• 제목/요약/키워드: $S_N1$ mechanism

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Limitations of the Transition State Variation Model(5) Dual Reaction Channels for Solvolysis of Dansyl Chloride

  • Koo In Sun;Lee Ocg-Kyeong;Lee Ikchoon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.4
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    • pp.395-398
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    • 1992
  • Rate of solvolysis of dansyl chloride in aqueous binary mixtures of acetone, methanol and ethanol are reported. Kinetic solvent isotope effects in methanol and product selectivities in alcohol-water mixtures are also reported. Kinetic data are interpreted with the Grunwald-Winstein and Kivinen equations. The value of $k_{CH3OH}/k_{CH3OD}=1.76$ suggests that a general have catalyzed and/or an $S_AN$ pathway is operative in methanol, a less polar solvent. Rate-rate profiles for solvolysis of dansyl chloride in the aqueous binary media indicate a change in reaction channel from $S_AN$ (in less polar media) to $S_N2$ (in more polar media) mechanism.

Dissolution of Nickel Matte in Hydrochloric Acid Solution (염산 용액에서 니켈 Matte의 용해반응)

  • Lee, Hak-Sung
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.686-693
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    • 1992
  • In order to investigate the mechanism of dissolutin of nickel from a matte composed essentially of heazlewoodite and ferronickel, the leaching in an aqueous solution of hydrochloric was carried out at $50-90^{\circ}C$, 0.5-3.ON HCl, and with the particle sizes between $100-160{\mu}m$ and $400-500{\mu}m$. The leaching rate of heazlewoodite was much rapider than that of ferronickel, and the two components were simultaneously dissolved with different reaction rates. Within the experimental range, NiS, an intermediate, was not formed. However a possibility to form a thin layer of NiS on particle surface upon saturating the reaction mixture with $H_2S$ was not excluded. At the initial stage, the activation energy was about 10 kcal/g mol. The reaction occurred at the particle surface, and consequently the particle size decreased with time. The rate of dissoultion for nickel was linearly proportional to the concentration of HCl up to 1.0N.

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Structure-Reactivity Relationship of Benzylbenzenesulfonates (Part Ⅰ.) Mechanism of the Reaction of Benzylbenzenesulfonates with Pyridines (Benzylbenzenesulfonate류의 구조-반응성 관계 (1 보). Benylbenzenesulfonate류와 피리딘류의 반응 메카니즘)

  • Duk-Young Cheong;Jong-Hwan Park;Jeong-Min Kweon;Soo-Dong Yoh;Kwang-Taik Shim
    • Journal of the Korean Chemical Society
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    • v.38 no.12
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    • pp.915-920
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    • 1994
  • The Menschutkin type reactions of substituted (Z)-benzyl (X)-arenesulfonates with substituted(Y)-pyridines were studied by the electroconductometric method in acetonitrile at $35\circC$. Hammett $\rho$ values were calculated by the second order rate constants for the reaction of substituted (Z)-benzyl (X)-arenesulfonates with substituted (Y)-pyridines. The negative $\rho_Y$ values meant positive charge development on the nitrogen of pyridine at transition state owing to the charge development on the oxygen atom of benzenesulfonate. And the negative $\rho_Z$ values meant positive charge development on the benzylic carbon. Application of the multi-Hammett interaction,│$\rho_YZ$│ > │$\rho_XY$│ > │$\rho_ZX$│, the Menschutkin type reaction of substituted benzyl arenesulfonates with substituted pyridines was shown to be dissociative $S_N2$ mechanism.

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Design of Defence Mechanism against DDoS Attacks in NCP-based Broadband Convergence Networks (NCP 기반의 광대역 융합 망에서 DDoS 공격 대응 기법 설계)

  • Han, Kyeong-Eun;Yang, Won-Hyuk;Yoo, Kyung-Min;Yoo, Jae-Young;Kim, Young-Sun;Kim, Young-Chon
    • The Journal of Korean Institute of Communications and Information Sciences
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    • v.35 no.1B
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    • pp.8-19
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    • 2010
  • In this paper, we propose the NCP (Network Control Platform)-based defense mechanism against DDoS (Distributed Denial of Service) attacks in order to guarantee the transmission of normal traffic and prevent the flood of abnormal traffic. We also define defense modules, the threshold and packet drop-rate used for the response against DDoS attacks. NCP analyzes whether DDoS attacks are occurred or not based on the flow and queue information collected from SR (Source Router) and VR (Victim Router). Attack packets are dopped according to drop rate decided from NCP. The performance is simulated using OPNET and evaluated in terms of the queue size of both SR and VR, the transmitted volumes of legitimate and attack packets at SR.

Characterization of Putrescine Uptake in Hamster Amelanocytic Melanoma AMEL-3 Cells

  • Garcia-Fernandez, Antonio J.;Rodriguez, Rosa A.;Perez-Pertejo, Yolanda;Balana-Fouce, Rafael
    • Molecules and Cells
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    • v.20 no.1
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    • pp.127-135
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    • 2005
  • The uptake of putrescine, spermidine and spermine by Fortner's hamster amelanocytic melanoma AMEL-3 cells was observed in this study to be time-dependent, temperature-sensitive, pH-dependent and saturable. Metabolic poisons nullified polyamine uptake, an indication that this is an energy-requiring mechanism. The presence of $Na^+$ ions was found to be requisite to full activity. Valinomycin, gramicidin, monensin and the calcium ionophore calcimycin were also observed to inhibit the process substantially. The transporter active site would seem to contain sulfhydryl groups. Other diamines and polyamine analogues, as well as cationic diamidines, suppressed putrescine uptake. The presence of the ornithine decarboxylase inhibitor DFMO in the culture medium induced putrescine inflows. Putrescine, in turn, induced the negative expression of the carrier, thus suggesting that this influx mechanism is governed by up/down regulation. The cationic diamidine CGP 40215A and its analogue CGP039937A competitively inhibited putrescine transport, with Ki values of 1.9 and $15{\mu}M$, respectively. The role of polyamine uptake in these cultures is discussed.

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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$\pi$-A Isotherms and Electrical Properties of Polyamic acid Alkylamine salts(PAAS) Langmuir-Blodgett Films

  • Kim, Tae-Wan;Park, Jun-Su;Cho, Jong-Sun;Kang, Dou-Yol
    • Electrical & Electronic Materials
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    • v.11 no.10
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    • pp.60-65
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    • 1998
  • Deposition conditions, surface morphology, and electrical properties of polyamic acid alkylamine salts (PAAS) Langmuir-Blodgett(LB) films have been investigated through a study of surface pressure-area $\pi$-A isotherms, AFM (atomic force microscopy), and current-voltage characteristics. To obtain the optimum conditions of film deposition, the $\pi$-A isotherms were examined by varying temperature, barrier moving speed, dipping speed, spreading amount of solution etc. The Z-type LB films were made at the surface pressure of 5 mN m-1 and 25 mN m-1 for the AFM study; the former surface pressure forms the gas phase and the latter one forms the solid phase. The LB film made in the gas phase show domains with a size of about 200 A diameter and 70 A height. However, the LB films made in the solid phase show a very smooth surface with 2 A surface roughness. In the current-voltage characteristics measured along the perpendicular direction of the films, ohmic conduction has been observed below 105 V cm-1 and the calculated electrical conductivity is about 10-13 S cm-1. Nonohmic conduction has been observed above = 10-11 V cm and the conduction mechanism can be explained by the Schottky effect.

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Effects of Isopropyl Alcohol Infusions on the Ruminating Behavior of Goats

  • Asato, N.;Hirata, T.;Hirayama, T.;Onodera, R.;Shinjo, A.;Oshiro, S.
    • Asian-Australasian Journal of Animal Sciences
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    • v.14 no.8
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    • pp.1085-1089
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    • 2001
  • Metabolites, such as isopropyl alcohol (IPA) produced by rumen fermentation, were intravenously infused into a jugular vein of goats during feeding to explore the mechanism and roles of IPA in ruminating behavior (number of boli and ruminating time). Three female goats were confined in metabolism cages with a stanchion, The ruminating behavior measured by the number of ruminations, ruminating time, number of remastications, and remasticating time decreased (p<0,05) with intravenous IPA infusion. The IPA concentrations and VFA concentrations increased in the blood circulation. Our data suggest that sensitive receptors of rumination to IPA are more likely to be in an area such as the brain stem where they can respond to blood metabolite levels.

Kinetics in Phase Transfer Catalysis with Heterogeneous Liquid-Liquid System (액-액 불균일계에서 상이동촉매의 반응속도론 해석)

  • Park, Sang-Wook;Moon, Jin-Bok;Hwang, Kyong-Son
    • Applied Chemistry for Engineering
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    • v.5 no.2
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    • pp.230-237
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    • 1994
  • The reaction conversions of n-butyl acetate in the alkaline hydrolysis of n-butyl acetate by Aliquat 336 were measured in a flat agitator and a dispersion agitator. These measured data was used to analyze the complicated reaction mechanism of the liquid-liquid heterogeneous reaction by a phase transfer catalyst with a pseudo-first order reaction model, a interfacial reaction model and a bulk-body reaction model. The pseudo-firsts order reaction model and the interfacial reaction model could be explained by the experimental data from the dispersion agitator and the bulk-boby reaction model could be explained by those from the flat agitator and the reaction rate constants were $3.1{\times}10^{-4}$, $7.3{\times}10^{-4}$, $6.6m^3/kmol.s$ from these models at $25^{\circ}C$, respectively.

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Chemiluminescence Determination of Balofloxacin Based on Europium (III)-Sensitized KBrO3-Na2S2O4 Reaction in Micellar Medium

  • Zhao, Fang;Qi, Yu;Xiong, Wei
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.204-208
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    • 2012
  • A novel chemiluminescence (CL) flow injection method for the determination of balofloxacin is described. The method is based on the weak CL signal arising from the reaction of $KBrO_3$ with $Na_2S_2O_4$ in acidic medium being significantly enhanced by balofloxacin in the presence of europium (III) ion and sodium dodecyl benzene sulfonate (SDBS). The experimental conditions that affected CL intensity were carefully optimized and the CL reaction mechanism was briefly discussed. Under the optimum conditions, the relative CL intensity was proportional to the concentration of balofloxacin in the range of $7.0{\times}10^{-11}$ to $3.0{\times}10^{-7}g\;mL^{-1}$. The detection limit was $2.7{\times}10^{-11}g\;mL^{-1}$ and the relative standard deviation was 2.1% for $7.0{\times}10^{-10}g\;mL^{-1}$ balofloxacin (n = 13). The proposed method was successfully applied to the determination of balofloxacin in pharmaceutical formulations and biological fluids.