• Title/Summary/Keyword: $S_N1$ mechanism

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Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures (압력변화에 따른 퀴놀린 유도체와 p-치환 염화벤조일류의 속도론적 연구)

  • Jong-Wan Lim;Se-Kyong Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.206-212
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    • 2003
  • The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

NICKEL INCORPORATION INTO Klebsiella aerogenes UREASE (Klebsiella aerogenes Urease로의 닉켈의 도입)

  • Lee, Mann-Hyung-
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1994.11a
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    • pp.69-80
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    • 1994
  • Although ureases play important roles in microbial nitrogen metabolism and in the pathogenesis of several human diseases, little is known of the mechanism of metallocenter biosynthesis in this Ni-Containing enzyme. Klebsiella aerogenes urease apo-protein was purified from cells grown in the absence of Ni. The purified apo-enzyme showed the same native molecular weight, charge, and subunit stoichiometry as the holo-enzyme. Chemical modification studies were consistent with histidinyl ligation of Ni. Apo-enzyme could not be activated by simple addition of Ni ions suggesting a requirement for a cellular factor. Deletion analysis showed that four accessory genes (ureD, ureE, ureF, and ureG) are necessary for the functional incorporation of the urease metallocenter. Whereas the $\Delta$ureD, $\Delta$ureF, and $\Delta$ureG mutants are inactive and their ureases lack Ni, the $\Delta$ureE mutants retain partial activity and their ureases possess corresponding lower levels of Ni. UreE and UreG peptides were identified by SDS-polyacrylamide gel comparisons of mutant and wild type cells and by N-terminal sequencing. UreD and UreF peptides, which are synthesized at ve교 low levels, were identified by using in vitro transcription/translation methods. Cotransformation of E. coli cells with the complementing plasmids confirmed that ureD and ureF gene products act in trans. UreE was purified and characterized. immunogold electron microscopic studies were used to localize UreE to the cytoplasm. Equilibrium dialysis studies of purified UreE with $^{63}$ NiC1$_2$ showed that it binds ~6 Ni in a specific manner with a $K_{d}$ of 9.6 $\pm$1.3 $\mu$M. Results from spectroscopic studies demonstrated that Ni ions are ligated by 5 histidinyl residues and a sixth N or O atom, consistent with participation of the polyhistidine tail at the carboxyl termini of the dimeric UreE in Ni binding. With these results and other known features of the urease-related gene products, a model for urease metallocenter biosynthesis is proposed in which UreE binds Ni and acts as a Ni donor to the urease apo-protein while UreG binds ATP and couples its Hydrolysis to the Ni incorporation process.ouples its Hydrolysis to the Ni incorporation process.s.

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The effects of addition elements on the formation of the hard spots in High strength brass (고력황동의 Hard Spots형성에 미치는 첨가원소의 영향)

  • Park, Hyun-Sik;Ra, Hyung-Yong
    • Journal of Korea Foundry Society
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    • v.6 no.1
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    • pp.12-19
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    • 1986
  • This study was undertaken to understand the formation mechanism of the hard spots in high strength brass. To investigate the behavior of the hard spots in the isothermal liquid state with varying silicon content, the rapidly quenched specimens were obtained by suctioning the melt into the silica tube and water quenching. To examine the growth process of the hard spots with holding time, the unidirectional solidification technique was used. The results of this study are summarized as follows: 1) With the addition of Fe in order to get the effects of grain refinement in high strength brass, the two different type of Fe-rich phases are occurred, which are defined as dendritic and globular phase. The chemical composition of the globular phase was different from that of the dendritic phase in that the globular phase contained Si. 2) With increasing Si content, the Fe-rich phase had a tendency to form globular phase. 3) As the holding time increased in the liquid state, globular was also prone to coalesce. The further growth of globular phase to large size was due to reducing the interfacial energy. 4) The primary phase of copper alloy was nucleated preferentially on the dendritic phase. It was noticeable that the dendritic phase acted as a grain refiner. However, the agglomerate (hard spots) which was composed of the globular phase decreased the mechanical properties of high strength brass. 5) Once the hard spots formed in the high strength brass casting, it was very difficult to remove them. This is due to the fact that their meting temperature is higher than the pouring temperature of high strength brass.

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The research on static and dynamic mechanical properties of concrete under the environment of sulfate ion and chlorine ion

  • Nie, Liangxue;Xu, Jinyu;Bai, Erlei
    • Computers and Concrete
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    • v.20 no.2
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    • pp.205-214
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    • 2017
  • The Hydraulically driven test system and ${\Phi}100mm$ split Hopkinson pressure bar(SHPB) test device were employed to research the quasi-static and dynamic mechanical properties of concrete specimens which has been immersed for 60 days in sodium sulfate (group S1) and sodium chloride (group S2) solution, the evolution of their mass during corrosive period was explored at the same time, and the mechanism of performances lost was analyzed from the microscopic level by using scanning electron microscope. Results of the experimental indicated that: their law of mass both presents the trend of continuous rising during corrosive period, and it increases rapidly on the early days, the mass growth of group S1 and group S2 in first 7 days are 76.78% and 82.82% of their total increment respectively; during the corrosive period, the quasi-static compressive strength of specimens in two groups are significantly decreased, both of which present the trend of increase first and then decrease, the maximum growth rate of group S1 and group S2 are 7.52% and 12.71% respectively, but they are only 76.23% and 82.84% of specimens which under normal environment (group N) on day 60; after immersed for 60 days, there were different decrease to dynamic compressive strength and specific energy absorption, and so as their strain rate sensitivities. So the high salinity environment has a significant effect of weaken the quasi-static and dynamic mechanical performance of concrete.

Intergranular Corrosion Mechanism of Slightly-sensitized and UNSM-treated 316L Stainless Steel

  • Lee, J.H.;Kim, K.T.;Pyoun, Y.S.;Kim, Y.S.
    • Corrosion Science and Technology
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    • v.15 no.5
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    • pp.226-236
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    • 2016
  • 316L stainless steels have been widely used in many engineering fields, because of their high corrosion resistance and good mechanical properties. However, welding or aging treatment may induce intergranular corrosion and stress corrosion cracking etc. Since these types of corrosion are closely related to the formation of chromium carbide in grain boundaries, the alloys are controlled by methods such as the lowering of carbon content, solution heat treatment. This work focused on the intergranular corrosion mechanism of slightly-sensitized and Ultrasonic Nano-crystal Surface Modification (UNSM)-treated 316L stainless steel. Samples were sensitized for 1, 5, and 48 hours at $650^{\circ}C$ in $N_2$ gas atmosphere. Subsequently UNSM treatments were carried out on the surface of the samples. The results were discussed on the basis of the sensitization by chromium carbide and carbon segregation, the residual stress and grain refinement. Even though chromium carbide was not precipitated, the intergranular corrosion rate of 316L stainless steel was drastically increased with aging time, and it was confirmed that the increased intergranular corrosion rate of slightly-sensitized (not carbide formed) 316L stainless steel was due to the carbon segregation along the grain boundaries. However, UNSM treatment improved the intergranular corrosion resistance of aged stainless steels, and its improvement was due to the reduction of carbon segregation and the grain refinement of the outer surface, including the introduction of compressive residual stress.

Study on Intestinal Flora and IgA Concentration Analysis in Newborn Mice by Stress and Diet in Pregnant Mice to Investigate the Effect of Taedok on the Intestinal Flora (태독이 장내 세균총에 미치는 영향을 규명하기 위한 임신쥐의 스트레스 및 식이에 따른 신생쥐의 장내 세균총 및 IgA 농도 분석 시험)

  • Jeong, Jieun;Choi, Yoomin;Jeong, Minjeong
    • The Journal of Pediatrics of Korean Medicine
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    • v.35 no.4
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    • pp.96-111
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    • 2021
  • Objectives The purpose of this study is to look for pathological mechanism of disease development caused by Taedok, by studying whether stress and diet in pregnant ICR mice affect the intestinal flora and IgA (Immunoglobulin A) concentration. Methods The mice were divided into 4 groups (n=5 per group) based on the concept of Taedok: the control group (G1), stress group (G2), capsaicin diet group (G3), high fat diet group (G4). We collected and analyzed intestinal flora from maternal feces and cecal flora from neonatal mice by group. Then, IgA concentration in the maternal feces and sIgA (secretory Immunoglobulin A) concentration in the cecal contents of newborn mice were analyzed. In addition, serum corticosterone was analyzed before and after stress application. Results Changes in maternal intestinal flora and neonatal mice cecal flora by stress and diet were observed. There were no significant changes in the IgA concentration in maternal feces and the sIgA concentration in the cecal contents of neonatal mice. No significant changes compared to the control group were observed between groups before and after applying stress. However, when comparing within one subject, a significant increase was confirmed after stress application in the stress group (G2). Conclusions Based on the results, we observed stress and diet in pregnant mice affect the intestinal flora of maternal and neonatal. We were able to interpret the pathological mechanism of Taedok based on the principle of interaction between mother and newborn intestinal flora.

Removal of Nitrosomethylamine at Extremely Low Concentration by Powdered Activated Carbon (분말활성탄을 이용한 극미량 농도 Nitrosomethylamine의 흡착 제거)

  • Lee, Sung-Bum;Yoon, Yeo-Min;Choi, Chang-Kyoo;Kim, Moon-Il
    • 한국방재학회:학술대회논문집
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    • 2008.02a
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    • pp.413-416
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    • 2008
  • Recently, the results of vital tissue test showed that nitrosodimethylamine (NDMA) as a disinfection by-product (DBP), could be regarded as a carcinogen because a tumor was observed in organs. U.S.EPA indicated 0.7 ng/L as exposure concentration of NDMA based on a risk assessment target with a lifetime cancer risk of $10^{-6}$. Several recent studies have shown that UV oxidation could remove NDMA. However, UV oxidation is uneconomical and can reform NDMA after treating. In addition, the treatment mechanism of adsorption has not been founddue to the uncertainty of NDMA pathway. In addtion, NDMA has a radioisotope $^{14}C$-labeled which can be analyzed at low concentration of NDMA by Liquid Scintillation Counter (LSC). This study has investigated NDMA determination using LSC at an extremely low range from 1 to 100 ng/L and NDMA removal by powdered activated carbon (PAC) adsorption. For $^{14}C$-NDMA by LSC, the highest correlation over 99% between count number and NDMA concentrationwas obtained with possibility of $^{14}C$-NDMA concentration up to 1 ng/L. In the presence of PAC ranging from 50 to 10,000 mg/L, $^{14}C$-NDMA was removed from 18% to 97% for Sigma-Aldrich corporation (S-A co.) and from 9% to 93% by PAC for Daejung corporation (Dj co.). Hence it was found that the removal efficiency by PAC adsorption could vary depending on PAC types from different companies. For PAC adsorption capacity of $^{14}C$-NDMA using the Freundlich isotherm, $K_f$ and 1/n of PAC from S-A co. were $2.67\times10^{-3}$ ng/mg and 1.009, while those of PAC from Dj co. were $1.30\times10^{-3}$ ng/mg and 0.994, respectively. Thus, PAC from S-A co. showed twice higher adsorption capacity than Dj co.

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Solvolysis of Anthraquinone-2-Carbonyl Chloride in Binary Solvent Mixtures (이성분 혼합용매계에서 염화 안트라퀴논-2-카르보닐의 가용매 분해반응$^{1,2}$)

  • Jong Pal Lee;Dae Dong Sung;Tae Sup Uhm;Ikchoon Lee;Se Chul Sohn
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.465-471
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    • 1985
  • The rate constants for the solvolysis of anthraquinone-2-carbonyl chloride in binary solvent mixtures, methanol-acetonitrile, methanol-acetone, ethanol-acetonitrile and ethanol-acetone, have been studied by means of conductometry. Maximum rate phenomena were observed at the methanol mole fraction, $X_{MeOH}$ = 0.73~0.81 for methanol-acetonitrile and at $X_{MeOH}$ = 0.83 for methanol-acetone mixtures. The Kivinen and Grunwald-Winstein plots indicated that the reaction proceeds via $S_N2$ type mechanism. Application of Taft's solvatochromic correlation on the solvolysis rate revealed that both $\alpha$ and ${\pi}^*$ are important for reactions in methanol-acetonitrile and methanol-acetone mixtures, while only ${\alpha}$ influences significantly on the rate in ethanol-acetonitrile and ethanol-acetone mixtures.

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Fatigue crack effect on magnetic flux leakage for A283 grade C steel

  • Ahmad, M.I.M.;Arifin, A.;Abdullah, S.;Jusoh, W.Z.W.;Singh, S.S.K.
    • Steel and Composite Structures
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    • v.19 no.6
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    • pp.1549-1560
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    • 2015
  • This paper presents the characterization of fatigue crack in the A283 Grade C steel using the MMM method by identifying the effects of magnetic flux leakage towards the crack growth rate, da/dN, and crack length. The previous and current research on the relation between MMM parameters and fatigue crack effect is still unclear and requires specific analysis to validate that. This method is considered to be a passive magnetic method among other Non-Destructive Testing (NDT) methods. The tension-tension fatigue test was conducted with a testing frequency of 10 Hz with 4 kN loaded, meanwhile the MMM response signals were captured using a MMM instrument. A correlation between the crack growth rate and magnetic flux leakage produces a sigmoid shape curve with a constant values which present the gradient, m value is in the ranges of 1.4357 to 4.0506, and the y-intercept, log C in the ranges of $4{\times}10^{-7}$ to 0.0303. Moreover, a linear relation was obtained between the crack length and magnetic flux leakage which present the R-Squared values is at 0.830 to 0.978. Therefore, MMM method has their own capability to investigate and characterize the fatigue crack effects as a main source of fracture mechanism for ferrous-based materials.

Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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