by 1 keV Ar+ ion beam in an $O_2$ environment. Hydrophilic functional groups (such as -(C-O)-,-(C=O)-,-(C=O)-O- and so on) were formed on fluoropolymers. Contact angles of water to PVDF were reduced from $75^{\circ}$ to $31^{\circ}$. Re-increase of contact angle was originated from carbonization phase in case of high dose irradiation above $1{\times}10^{16} Ar^+cm^2$. Contact angles to PTFE decreased at low dose irradiation and were exaggerated to about $140^{\circ}$ due to cone type surface at high dose irradiation. Hydrophilic functional groups have played an important role on adhesion between metal and fluoropolymers by acid-base interaction and chemical bond formation. Adhesion of Pt/PVDF was enhanced by acid-base interaction because Pt is inert metal. Chemical bond formation between Cu and PTFE could enlarge the adhesion strength of Cu/PTFE.

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Synthesis of Potential COX-2 Inhibitory 1,5-Diarylhydantoin Derivatives (잠재적 COX-2 억제작용이 있는 1,5-Diarylhydantoin유도체의 합성)

  • 권순경;박해선
    • YAKHAK HOEJI
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    • v.48 no.2
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    • pp.135-140
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    • 2004
  • For the development of new COX-2 inhibitors, 1,5-diarylhydantoins 5a∼5c and 1,5-diaryl-2-thiohydantoin 6a∼6c were synthesized from commercially available phenylacetic acids through esterification, bromination, C-N bond formation and cyclization. Esters 2a∼c were efficiently synthesized from the starting materials 1a∼c by refluxing in absolute methanol for 3 hours with catalytic concentrated sulfuric acid. Bromination of 2a∼c was carried out with use of N-bomosuccinimide at rt in dichloromethane. The bromine of 3a∼c was substituted with aniline in ethanol or N,N-dimethylformamide to provide 4a∼c. Hydantoins and 2-thiohydantoins were synthesized from 4a∼c by treatment of potassium isocyanate or potassium thiocyanate in dil-ethanol with triethylamine.

Bonding Behavior of Alumina Ceramic to Metals (알루미나 세라믹과 금속과의 접합거동)

  • 김종희;김정태
    • Journal of the Korean Ceramic Society
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    • v.16 no.3
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    • pp.169-177
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    • 1979
  • The effect of apparent porosity of the fired ceramics, metallizing temperature, and metallizing mixtures on the bond strength in metal-to-ceramic seals was investigated. Three different metallizing compounds were metallized on dense alumina bodies at 1300~$1500^{\circ}C$ in dry hydrogen atmosphere. Bond strength between metal and alumina body was measured by means of nstron test machine. The greater bond strength was observed as the apparent porosity and metallizing temperature was increased. This work indicated that the glassy phase in metallizing mixture, having had sufficient fluidity to migrate into the alumina body, reacted with alumina and thereby forming strong metal-ceramic interface bond. It also showed that the glassy phase having higher thermal expansion cofficient than molybdenum might contribute to the strong bond formation by providing compressive stress around the molybdenum particle.

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