• Title/Summary/Keyword: Ion formation mechanism

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K+ Ion Catalysis in Nucleophilic Displacement Reaction of Y-Substituted-Phenyl Picolinates with Potassium Ethoxide: Effect of Substituent Y on Reactivity and Transition State Structure

  • Im, Hyun-Ju;Lee, Jieun;Kim, Mi-Yeon;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1749-1753
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    • 2014
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.

Rates and Mechanism of Reduction of Vanadium(V) by Ethanol in Sulfuric Acid (황산용액에서 에탄올에 의한 바나듐(V) 의 환원반응의 속도와 메카니즘)

  • Chang-Su Kim;Woo-Sik Lee
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.409-414
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    • 1986
  • The reduction of $VO_2^+$ ion by ethanol in sulfuric acid leads to the formation of vanadyl sulfate. Spectrophotometric measurements on the solution containing products, vanadyl sulfate, are also reported. Kinetic studies on reduction of $VO_2^+$ by ethanol have been carried out at 35${\circ}C$ and 50${\circ}C$. The reaction mechanism for reduction of $VO_2^+$ is discussed.

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INVESTIGATION OF ENERGETIC DEPOSITION OF Au/Au (001) THIN FILMS BY COMPUTER SIMULATION

  • Zhang, Q. Y.;Pan, Z. Y.;Zhao, G. O.
    • Journal of the Korean Vacuum Society
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    • v.7 no.s1
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    • pp.183-189
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    • 1998
  • A new computer simulation method for film growth, the kinetic Monte Carlo simulation in combination with the results obtained from molecular dynamics simulation for the transient process induced by deposited atoms, was developed. The behavior of energetic atom in Au/Au(100) thin film deposition was investigated by the method. The atomistic mechanism of energetic atom deposition that led to the smoothness enhancement and the relationship between the role of transient process and film growth mechanism were discussed. We found that energetic atoms cannot affect the film growth mode in layer-by-layer at high temperature. However, at temperature of film growth in 3-dimensional mode and in quasi-two-dimensional mode, energetic atoms can enhance the smoothness of film surface. The enhancement of smoothness is caused by the transient mobility of energetic atoms and the suppression for the formation of 3-dimensional islands.

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Kinetic Investigation of Styrene Derivatives Oxidation Mechanism by Mn(III)-porphyrin (Mn(III)-porphyrin에 의한 Styrene 유도체의 산화반응 메카니즘 연구)

  • Na, Hun-Gil
    • Journal of the Korean Applied Science and Technology
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    • v.19 no.3
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    • pp.206-212
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    • 2002
  • The catalytic activities of several metalloporphyrin, wherein the porphyrins are TPP(5,lO,l5,20-Tetraphenyl-21H,23H-porphyrin) and (p-X)TPP (X =$CH_{3}O$, $CH_{3}$, F, Cl), are reported for the oxidation of styrene and it's derivatives. The electronic effects of substrates and porphyrins on the catalytic activity of metalloporphyrin containing the transition metal ion such as Mn(III) was discussed. Investigating the correlation between the Michaelis-Menten's rate parameters and the substituent constants, we are going to analyze the influences on the changes of catalytic activity or rate determining step during the processes of the formation and the dissociation of the M-oxo-olefin.

Reaction Mechanism on the Synthesis of $SrTiO_3$ by Direct Wet Process ($SrTiO_3$ 습식 직접 합성 반응기구에 관한 연구)

  • 이경희;이병하;김대웅
    • Journal of the Korean Ceramic Society
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    • v.23 no.6
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    • pp.45-51
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    • 1986
  • $SrTiO_3$ reaction mechanism formed from $TiCl_4$ and $SrCl_2$ solution by direct-wet-process was studied. Through this study it is identified that crystalline $SrTiO_3$ is formed above pH 13.8 amorphous $SrTiO_3$ above pH7 and crystallization temperature of amorphous $SrTiO_3$ is at 37$0^{\circ}C$. the final products are composed of 60% crystalline $SrTiO_3$ and 40% amorphous $SrTiO_3$ The amorphous $SrTiO_3$ is identified with the IR absorption spectrum of Sr-Ti-O by FT-IR spectrometer. Under pH 7 gelationus metatitanate (H2TiO3) is formed from TiCl4 but above pH7 the activity by the formation of metatitnic acid ion $[TiO_3]^{2-}$ is so high that $SrTiO_3$is formed more easily through the reaction with $Sr^{2+}$.

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Efficiency of an SCM415 Alloy Surface Layer Implanted with Nitrogen Ions by Plasma Source Ion Implantation

  • Lyu, Sung-Ki;He, Hui-Bo;Lu, Long;Youn, Il-Joong
    • International Journal of Precision Engineering and Manufacturing
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    • v.7 no.4
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    • pp.47-50
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    • 2006
  • SCM415 alloy was implanted with nitrogen ions using plasma source ion implantation (PSII), at a dose range of $1{\times}10^{17}\;to\;6{\times}10^{17}\;N^+cm^{-2}$ Auger electron spectrometry (AES) was used to investigate the depth profile of the implanted layer. Friction and wear tests were carried out on a block-on-ring wear tester. Scanning electron microscopy (SEM) was used to observe the micro-morphology of the worn surface. The results revealed that after being implanted with nitrogen ions, the frictional coefficient of the surface layer decreased, and the wear resistance increased with the nitrogen dose. The tribological mechanism was mainly adhesive, and the adhesive wear tended to become weaker oxidative wear with the increase in the nitrogen dose. The effects were mainly attributed to the formation of a hard nitride precipitate and a supersaturated solid solution of nitrogen in the surface layer.

Effect of Transition Metal Ion on the Reaction of Benzylbromide with Grignard Reagent (Grignard 시약과 브로모벤질과의 반응에서 첨가전이 금속이온의 영향 연구)

  • Jack C. Kim;Young-Sim Koh;Ung-Chan Yoon;Min-Sook Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.2
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    • pp.228-236
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    • 1993
  • The effect of ferric ion on the reaction of CH_3$MgI with benzylbromide was investigated by determining the product ratio between cross-coupling product, ethylbenzene (A) and homocoupling product, bibenzyl (B) in the presence of ferric ion. When CH_3$MgI prepared with pure magnesium was used, the ratio of A to B was 22 to 78 and with reagent grade magnesium, the ratio became 33 to 67 indicating that metallic impurities in magnesium affect the reaction mechanism to lead less homocoupling product, B. The ratio changes became significant when ferric chloride was added in the reaction mixture in catalytic amounts and the ratio of A to B reached to 80 to 20 at maximum. The reaction in the presence of ferric ion seems to follow mainly an ionic mechanism which involves iron-benzyl bromide ${\pi}$-complex formation. The complex formation is expected to be able to enhance ionic attack of CH_3$MgI on benzyl carbon to give more A.

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All-trans Retinoic Acid-Associated Low Molecular Weight Water-Soluble Chitosan N anoparticles Based on Ion Complex

  • Kim Dong-Gon;Choi Changyong;Jeong Young-Il;Jang Mi-Kyeong;Nah Jae-Woon;Kang Seong-Koo;Bang Moon-Soo
    • Macromolecular Research
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    • v.14 no.1
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    • pp.66-72
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    • 2006
  • The purpose of this study is to develop novel nanoparticles based on polyion complex formation between low molecular weight water-soluble chitosan (LMWSC) and all-trans retinoic acid (atRA). LMWSC nanoparticles encapsulating atRA based on polyion complex were prepared by mixing of atRA into LMWSC aqueous solution using ultrasonication. In FTIR spectra, the carbonyl group of atRA at 1690 $cm^{-1}$ disappeared or decreased when ion complexes were formed between LMWSC and atRA. In ${1}^H$ NMR spectra, specific peaks of atRA disappeared when atRA-encapsulated LMWSC (RAC) nanoparticles were reconstituted into $D_{2}O$ while specific peaks both of atRA and LMWSC appeared in $D_{2}O$/DMSO (1/3, v/v) mixture. XRD patterns also showed that the crystal peaks of atRA were disappeared by encapsulation into LMWSC nanoparticles. LMWSC nanoparticles encapsulating atRA have spherical shapes with particle size below 200 nm. The mechanism of encapsulation of atRA into LMWSC nanoparticles was thought to be an ion complex formation between LMWSC and atRA. LMWSC nanoparticles showed high atRA loading efficiency over 90$\%$ (w/w). AtRA was continuously released from nanoparticles over 10 days. In in vitro cell cytotoxicity test, free atRA showed higher cytotoxic effect against CT 26 colon carcinoma cell line on 1 day. However, RAC nanoparticles showed similar cytotoxicity against CT 26 cells on 2 day. These results suggest the potential for the introduction of LMWSC nanoparticles into various biomedical fields such as drug delivery.

Antifungal Mechanism of Antifungal Peptide Derived from Cecropin A(1-8)- Melittin(1-12) Hybrid against Aspergillus fumigatus

  • Lee, Dong-Gun;Jin, Zhe-Zhu;Maeng, Cheol-Young;Shin, Song-Yub;Seo, Moo-Yeol;Kim, Kil-Lyong;Hahm, Kyung-Soo
    • Journal of Microbiology and Biotechnology
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    • v.9 no.2
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    • pp.168-172
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    • 1999
  • The antifungal mechanism of the antifungal peptide against Aspergillus fumigatus, $K^{18,19}$-CA(l-8)-ME(l-12), derived from cecropin A(l-8)-melittin(l-12) was investigated by confocal laser scanning microscopy, cell wall regeneration, ATPase activity inhibition, and released potassium ion. By confocal laser scanning microscopy, $K^{18,19}$-CA(l-8)-ME(l-12) was detected on the surface of A. fumigatus, while cecropin A used as a negative control peptide was not detected. The protoplast of A. fumigatus treated with$K^{18,19}$-CA(1-8)-ME(1-12) failed to regenerate the fungal cell walls. Compared with cecropin A, the amount of potassium ion released by $K^{18,19}$-CA(l-8)-ME(l-12) was increased. Furthermore, $K^{18,19}$-CA(l-8)-ME(l-12) inhibited the ATPase activity on the plasma membrane. These results suggested that $K^{18,19}$-CA(l-8)-ME(1-12) acts on the plasma membrane of A. fumigatus and its antifungal action is due to the ion channel or pore formation on the plasma membrane.

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Molecular dynamics study of redeposition effect by Ar ion bombardments on Au, Pd(001) (Ar이온 충돌에 의한 Au, Pd(001) 표면에서 재증착 효과의 분자동역학 연구)

  • Kim, S.P.;Kim, S.J.;Kim, D.Y.;Chung, Y.C.;Lee, K.R.
    • Journal of the Korean Vacuum Society
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    • v.17 no.2
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    • pp.81-89
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    • 2008
  • Atomic behavior during ion beam sputtering was investigated by using classical molecular dynamics simulation. When Ar ion bombards on Au and Pd(001) surface with various incidence energies and angles, some atoms which gained substantial energy by impacting Ar ion were sputtered out and, simultaneously, others were landed on the surface as if surface atoms were redeposited. It was observed that the redeposited atoms are five times for Au and three times for Pd as many as sputtered atoms irrespective of both incidence energy and angle. From sequential ion bombarding calculations, contrary to the conventional concepts which have described the mechanism of surface pattern formation based only on the erosion theory, the redeposition atoms were turned out to play a significant role in forming the surface patterns.