• 제목/요약/키워드: C-C bond activation

검색결과 79건 처리시간 0.023초

Effect of silane activation on shear bond strength of fiber-reinforced composite post to resin cement

  • Kim, Hyun-Dong;Lee, Joo-Hee;Ahn, Kang-Min;Kim, Hee-Sun;Cha, Hyun-Suk
    • The Journal of Advanced Prosthodontics
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    • 제5권2호
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    • pp.104-109
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    • 2013
  • PURPOSE. Among the surface treatment methods suggested to enhance the adhesion of resin cement to fiberreinforced composite posts, conflicting results have been obtained with silanization. In this study, the effects of silanization, heat activation after silanization, on the bond strength between fiber-reinforced composite post and resin cement were determined. MATERIALS AND METHODS. Six groups (n=7) were established to evaluate two types of fiber post (FRC Postec Plus, D.T. Light Post) and three surface treatments (no treatment; air drying; drying at $38^{\circ}C$). Every specimen were bonded with dual-curing resin cement (Variolink N) and stored in distilled water for 24 hours at $37^{\circ}C$. Shear-bond strength (MPa) between the fiber post and the resin cement were measured using universal testing device. The data were analyzed with 1-way ANOVA and by multiple comparisons according to Tukey's HSD (${\alpha}$=0.05). The effect of surface treatment, fiber post type, and the interactions between these two factors were analyzed using 2-way ANOVA and independent sample T-tests. RESULTS. Silanization of the FRC Postec Plus significantly increased bond strength compared with the respective non-treated control, whereas no effect was determined for the D.T. Light Post. Heat drying the silane coupling agent on to the fiberreinforced post did not significantly improve bond strength compared to air-syringe drying. CONCLUSION. The bond strength between the fiber-reinforced post and the resin cement was significantly increased with silanization in regards to the FRC Postec Plus post. Bond strength was not significantly improved by heat activation of the silane coupling agent.

$^{13}C$ NMR Studies of the Chelate Ring Opening-Closing Process in (Nitrilotriacetato)vanadate(V) dioxovandate(V) Ion

  • Lee, Man-Ho;Schaumburg, Kjeld
    • Bulletin of the Korean Chemical Society
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    • 제11권5호
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    • pp.399-402
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    • 1990
  • Activation parameters of the exchange between two types of glycinate groups in (nitrilotriacetato)dioxovanadate(V) ion, $[VO_2(NTA)]^{2-}$, have been determined as the results of $^{13}C$ NMR measurements over a range of temperatures between 277 and 306$^{\circ}K$. The exchange mechanism is proposed on the basis of the chelate ring opening-closing process, assuming rupture of the metal-oxygen (glycinate) bond trans to V = O bond to give a five-coordinated intermediate.

Transition Metal-Catalyzed Ortho-Functionalization in Organic Synthesis

  • Park, Young-Jun;Jun, Chul-ho
    • Bulletin of the Korean Chemical Society
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    • 제26권6호
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    • pp.871-877
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    • 2005
  • Recent progress in the filed of transition-metal mediated C-H bond activation has had a great influence on organic synthesis. Among such transition-metal catalyzed reactions, ortho-functionalization via the chelationassisted strategy has been paid great attentions as one of the powerful methodologies for converting aromatic compounds into ones that are more functionalized at the exclusively ortho-position. In this context, various transition metal-catalyzed ortho-functionalizations such as alkylation, alkenylation, silylation and carbonylation are described briefly and their prospects are suggested.

Geometries and Energies of S$_N$2 Transition States$^\dag$

  • Lee, Ik-Choon;Kim, Chan-Kyung;Song, Chang-Hyun
    • Bulletin of the Korean Chemical Society
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    • 제7권5호
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    • pp.391-395
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    • 1986
  • MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

Ab initio Studies on the Hetero Diels-Alder Cycloaddition

  • 이본수;김찬경;최정욱;이익준
    • Bulletin of the Korean Chemical Society
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    • 제17권9호
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    • pp.849-853
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    • 1996
  • Hetero Dieis-Alder reactions containing phosphorus atom at various positions of diene and dienophile as well as standard Dieis-Alder reaction between ethylene and cis-l,3-butadiene have been studied using ab initio method. Activation energy showed a good linear relationship with the FMO energy gap between diene and dienophile, which can be normally used to explain Dieis-Alder reactivity. Since π-bond cleavage and σ-bonds formation occur concertedly at the TS, geometrical distortion of diene and dienophile from the reactant to the transition state is the source of barrier. Based on the linear correlations between activation barrier and deformation energy, and between deformation energy and π-bond order change, it was concluded that the activation barrier arises mainly from the breakage of π-bonds in diene and dienophile. Stabilization due to favorable orbital interaction is relatively small. The geometrical distortions raise MO levels of the TS, which is the origin of the activation energy. The lower barrier for the reactions of phosphorus containing dienophile (reactions C, D, and E) can be explained by the electronegativity effect of the phosphorus atom.

Zeolite-catalyzed Isomerization of 1-Hexene to trans-2-Hexene: An ONIOM Study

  • Li, Yan-Feng;Zhu, Ji-Qin;Liu, Hui;He, Peng;Wang, Peng;Tian, Hui-Ping
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1851-1858
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    • 2011
  • Details of the double-bond isomerization of 1-hexene over H-ZSM-5 were clarified using density functional theory. It is found that the reaction proceeds by a mechanism which involves the Br${\o}$nsted acid part of the zeolite solely. According to this mechanism, 1-hexene is first physically adsorbed on the acidic site, and then, the acidic proton transfers to one carbon atom of the double bond, while the other carbon atom of the double bond bonds with the Br${\o}$nsted host oxygen, yielding a stable alkoxy intermediate. Thereafter, the Br${\o}$nsted host oxygen abstracts a hydrogen atom from the $C_6H_{13}$ fragment and the C-O bond is broken, restoring the acidic site and yielding trans-2-hexene. The calculated activation barrier is 12.65 kcal/mol, which is in good agreement with the experimental value. These results well explain the energetic aspects during the course of double-bond isomerization and extend the understanding of the nature of the zeolite active sites.