• Title/Summary/Keyword: C-O bond

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Insecticidal Activation Mechanism of m-Methylphenyl N-methylcarbamate Derivatives (m-Methylphenyl N-methylcarbamate 유도체들의 살충활성 메카니즘)

  • Park, Seung-Heui;Nam, Sang-Kil;Sung, Nack-Do
    • Korean Journal of Agricultural Science
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    • v.22 no.2
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    • pp.127-133
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    • 1995
  • A Series of meta and para-substituted phenyl N-methylcarbamate derivatives were synthesized and influence of substituents(X) on the molecular orbital(MO) quantities of carbonyl group, carbamylation reaction center, and insecticidal activities($pI_50$) were discussed quantitatively. From these findings, the most stable streo conformer(Z) shows that the planer phenyl group occupies vertical(${\theta}=90^{\circ}$) position on the plane of the N-methylcarbamyl group. The carbamylation mechanism was proposed that the carbamylation process of acetylcholinesterase(ACh.E) by m-methyl substituted phenyl N-methylcarbamate derivatives proceeds via hyperconjugation of m-methyl group and carbonyl oxygene protonation, theromodynamically control reaction with acidic site of ACh.E.

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LS-MOCVD OF BARIUM STRONTIUM TITANATE THIN FILMS USING NOVEL PRECURSORS

  • Kwon, Hyun-Goo;Oh, Young-Woo;Park, Jung-Woo;Lee, Young-Kuk;Kim, Chang-Gyoun;Kim, Do-Jin;Kim, Yunsoo
    • Proceedings of the Korea Crystallographic Association Conference
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    • 2002.11a
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    • pp.19-19
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    • 2002
  • Perovskite-type titanate dielectrics have attracted much attention in memory devices such as DRAMs or FeRAMs due to their high dielectric constants. However, low volatility of the Ba, Sr, Pb or Zr precursors with only thd ligands has limitations in obtaining high quality thin films by liquid source metal organic chemical vapor deposition (LS-MOCVD) processes. To improve the volatility of these precursors, many attempts have been made such as adding polyether ligands to satisfy the coordinative saturation. We report the synthesis of new precursors Ba(thd)₂(tmeea) and Sr(thd)₂(tmeea), where tmeea = tris[2-(2-methoxyethoxy)ethyl]amino, and LS-MOCVD of barium strontium titanate (BSTO) thin films using these precursors. Due to increased basicity of amines compared with ethers, it is expected that the nitrogen-donor ligand will make a strong bond to a metal than an analogous oxygen-donor ligand, consequently improving the volatility and thermal behavior of these precursors. Thin films of BSTO were grown on Pt(111)/SiO₂/Si(100) substrates by LS-MOCVD using a cocktail source consisting of the conventional Ti precursor Ti(thd)₂(O/sup i/Pr), and these new Ba and Sr precursors. As-grown films were characterized by XPS, SEM, XRD, XRF, and C-V and I-V measurements. BSTO films grown at 420℃ were stoichiometric barium strontium titanate with very smooth surface morphology and their dielectric constants were found to be as targe as 450. Dependence of the composition, microstructure and the electrical properties of the BSTO films on the growth temperature, annealing temperature, working pressure, and the composition of the cocktail source will be discussed.

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Effects of Plasma Surface Treatments Using Dielectric Barrier Discharge to Improve Diamond Films

  • Kang, In-Je;Ko, Min-Guk;Rai, Suresh;Yang, Jong-Keun;Lee, Heon-Ju
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.552-552
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    • 2013
  • In our study we consider Al2O3 ceramic substrates for Plasma Surface Treatments in order to improve deposited diamond surface and increase diamond deposition rate by applying DBD (Dielectric Barrier Dischrge) system. Because Plasma Surface Treatments was used as a modification method of material surface properties like surface free energy, wettability, and adhesion. By applying Plasma Surface Treatments diamond films are deposited on the Al2O3 ceramic substrates. DC Arc Plasmatron with mathane and hydrogen gases is used. Deposited diamond films are investigated by SEM (Scanning Electron Microscopy), AFM (Atomic Force Microscopy) and XRD (X-ray Diffractometer). Then the C-H stretching of synthetic diamond films by FTIR (Fourier Transform Infrared Spectroscopy) is studied. As a result, nanocrystalline diamond films were identified by using SEM and diamond properties in XRD peaks at (111, $43.8{\Box}$, (220, $75.3{\Box}$ and (311, $90.4{\Box}$ were shown. Absorption peaks in FTIR spectrum, caused by CHx sp3 bond stretching of CVD diamond films, were identified as well. Finally, we improved such parameters as depostion rate ($2.3{\mu}m$/h), diamond surface uniformity, and impurities level by applying Plasma Surface Treatments. These experimental results show the importance of Plasma Surface Treatments for diamond deposition by a plasma source.

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Macro and Micro-electrochemical Characteristics on Dissimilar Welding Metal of Double Wall Gas Pipe for Duel Fuel Engine (이중 연료 엔진용 이중벽 가스 배관 이종 용접부의 매크로 및 마이크로 전기화학적 특성)

  • Kim, Seong-Jong;Park, Jae-Cheul;Han, Min-Su;Jang, Seok-Ki
    • Corrosion Science and Technology
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    • v.9 no.6
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    • pp.331-337
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    • 2010
  • This study compared the macro and micro electrochemical characteristics at the local area of welding metal on dissimilar welding parts for type 304 stainless steel (SS) and type 316L SS. The materials are used for double wall gas pipe of duel fuel engine for a ship. The various potentiodynamic experiments were performed several times in 10% ${H_2C_2O_2}{\cdot}{H_2O}$ solution using macro and micro methods, respectively. The micro electrochemical experiments conducted to resolve at local area on cross-section of dissimilar welding materials by micro-droplet cell device. The micro-droplet cell techniques can be used almost electrochemical experiments to resolve corrosion characteristics of the limited electrode area of the metallic surface between wetted spot of working electrode and tip of sharpened capillary tube. The results of macro electrochemical experiments show that resistance of active dissolution reaction at welding zone was high due to low current density by formation of passivation protection film at passive region. According to the micro electrochemical experiment, the corrosion current density of welding zone and bond zone were relatively high.

Electrospray ionization tandem mass fragmentation pattern of camostat and its degradation product, 4-(4-guanidinobenzoyloxy)phenylacetic acid (Camostat 및 분해산물 4-(4-guanidinobenzoyloxy)phenylacetic acid의 전자분무 이온화 텐덤 질량 fragmentation 패턴)

  • Kwon, Soon-Ho;Shin, Hye-Jin;Park, Ji-Myeong;Lee, Kyoung-Ryul;Kim, Young-Jin;Lee, Sang-Hoo
    • Analytical Science and Technology
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    • v.24 no.2
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    • pp.78-84
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    • 2011
  • The fragmentation patterns of a serine protease inhibitor, camostat, and its degradation product, 4-(4-guanidinobenzoyloxy)phenylacetic acid (GBPA), were for the first time investigated by a triple quadrupole tandem mass spectrometry equipped with an electrospray source (ESI-MS/MS) in positive and/or negative ion mode under collision-induced dissociation (CID). The positive CID spectrum of camostat showed distinctly that the single bond (C-O) cleavage between carbonyl group and oxygen atom of the ester bonds of the compound favorably occurred and then the loss of N,N-dimethylcarbamoylmethyl group was more susceptible than that of guanidine moiety. In the positive ion CID spectrum of GBPA, the initial cleavage between the carbonyl group and oxygen atom of 4-guanidinobenzoyloxy group also occurred, yielding the most abundant fragment ion at m/z 145. On the other hand, the negative CID spectrum of GBPA characteristically showed the occurrence of the most abundant peak at m/z 226 resulting from the sequential neutral losses of $CO_2$ and HN=C=NH from the parent ion at m/z 312.

Studies on the Quaternization of Tertiary Amines (I). Kinetics and Mechanism for the Reaction of Phenethyltosylate with Substituted Pyridines (3 차아민의 4 차화반응에 관한 연구 (제1보). Phenethyltosylate 와 치환 피리딘류의 반응에 관한 반응 속도론적 연구)

  • Kyung-A Lee;Kyu-Tag Howang;Soo-Dong Yoh
    • Journal of the Korean Chemical Society
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    • v.23 no.4
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    • pp.243-247
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    • 1979
  • Kinetics of the reaction of phenethyltosylate with substituted pyridines at 50, 60 and 70$^{\circ}C$ in acetonitrile were investigated by an electric conductivity method. The effects of substituents on the reaction of phenethyltosylate with pyridines were discussed. The rates of reaction were increased with electron donating power of substituents of pyridines. The isokinetic relationship was shown $E_{\alpha}$ and ${\Delta}S^{\neq}$, it's temperature was 240$^{\circ}$K. Bronsted plots were excellent linear except for 4-amino pyridine given by the following equation, logk=O. 22pKa-3.71 (r=O. 986). According to a plot of log k against Hammett substituent constants, the Iinearity was good except for bamino pyridine too, log k= -1.330${\sigma}$+0.08 (r= -0.987). In both cases, deviation of 4-amino pyridine from linearity was considered to solvent effect, resonance effect and ${\sigma}$ value itself. From all the above results, this reaction was found typical $S_N2$ reaction which the rates of reaction was determined by C…N bond formation at transition state.

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Biosorption and Desorption of Heavy Metals using Undaria sp. (미역 폐기물의 중금속 흡탈착 특성)

  • Cho, Ju-Sik;Park, Il-Nam;Heo, Jong-Soo;Lee, Young-Seak
    • Korean Journal of Environmental Agriculture
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    • v.23 no.2
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    • pp.92-98
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    • 2004
  • The adsorption and desorption of Pb, Cd, Co, Zn, Cr, Co, Ni, and Mo on the waste Undaria sp. were studied. Except for Pb. the mono adsorption rate for all heavy metals were lower than that of the heavy metals mixed. However, the adsorption capacity of the heavy metals by 1g of biosorption, in mixed heavy metals increased According to FT-IR analysis of the biosorbent after heavy metal biosorption, the replacement of the functional group by the heavy metals ions could be confirmed and the inverted peaks became larger after heavy metals adsorption. The adsorption equilibrium of heavy metals was reached in about 1 hour. The equilibrium parameters were determined based on Langmuir and Freundlich isotherms. The affinity of metals on the biosorbent decreased in the following order: Pb>Cu>Cr>Cd>Co. The desorption rate decreased in the following sequence: NTA>$H_2SO_4$>HCl>EDTA. The desorption rate of heavy metals by NTA increased with increase in the concentration from 0.1 to 0.3% but the desorption rate became constant beyond 0.3%. Therefore, it represented that desorption rate of heavy metals was suitable under optimized condition ($30^{\circ}C$, pH 2 and 0.3% NTA solution) and was fast with 80% or more the uptake occurring within 10 min of contact time.

Origin of Decreasing the Dielectric Constant and the Effect of Ionic Polarization (유전상수가 낮아지는 원인과 이온 분극의 효과)

  • Oh, Teresa
    • Journal of the Korean Vacuum Society
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    • v.18 no.6
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    • pp.453-458
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    • 2009
  • SiOC film was deposited by the chemical vapor deposition using BTMSM and oxygen mixed precursor. The characteristic of SiOC film varied with increasing of the gas flow rate ratios. The dielectric constant was obtained by C-V measurement using the structure of metal/SiOC film/Si. The space effect due to the steric hindrance between alkyl group at terminal bond of Si-$CH_3$ made the pores, and increased the thickness. However, the SiOC film due to the lowering of the polarization decreased the thickness and then decreased the dielectric constant. After annealing process, the dielectric constant decreased because of the evaporation of the OH or $H_2O$ sites. The thickness was related to the lowering of the dielectric constant by the reduction of the polarization and the thickness decreased with the decrease of the dielectric constant. The refractive index was in inverse proportion to thickness. The trends of the thickness and refractive index did not change after annealing.

Preparation of Tenoxicam Salt with Ethanolamine to Enhance the Percutaneous Absorption (테녹시캄의 피부 흡수율을 증진시키기 위한 에탄올아민염의 제조)

  • Gwak, Byung-Tae;Chun, Myung-Kwan;Choi, Hoo-Kyun
    • Journal of Pharmaceutical Investigation
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    • v.36 no.3
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    • pp.169-174
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    • 2006
  • The aim of this work was to prepare tenoxicam-ethanolamine salt with improved physicochemical properties for transdermal application. Tenoxicam-ethanolamine salt was prepared in methylene chloride and its physicochemical properties were investigated by DSC and FT-lR. The broad peak of tenoxicam around 3600-3200 $cm^-1$ was shifted to lower wavenumber and more broadened. The characteristic endothermic melting peak of tenoxicam appeared at $223^{\circ}C$. The melting peak of tenoxicam-ethanolamine salt was shifted to $159^{\circ}C$. In contrast to relatively small difference in the partition coefficients of tenoxicam and the tenoxicam-ethanolamine salt, large difference in aqueous solubility was observed. $Crovol^{\circledR}$ PK4O (PEG-12 palm kernel glycerides) provided the highest skin flux for both compounds. The order of the enhancing effect of the various vehicles tested was similar for tenoxicam and tenoxicam-ethanolamine salt, which indicated that their enhancing mechanism for tenoxicam and tenoxicam-ethanolamine salt is similar. Tenoxicam-ethanolamine salt had a higher skin flux than tenoxicam by 1.2- to 31.7-fold, depending on the vehicles used. It is suggested that the vehicles with medium HLB value, 1 double bond, and lower ethylene oxide chain length have a better ability to modify the permeability of the stratum corneum and to promote the effective penetration of tenoxicam and tenoxicam-ethanolamine salt.

Substituents Effect on Aziridine Chemistry: N-Inversion Energy, Reactivity and Regioselectivity of Nucleophilic Ring-opening

  • Park, Gyoo-Soon;Kim, Seok-Chan;Kang, Han-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1339-1343
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    • 2005
  • The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.