• Title/Summary/Keyword: Expulsion

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Aminolysis of Aryl Thiol-2-furoates and Thiol-2-thiophenates in Acetonitrile

  • 오혁근;이준용;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.19 no.11
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    • pp.1198-1202
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    • 1998
  • Aminolysis of aryl thiol-2-furoates and thiol-2-thiophenates with benzylainines are investigated in acetonitrile at 50.0 ℃. Relatively large selectivity parameters, ρx(βx), ρz(βx) and ρxz (> 0) together with the valid reactivity-selectivity principle are consistent with a stepwise acyl transfer mechanism with rate-limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T±. The first-order kinetics with respect to the benzylamine concentration and the relatively large secondary kinetic isotope effect involving deuterated benzylamine nucleophiles suggest a four-center type transition state in which concurrent leaving group departure and proton transfer are involved.

Kinetics and Reaction Mechanism of Aminolyses of Benzyl 2-Pyridyl Carbonate and t-Butyl 2-Pyridyl Carbonate: Effect of Nonleaving Group on Reactivity and Reaction Mechanism

  • Kang, Ji-Sun;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1551-1555
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    • 2012
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{7}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{8}$ with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. Substrate $\mathbf{8}$ is less reactive than $\mathbf{7}$. Steric hindrance exerted by the bulky $t$-Bu group of $\mathbf{8}$ has been suggested to be responsible for the decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{7}$ and $\mathbf{8}$ are linear with ${\beta}_{nuc}=0.49$ and 0.44, respectively, which is typical for reactions reported previously to proceed through a concerted mechanism. Aminolyses of $\mathbf{7}$ and $\mathbf{8}$ were expected to proceed through a zwitterionic tetrahedral intermediate $T^{\pm}$, which would be stabilized through an intramolecular H-bonding interaction. However, the kinetic results suggest that the reactions proceed through a concerted mechanism. The H-bonding interaction in $T^{\pm}$ has been suggested to accelerate the rate of leaving-group expulsion from $T^{\pm}$. Another factor that might accelerate expulsion of the leaving group is the "push" provided by the RO group in $T^{\pm}$ through resonance interactions. Thus, it has been concluded that the enhanced nucleofugality through the H-bonding interaction and the "push" provided by the RO group forces the reactions to proceed through a concerted mechanism.

Kinetics of Goblet Cells and Mast Cells in the Intestine of C3H/HeN and BALB/c Mice Infected with Echinostoma hortense

  • Im, Jee-Aee;Kim, Insik;Jo, Yoon-Kyung;Lee, Kyu-Jae;Ryang, Yong-Suk
    • Biomedical Science Letters
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    • v.10 no.2
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    • pp.121-128
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    • 2004
  • Mast cells and goblet cells have the ability to protect against parasites by increasing mucus production that traps and excludes worms and prevents their intimate contact with the gut mucosa in the host. In this study, we investigated the function of mast cells and goblet cells for the rejection of Echinostoma hortense (E. hortense). In addition, we used both C3H/HeN and BALB/c mice in order to examine whether mast cells and goblet cells function differentially according to the strains of mice. After an oral infection with 30 E. hortense metacercariae, the number of mucosal mast cells and goblet cells, as well as worm recovery rate, were observed in experimentally infected mice between 1 week and 8 weeks post-infection (PI). Worm recovery rates in C3H/HeN and BALB/c mice were 65.7% and 23%, respectively, in week 1 P.I., indicating that worm expulsion in C3H/HeN mice was higher than in BALB/c mice. Our results demonstrate that the period (week 3 P.I.) in which worm recovery falls rapidly is the same period that the number of goblet cells and mast cells reaches a peak. These results indicate that worm recovery significantly correlates with the growth rate of goblet cells and mast cells (P=0.0482). However, worm expulsion is not associated with goblet cells or mast cells in BALB/c mice.

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Studies on the Desalinization in Reclaimed Tide Lads (II) - by the Open Conduit- (간척지 제염에 관한 시험(II) - 개거에 의한 제염효과 시험-)

  • 정두호
    • Magazine of the Korean Society of Agricultural Engineers
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    • v.12 no.3
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    • pp.2029-2034
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    • 1970
  • This research was attempted to study on the effects of desalinization by the depth and interval of open conduit in Kang-Hwa polder where is located at the Kil-sang Myun, Kang-Hwa Gun, Kyung-gi Do, and it has been continued for the three years from 1967 to 1969. The results obtained are as follows; 1. The depths of saline expulsion by supplying of irrigation water are approximately 30cm to 50cm under the ground surface, but saline expulsion is hardly done in case of the depth which is deeper than the above mentioned, because the moisture and saline content hardly change in such a condition. 2. The speed of vertical percolation gradually decreases below the 30cm depth, but it is noticed that there is a tendency to make the percolation of the horizental direction from its layer in Kang-Hwa reclaimed tidal land. 3. Comparing experimental treatments-varing depths and intervals of open conduits, the interval of open conduit has a more effect upon the promotion of desalinization and increasing of the rice yields than the depth of it. Therefore, according to the results of experimental data, the optimum depth of open conduit is about 0.9m, the effective interval of it is about 18m. 4. Considering the loss of arable area by the layout of open conduit, the reasonable interval of it could extend to 36m.

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The Alteration of Cytokine Expression and Goblet Cell Response by Cyclosporin A and Histamine Receptor Antagonists in C3H/HeN Mice Infected with Echinostoma hortense

  • Jo, Yong-Hee;Kim, In-Sik;Lee, Kyu-Jae;Kim, Jeong-Lye;Lee, Young-Mi;Cho, Kyung-Jin;Ryang, Yong-Suk
    • Biomedical Science Letters
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    • v.12 no.4
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    • pp.329-335
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    • 2006
  • Echinostoma hortense (E. hortense) is an intestinal trematode with the highest infection rate in South Korea. However, the immune response against E. hortense infection has not been explained well. In the present study, we investigated the effect of treatment with cyclosporin A (CsA) and histamine receptor antagonists on the cytokine expression and mucosal goblet cells in E. hortense-infected C3H/HeN mice. The alteration of cytokine mRNA expression ($TNF-{\alpha},\;IL-l{\beta},\;IL-4\;and\;IL-5$), intestinal worm recovery rate and goblet cell responses were measured weekly from 0 to 5 weeks post-infection (P.I.) in the control and the following three drug-treated groups: CsA, hydroxyzine and cimetidine. Compared with the control group, the expression of $TNF-{\alpha}$, IL-4 and IL-5 mRNAs decreased in the CsA- and hydroxyzine-treated groups, but only IL-4 mRNA expression did in the cimetidine-treated group. Worm recovery rate was significantly increased in the drug-treated groups. Mucosal goblet cells and their mucin response significantly decreased in the CsA-treated group (P<0.01), but significantly increased in the cimetidine- (P<0.05) and hydroxyzine- (P<0.01) treated groups. These data suggest that CsA treatment inhibits production of Th1- and Th2-type cytokines which are necessary for the worm expulsion. Histamine receptor increases goblet cells and their mucin activation, although it remains to be elucidated whether it directly affects the worm expulsion period of E. hortense in C3H/HeN mice.

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The α-Effect in SNAr Reaction of Y-Substituted-Phenoxy-2,4-Dinitrobenzenes with Amines: Reaction Mechanism and Origin of the α-Effect

  • Cho, Hyo-Jin;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2448-2452
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    • 2014
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for $S_NAr$ reactions of Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1g) with hydrazine and glycylglycine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Hydrazine is 14.6-23.4 times more reactive than glycylglycine. The magnitude of the ${\alpha}$-effect increases linearly as the substituent Y becomes a stronger electron-withdrawing group (EWG). The Br${\o}$nsted-type plots for the reactions with hydrazine and glycylglycine are linear with ${\beta}_{lg}=-0.21$ and -0.14, respectively, which is typical for reactions reported previously to proceed through a stepwise mechanism with expulsion of the leaving group occurring after rate-determining step (RDS). The Hammett plots correlated with ${\sigma}^{\circ}$ constants result in much better linear correlations than ${\sigma}^-$ constants, indicating that expulsion of the leaving group is not advanced in the transition state (TS). The reaction of 1a-1g with hydrazine has been proposed to proceed through a five-membered cyclic intermediate ($T_{III}$), which is structurally not possible for the reaction with glycylglycine. Stabilization of the intermediate $T_{III}$ through intramolecular H-bonding interaction has been suggested as an origin of the ${\alpha}$-effect exhibited by hydrazine.

Alkali-Metal Ion Catalysis and Inhibition in SNAr Reaction of 1-Halo-2,4-dinitrobenzenes with Alkali-Metal Ethoxides in Anhydrous Ethanol

  • Kim, Min-Young;Ha, Gyu Ho;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2438-2442
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    • 2014
  • A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

Design of DC current waveform for expulsion reduction in resistance spot welding (저항 점 용접에서 날림발생 저감을 위한 DC 펄스전류 파형설계에 관한연구)

  • Hwang, In-Sung;Yeun, Hyun-Joon;Kim, Dong-Cheol;Kang, Mun-Jin
    • Proceedings of the KWS Conference
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    • 2010.05a
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    • pp.39-39
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    • 2010
  • 최근 자동차 산업에서는 차체의 무게를 감소시켜 연비향상과 배기가스의 양을 줄이려는 목적으로 고강도 강재의 차체 적용이 증가하고 있다. 또한 다른 여러 산업에서도 두께 감소를 통한 경량화를 위해 고강도 강재가 사용되고 있다. 고강도 강재를 자동차 차체에 적용하면서 용접성에 대한 새로운 문제가 제기 되고 있으며 그 중 자동차 생산라인에서 차체의 조립공정의 대부분을 차지하는 저항 점 용접에 대한 연구가 중요한 이슈가 되고 있다. 이러한 고강도 강재의 저항 점 용접의 문제점으로는 잦은 날림발생을 들 수 있다. 이는 강도의 증가에 따른 비저항 증가와 필요 가압력의 증가로 인해 입열에 의한 가압부의 소성변형이 쉽게 발생하기 때문이다. 이를 방지하기 위해 현재 다단가압, 다단전류제어 등의 기법들이 시도되고 있다. 본 연구에서는 저항 점 용접의 펄스전류 파형설계를 통해 고강도강 용접의 날림발생을 저감하고자 하였다. 실험소재로는 Al-Si 도금의 1.5GPa 급 강재를 사용하였고 실험조건으로는 기존 로브곡선에서 날림이 발생하는 용접조건을 사용하였다. On/Off 방식의 펄스전류를 이용하여 On/Off 시간에 따른 용접성을 평가하여 이를 기존 용접성과 비교하였다. 또한 펄스전류 파형에 따른 입열과 냉각의 변화와 날림발생에 미치는 영향을 분석하였다.

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Mucosal Immune Responses of Mice Experimentally Infected with Pygidiopsis summa (Trematoda: Heterophyidae)

  • Chai, Jong-Yil;Park, Young-Jin;Park, Jae-Hwan;Jung, Bong-Kwang;Shin, Eun-Hee
    • Parasites, Hosts and Diseases
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    • v.52 no.1
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    • pp.27-33
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    • 2014
  • Mucosal immune responses against Pygidiopsis summa (Trematoda: Heterophyidae) infection were studied in ICR mice. Experimental groups consisted of group 1 (uninfected controls), group 2 (infection with 200 metacercariae), and group 3 (immunosuppression with Depo-Medrol and infection with 200 metacercariae). Worms were recovered in the small intestine at days 1, 3, 5, and 7 post-infection (PI). Intestinal intraepithelial lymphocytes (IEL), mast cells, and goblet cells were counted in intestinal tissue sections stained with Giemsa, astra-blue, and periodic acid-Schiff, respectively. Mucosal IgA levels were measured by ELISA. Expulsion of P. summa from the mouse intestine began to occur from days 3-5 PI which sustained until day 7 PI. The worm expulsion was positively correlated with proliferation of IEL, mast cells, goblet cells, and increase of IgA, although in the case of mast cells significant increase was seen only at day 7 PI. Immunosuppression suppressed all these immune effectors and inhibited worm reduction in the intestine until day 7 PI. The results suggested that various immune effectors which include IEL, goblet cells, mast cells, and IgA play roles in regulating the intestinal mucosal immunity of ICR mice against P. summa infection.

Effect of immunosuppression on Ascaris suum infection in undefinitive hosts II. Investigations in golden hamsters (비고유숙주(非固有宿主)에 있어서 면역억제(免疫抑制)가 돼지회충(蛔蟲)의 감염(感染)에 미치는 영향(影響) II. 햄스터에서의 실험소견(實驗所見))

  • Rhee, Jae-ku;Kim, Hyeon-cheol;Park, Bae-keun;Lee, Chang-hyun
    • Korean Journal of Veterinary Research
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    • v.34 no.1
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    • pp.127-134
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    • 1994
  • As a series of studies to investigate the effect of immunosuppression on Ascaris suum infection in undefinitive hosts, a delicate relationship between host and parasite, in the present studies golden hamsters were alloted to experiment 1(normal undefinitive host group) and experiment 2(immunosuppressive group treated with prednisolone acetate) and inoculated with a single dose of 1,500 embryonated Ascaris suum eggs. The recovery rates, sizes and features of the larvae and immunological responses in the hamsters were chronologically monitored according to somatic migration. In both experiments, the larvae failed to develop into the adults, but the more and larger larvae were observed for a longer period from experiment 2 in comparison with experiment 1. The numbers of the mast cells in the small intestinal mucosa and mesenteric lymph nodes, of the goblet cells in the small intestinal mucosa and of T-cells in the mesenteric lymph nodes, spleens and cardiac blood from experiment 2 were fewer than those from the experiment 1. In general, increasing of these cells followed by expulsion of the worms in the both groups. Profound leukopenia due to lymphopenia was found through trial period in experiment 2. Considering the experimental results, development or expulsion mechanism of somatic migrant larvae may be related to lymphopenia and temporary increasing tendency of the mast cells, the goblet cells and T-cells. In addition, patent infection of A suum in the hamsters was not obviously observed in spite of immunosuppression by prednisolone acetate.

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