• Title/Summary/Keyword: C-O bond

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Kinetic Study on Aminolysis of Y-Substituted-Phenyl X-Substituted-Benzoates: Effects of Substituents X and Y on Reactivity and Reaction Mechanism

  • Jeon, Seong Hoon;Kim, Hyun Soo;Han, Young Joon;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.471-476
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    • 2014
  • A kinetic study on aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (2a-k) in 80 mol % $H_2O/_20mol%$ DMSO at $25.0^{\circ}C$ is reported. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (2g) with a series of cyclic secondary amines curves downward (e.g., ${\beta}_1=0.25$, ${\beta}_2=0.85$ and $pK_a^o=10.3$), which is typical of reactions reported to proceed through a stepwise mechanism with a change in ratedetermining step (RDS). The Hammett plot for the reactions of 2a-k with piperidine consists of two intersecting straight lines, while the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X=1.15$ and r = 0.59. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in RDS but is caused by stabilization of substrates through resonance interactions between the electron-donating substituent and the C=O bond. Substrates possessing a substituent at the 2-position of the leaving aryloxide deviate negatively from the curved Br${\emptyset}$nsted-type plot for the reactions of Y-substituted-phenyl benzoates (3a-i), implying that the steric hindrance exerted by the substituent at the 2-position is an important factor which governs the reactivity of Y-substituted-phenyl benzoates.

Effects of air-abrasion pressure on the resin bond strength to zirconia: a combined cyclic loading and thermocycling aging study

  • Al-Shehri, Eman Z.;Al-Zain, Afnan O.;Sabrah, Alaa H.;Al-Angari, Sarah S.;Dehailan, Laila Al;Eckert, George J.;Ozcan, Mutlu;Platt, Jeffrey A.;Bottino, Marco C.
    • Restorative Dentistry and Endodontics
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    • v.42 no.3
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    • pp.206-215
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    • 2017
  • Objectives: To determine the combined effect of fatigue cyclic loading and thermocycling (CLTC) on the shear bond strength (SBS) of a resin cement to zirconia surfaces that were previously air-abraded with aluminum oxide ($Al_2O_3$) particles at different pressures. Materials and Methods: Seventy-two cuboid zirconia specimens were prepared and randomly assigned to 3 groups according to the air-abrasion pressures (1, 2, and 2.8 bar), and each group was further divided into 2 groups depending on aging parameters (n = 12). Panavia F 2.0 was placed on pre-conditioned zirconia surfaces, and SBS testing was performed either after 24 hours or 10,000 fatigue cycles (cyclic loading) and 5,000 thermocycles. Non-contact profilometry was used to measure surface roughness. Failure modes were evaluated under optical and scanning electron microscopy. The data were analyzed using 2-way analysis of variance and ${\chi}^2$ tests (${\alpha}=0.05$). Results: The 2.8 bar group showed significantly higher surface roughness compared to the 1 bar group (p < 0.05). The interaction between pressure and time/cycling was not significant on SBS, and pressure did not have a significant effect either. SBS was significantly higher (p = 0.006) for 24 hours storage compared to CLTC. The 2 bar-CLTC group presented significantly higher percentage of pre-test failure during fatigue compared to the other groups. Mixed-failure mode was more frequent than adhesive failure. Conclusions: CLTC significantly decreased the SBS values regardless of the air-abrasion pressure used.

High Selective Oxidation of Alcohols Based on Trivalent Ion (Cr3+ and Co3+) Complexes Anchored on MCM-41 as Heterogeneous Catalysts

  • Shojaei, Abdollah Fallah;Rafie, Mahboubeh Delavar;Loghmani, Mohammad Hassan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2748-2752
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    • 2012
  • Cr(III) and Co(III) complexes with acetylacetonate were anchored onto a mesoporous MCM-41 through Schiff condensation. The materials were characterized by XRD, FT-IR, BET, CHN and ICP techniques. Elemental analysis of samples revealed that one C=N bond was formed through Schiff condensation on MCM-41 surface. The catalysts were tested for the alcohol oxidations using t-butyl hydroperoxide (TBHP) and $H_2O_2$ as oxidant. The catalytic experiments were carried out at both room temperature and reflux condition. Various solvents such as dichloromethane, acetonitrile and water were examined in the oxidation of alcohols. Among the different solvents, catalytic activity is found more in acetonitrile. Further, the catalysts were recycled three times in the oxidation of alcohols and no major change in the conversion and selectivity is observed, which shows that the immobilized metal-acetylacetonate complexes are stable under the present reaction conditions.

Synthesis of Cysteine Capped Silver Nanoparticles by Electrochemically Active Biofilm and their Antibacterial Activities

  • Khan, Mohammad Mansoob;Kalathil, Shafeer;Lee, Jin-Tae;Cho, Moo-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2592-2596
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    • 2012
  • Cysteine capped silver nanoparticles (Cys-AgNPs) have been synthesized by employing electrochemically active biofilm (EAB), $AgNO_3$ as precursor and sodium acetate as electron donor in aqueous solution at $30^{\circ}C$. Cys-AgNPs of 5-10 nm were synthesized and characterized by UV-Vis, FT-IR, XRD and TEM. Capping of the silver nanoparticles with cysteine provides stability to nanoparticles by a thiolate bond between the amino acid and the nanoparticle surface and hydrogen bonding among the Cys-AgNPs. In addition, the antibacterial effects of as-synthesized Cys-AgNPs have been tested against two pathogenic bacteria Escherichia coli (O157:H7) and Pseudomonas aeruginosa (PAO1). The results demonstrate that the as-synthesized Cys-AgNPs can proficiently inhibit the growth and multiplication of E. coli and P. aeruginosa.

A Reinvestigation of the Fragmentation of 2-Carbena-1,3-dioxolane by CASSCF and CASPT2 Calculations

  • Park, Bong-Jin;Hrovat, David A.;Borden, Weston Thatcher
    • Bulletin of the Korean Chemical Society
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    • v.25 no.2
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    • pp.260-262
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    • 2004
  • In agreement with the results of previous MP2 calculations by Sauers, B3LYP, CASSCF, and CASPT2 calculations on the parent 2-carbena-1,3-dioxolane show that it fragments to ethylene plus $CO_2$ by a concerted pathway with only a small energy barrier. Not only is fragmentation via stepwise C-O bond cleavage computed to be a much higher energy pathway, but the singlet diradical that would be an intermediate along such a reaction path is not even computed to be a local minimum on the potential energy surface.

Optical Characterization of Azo-dye Attached on Photonic Crystal: The Cause of Large Absorption Band Shift

  • Kim, Byoung-Ju;Kwon, Ki-Chul;Yu, A-Reum;Kang, Kwang-Sun
    • Current Photovoltaic Research
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    • v.5 no.2
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    • pp.43-46
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    • 2017
  • Large absorption band shift has been observed for the azo-dye (disperse red-13, DR-13) attached on the surface of silica spheres. Urethane linkage has been utilized to form covalent bond between azo-dye (-OH) and 3-isocyanatopropyltriethoxysilane (ICPTES, -N=C=O). The synthesized ICPTES-DR-13 (ICPDR) molecules were attached to the silica spheres by the hydrolysis and condensation reaction. Although the absorption peak of DR-13 in methanol is at 510 nm, the absorption peak of the ICPDR-silica spheres shifts to 788 nm. The large absorption peak shift is due to the formation of intramolecular charge-transfer band with large aggregated ICPDR.

Cleaning efficiency for Alternative cleaning solvent of Screen printing (스크린 인쇄에서의 대체세정제에 대한 세정효율)

  • 김재해
    • Journal of the Korean Graphic Arts Communication Society
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    • v.15 no.2
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    • pp.117-130
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    • 1997
  • Studies have been conducted to explore thermal imidization of polyamic acid. Aromatic polyimides are well recognized as high temperature linear polymers, and polyimide are used as structural materials, fibers, and adhesive. Two different kinds of polyimide were prepared by theimidization of polyamic acid which were synthesized from 2,2-bis[4-(4-aminophenoxy)phenyl]- hexafluoropropane, 2,2-bis [4-(4-aminophenxy)phenyl] - hexamethylpropane and caprolactam and pyromelliti dianhydride under N-Methly-pyrrolidinone solvent. Polyamic acids were converted to polyimides containing imide bond by thermal imidization. The weight 50% loss temperatures of polyimide by TGA thermogram were recorded in the range of 700 ~ 720$^{\circ}$C in nitrogen gas. According, as a results, we conclued polyamic acid were cycliation after H2O molecule separationed, and this polyimide film could be used for Printed Circuit Boand.

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Indole Derivatives II. The Kinetics and Mechanism of the Hydrolysis of Indolylacrylophenone Derivatives (인돌 유도체 II. Indolylacrylophenone 유도체의 가수분해 반응에 대한 메카니즘과 그 반응 속도론적 연구)

  • Lee, Ki-Chang;Ryu, Jung-Wook
    • Journal of the Korean Applied Science and Technology
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    • v.9 no.2
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    • pp.119-126
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    • 1992
  • The kinetics of the hydrolysis of indolylacrylophenone derivatives(IA) was investigated by ultraviolet spectrophotometry in 30% dioxane-$H_2O$ at 25$^{\circ}C$ Rate equations were obtained over a wide pH range. On the basis of rate equation, general base catalysis and Hammett's plot, the mechanism of hydrolysis to the (IA) were proposed: Below pH 3.0, the hydrolysis of (IA) was proportional to hydronium ion concentration, between pH 4.0${\sim}$9.0 neutral water molecule and hydroxide ion were added to carbon-carbon double bond and over pH 10.0 hydrolysis of (IA) was proportional to hydroxide ion concentration.

Studies on the Optimum Surface Treatment Conditions and the Interfacial Bond Strength of Glass fiber/Nylon 6 Composites (유리섬유/Nylon 6 복합재료의 표면처리 최적조건과 개별결합력에 관한 연구)

  • 나성기;박종신
    • Proceedings of the Korean Fiber Society Conference
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    • 1997.04a
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    • pp.26-31
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    • 1997
  • 유리섬유/nylon 6 복합재료의 계면결합강도를 증가시키기 위하여 r-APS(r-Aminopropyltriethoxysilane)로 유리섬유의 표면을 처리 하였다. 이때 표면처리의 최적 조건을 찾기위해서 처리후 기기분석과 계면결합강도 측정 등을 하였다. 농도, pH, 처리시간, 온도를 변화시키면서 표면처리를 한 후 흡착량을 살펴본 결과 처리 농도에 의해서는 흡착량이 단조증가하였으며 처리시간에 따라서는 5분정도에서, 처리온도에 의해서는 30C 부근에서 최대 흡착량을 보였다. 또한 pH에 따른 흡착량은 silane의 고유 pH인 10.5부근에서 최대치를 나타냈다. FR-IR 분석에 의하면 NH2의 NH3 bending mode가 1607cm-1, 1575cm-1에서 나타났으며 SiOH의 SiO band는 960cm-1에서 나타났다. XPS를 통해서는 N ls와 Si 2p의 존재를 확인할 수 있었다. 표면처리된 유리섬유와 matrix인 nylon 6를 이용해 단섬유내장시편을 만들어 fragmentation test를 한 결과 계면결합강도는 약 5분의 처리시간과 1%(wt%)의 농도에서 최대값을 보였다.

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The Change of Mechanical Properties on Weld Heat Input in 60kg/mm2 Quenched and Tempered High Strength Steel (60kg/mm2급 조질고장력강의 용접입열량에 따른 기계적 특성 변화)

  • Kim, O.S.;Park, K.C.;Chung, I.S.
    • Journal of the Korean Society for Heat Treatment
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    • v.7 no.1
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    • pp.35-43
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    • 1994
  • For the purpose of studying the change of mechanical properties of weld parts, shielded metal are welding, one-pole and two-pole submerged arc welding were accomplished weldability on $60kg/mm^2$ quenched and tempered high strength steel. Charpy impact values of the weld metal in welded parts by SMAW and SAW were lower than those of the heat affected zone and increased in order of bond, coarsened, refined and carbon spheroidized regions in the heat affected zone. Grain size of prior austenite or M-A constituent did not significantly affect toughness of welded parts, but precipitated carbide films which forms at the grain boundaries or within matrix and volume fraction of pearilte were most important factor for toughness.

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