• Title/Summary/Keyword: Expulsion

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Kinetics and Mechanism of Nucleophilic Displacement Reactions of Y-Substituted Phenyl Benzoates with Z-Substituted Phenoxides

  • Min, Se-Won;Seo, Jin-A;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2403-2407
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    • 2009
  • Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

Origin of the α-Effect in Nucleophilic Substitution Reactions of Y-Substituted Phenyl Benzoates with Butane-2,3-dione Monoximate and Z-Substituted Phenoxides: Ground-State Destabilization vs. Transition-State Stabilization

  • Kim, Mi-Sun;Min, Se-Won;Seo, Jin-A;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.2913-2917
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    • 2009
  • Second-order rate constants (k$_{Nu–}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-i) with butane-2,3-dione monoximate ($Ox^-\;an\;\alpha$-nucleophile) and Z-substituted phenoxides in 80 mol% H$_2$O/20 mol% DMSO at 25.0${\pm}$0.1$^{\circ}C$. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for reactions of 1a-h with Ox$^–$ exhibit many scattered points. In contrast, the Yukawa-Tsuno plot results in a good linear correlation with ${\rho}_Y$ = 2.20 and r = 0.45, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS). A stepwise mechanism with expulsion of the leaving-group being the RDS has been excluded, since Y-substituted phenoxides are less basic and better nucleofuges than Ox$^–$. Thus, the reactions have been concluded to proceed through a concerted mechanism. Ox$^–$ is over 10$^2$ times more reactive than its reference nucleophile, 4-chlorophenoxide (4-ClPhO$^–$). One might suggest that stabilization of the transition-state (TS) through intramolecular general acid/base catalysis is responsible for the ${\alpha}$-effect since such general acid/base catalysis is not possible for the corresponding reactions with 4-ClPhO$^–$. However, destabilization of the ground-state (GS) of Ox$^–$ has been concluded to be mainly responsible for the ${\alpha}$-effect found in this study on the basis of the fact that the magnitude of the ${\alpha}$-effect is independent of the nature of the substituent Y.

An Application Plan of Cost Information through Actual Date Information DB Construction (공사실적정보 DB구축을 통한 원가정보 활용방안)

  • Kim, Soung-Jik;Kim, Tae-Hui;Min, Kyung-Seok;Kim, Ok-Gyu;Kim, Chan-Kyu
    • Proceedings of the Korean Institute Of Construction Engineering and Management
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    • 2007.11a
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    • pp.495-498
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    • 2007
  • The latest parceling-out price upper limit ancestor memorial service enforcement, Sale in lots circle is elated interest of society each floor for construction working expenses by open etc. but private investment law for society basis facilities, because circle that is presenting in parceling-out price upper limit ancestor memorial service back is different system (configuration item), cross is expected. A lot of study results connected with cost control expense arbor in the mountains etc. were presented until present, but persistent DB expulsion prohibition. Cost information is standardization unpreparedness of system. It is real condition that is hoarded since research and development by practical use plan presentation unpreparedness etc. Therefore, in this study, desire does actual date use plan presentation by purpose through DB construction after process by information form of good quality so that can collects efficiently and manages and utilizes at construction production step flag firm' s results data which is achieved. Can utilize to data of tool development that maximize ultimately comprehension about employer' s business and business order ability through persuasion, and diverts in cost control business hereafter.

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Auto Dispatch Device of Parturition Beginning Signal by Temperature and a Load Sensor at Ubiquitous Circumstance in Pig Industry (양돈산업에 있어서 유비쿼터스 환경에서 온도 및 하중 센서에 의한 자동 분만 알림 시스템 개발)

  • Lee, Jang-Hee;Baek, Soon-Hwa;Yon, Seung-Ho
    • Reproductive and Developmental Biology
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    • v.33 no.3
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    • pp.139-146
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    • 2009
  • This study tried to develop the system (device) that automatically notify a manager of condition just before and after farrowing to extend ubiquitous-based technology and to increase efficiency of delivery care and productivity by reducing human labor and time on standby when farrowing management is done in the difficult and hard working environment of farrowing such as night or holidays in field sand especially in pig industry. In this test, selected 10 gilts were executed timed artificial insemination and were set up each temperature sensor and load sensor to them 3 days before the estimated farrowing day and were observed the farrowing situation. This study was embodied the NESPOT-based (KT Corporation) monitoring system, the system to transmit data in real time by utilization of wireless LAN and the sensor module to apply the ubiquitous environment to them. And this study was observed the situation to automatically notify situations of 10 gilts that first bore just before and after farrowing. The result obtained the farrowing situations of them in real time by setup of the NESPOT-based monitoring system to check farrowing situation directly is as follow. The average time of the automatic notice about situation just before farrowing by the temperature sensor was 27.5 minutes before the beginning of farrowing (the expulsion time of a piglet). 6 of 8 pregnant gilts that first bore automatically were notified situations just before farrowing and the temperature sensors inserted into 2 ones before farrowing were omitted. (The automatic notice rate 75%) The average time of the automatic notice of situation just after farrowing by the load sensor was taken 46.5 minutes after the beginning of farrowing (the expulsion time of a first piglet). The average gestation period of 8 ones that first bore and were tested by the automatic notice of farrowing situation was 115.6 days. This result found that the automatic farrowing notice system by the temperature sensor is more efficient than the load sensor as the automatic farrowing alarm device and sanitary treatment and improvement of the omission rate were required.

Effect of Panax ginseng on the Graft-versus-Host Reaction, Production of Leucocyte Migration Inhibitory Factor and Expulsion of Adult Trichinella spiralis in Mice (인삼이 이식편대숙주반응, 대식세포유주저지반응 및 Trichinella spiralis의 expulsion에 미치는 영향)

  • Ha, Tai-You;Lee, Jeong-Ho;Kim, Sang-Hyung
    • The Journal of the Korean Society for Microbiology
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    • v.21 no.1
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    • pp.133-144
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    • 1986
  • This study was undertaken to assess the effect of ginseng administration on T lymphocyte induced local xenogenic graft-versus-host(GVM) reactions which were induced with thymocyte, spleen cell and lymph node cell of ICR mice. Mice received daily 10mg of 70% alcohol ginseng extract oral1y for 100days and control mice remained untreated for the same period of time. The cells from donor mice were injected intradermally into the closely shaven abdominal skin of Sprague-Dawley rats for GVH tests. The thymocyte from control(ginseng-untreated) mice showed a negative local GVH reaction, whereas thymocyte from experimental(ginseng-treated) mice showed a positive reaction with the rate of 17.4%. When spleen cells were injected, the incidence of positive local GVH reaction was 66.7% among ginseng-treated mice, as opposed to incidence of 45.5% of positive local GVH reaction among control mice. The incidence of positive local GVH reaction of the lymph node cells when injected into a recipient was 71.4% among ginseng-treated mice as compared with that of 18.9% among control mice. The relationship between spleen cell inoculum and intensity of the local GVH reaction was assessed in ginseng-untreated mice. The intensity of GVH reaction clearly appears to be dose related. In ginseng-treated mice, a minimum of $1{\times}10^7$ spleen cell was required for production of positive local GVH reaction with almost linear relationship up to an inoculum of $5{\times}10^8$ cells. In control mice, however, a minimum of $1{\times}10^8$ spleen cells was required for positive GVH reaction. These results strongly suggest that the ginseng administration augments significantly the local xenogenic GVH reaction which was used to assess T lymphocyte function and immunocompetence of mice and in addition to this, these results appear to support previous suggestions that the local GVH reaction consitutes a qualitative test of the functional activity of T lymphocytes. These results may be the first to induce local GVH reaction, employing rats as recipient and mice as donor. This study was also desingned to investigate some of the effects of ginseng extract on lymphocyte-macrophage interactions. This was accomplished by in vitro quantification of 1) migratory inhibitory factor(MIF) synthetic capacity of splenic lymphocytes in mice previously primed with ginseng 2) MIF responsiveness of mouse peritoneal macrophages or chicken peripheral leucocytes under the presence of ginseng extract 3) migration ability of chicken peripheral leucocytes by direct stimulation of ginseng extract or ginseng saponin and 4) immunosuppressive effects of immunosuppressants such as cyclophosphamide, cyclosporin A or dexamethasone. Mice divided equally into the ginseng and the saline groups, which received intraperitoneally daily 0.2ml of ginseng absolute alcohol-extract(5mg/ml) and same amount of saline for 15 days, respectively. The cellular immune responsiveness of these mice was assayed 15 days after ginseng pretreatment. Splenic lymphocytes of mice treated with ginseng, when stimulated with sensitized specific-antigen such as sheep red blood cells or toxoplasmin, or with polyclonal activator concanavalin A, produced significantly more MIF than those of control saline group. MIF responsiveness of normal mouse macrophages was significantly augmented when assayed under the presence of ginseng extract (1mg/ml). The migratory ability of normal chicken leucocytes in the absence of MIF was significantly decreased by the stimulation of ginseng extract alone. MIF response was significantly decreased by immunosuppressants and this impaired response was not restored by ginseng pretreatment. This study was additionally performed to evaluate the effect of ginseng on the expulsion of adult Trichinella spiralis in mice. ICR mice were infected experimentally by esophageal incubation of 300 T. spiralis infective muscle larvae prepared by acid-pepsin digestion of infected mice. and received oral administration of 70% alcohol ginseng extract(10mg/mouse/day) for the indicated days plus 4 days before infection. At various times after infection, the number of adult T. spiralis worms in small intestines was determined. Interestingly, ginseng-treatment was accompanied by accelerated expulson of T. spiralis. These results led to the conclusion that Panax ginseng caused some enhancing effect on GVH reaction, macrophage migration inhibition reaction and expulsion of T. spiralis. In addition these results suggested that the mechanisms responsible for this enhancement of ginseng may be chiefly or partially due to nonspecific stimulation of cell-mediated immune response.

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A Study on Maintainability Improvement for Underwater Weapon Training Vehicle (수중무기 훈련탄의 정비성 향상방안 연구)

  • Jeong, Jinseob
    • Journal of the Korea Institute of Military Science and Technology
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    • v.16 no.2
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    • pp.111-117
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    • 2013
  • In this paper, we have proposed novel technique to improve maintainability for training vehicle of underwater weapon system. In case of under water weapon, the fire procedure is related with operation of expulsion system in submarines. So the submarine crews should practice the complex fire procedure of weapon system by using training vehicle, which is safer and cheaper than operational weapon. After emitted from submarine, the training vehicle rise to the surface and should be withdrawn from the sea. The recovered training vehicle is transported to maintenance depot and pass through the recycling procedure including disassembling the vehicle, data acquisition & analysis, battery charge, replacing expandable components, testing the captive equipment, and assembling the vehicle. The disassembling & assembling of training vehicle which is composed of watertight section or airframe, is time-consuming work. So in this paper, we have studied the elements of recycling procedure and propose the method to exclude the assembling & disassembling work for maintainability improvement.

Kinetics and Mechanism of the Pyridinolysis of Diethyl Isothiocyanophosphate in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.1042-1046
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    • 2012
  • The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of diethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit the two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with rate-limiting expulsion of the isothiocyanate leaving group from a trigonal bipyramidal pentacoordinated intermediate. The relatively large ${\beta}_x$ values with more basic and less basic pyridines imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb.

Supersonic flow bifurcation in twin intake models

  • Kuzmin, Alexander;Babarykin, Konstantin
    • Advances in aircraft and spacecraft science
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    • v.5 no.4
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    • pp.445-458
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    • 2018
  • Turbulent airflow in channels of rectangular cross section with symmetric centerbodies is studied numerically. Shock wave configurations formed in the channel and in front of the entrance are examined. Solutions of the unsteady Reynolds-averaged Navier-Stokes equations are obtained with finite-volume solvers of second-order accuracy. The solutions demonstrate an expulsion/swallowing of the shocks with variations of the free-stream Mach number or angle of attack. Effects of the centerbody length and thickness on the shock wave stability and flow bifurcation are examined. Bands of the Mach number and angle of attack, in which there exist non-unique flow fields, are identified.

Numerical Analysis on the Mode Transition of Integrated Rocket-Ramjet and Unstable Combusting Flow-Field (일체형 로켓-램제트 모드 천이 및 불안정 연소 유동장 해석)

  • Ko Hyun;Park Byung-Hoon;Yoon Woong-Sup
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • v.y2005m4
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    • pp.334-342
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    • 2005
  • A numerical analysis is performed using two dimensional axisymmetric RANS (Reynolds Averaged Navier-Stokes) equations system on the transition sequence of the Integrated Rocket Ramjet and the unsteady reacting flow-field in a ramjet combustor during unstable combustion. The mode transition of an axisymmetric ramjet is numerically simulated starting from the initial condition of the boost end phase of the entire ramjet. The unsteady reacting flow-field within combustor is computed for varying injection area. In calculation results of the transition, the terminal normal shock is occurred at the downstream of diffuser throat section and no notable combustor pressure oscillation is observed after certain time of the inlet port cover open. For the case of a small injection area at the same equivalence ratio, periodic pressure oscillation in the combustor leads to the terminal shock expulsion from the inlet and hence the buzz instability occurred.

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An Evaluation of the Weldability Characteristics on the 4 Lap Spot Welded Joint of Structural Steel Sheets in Automobile (자동차용 강판의 4겹 다층 점용접물의 용접특성 평가)

  • Kim, Hoi-Hyun;Kim, Seong-Su;Baek, Seung-Se;Kwon, Il-Hyun;Yang, Seong-Mo;Yu, Hyo-Sun
    • Proceedings of the KSME Conference
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    • 2004.11a
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    • pp.314-318
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    • 2004
  • This research is conducted to investigate weldability characteristics with various welding conditions on the 4 lap spot welded joint of structural steel sheets in automobile. The relationship between the tensile-shear strength and the indentation depth has been investigated to evaluate the weldability and the optimum welding conditions. The welding current and the welding time have a greatly affect to the tensile-shear strength compared to the electrode force. It was found that the indentation depth has a relatively close relationship with the expulsion occurrence. The optimum welding conditions were proposed for the 4 lap spot welded joint.

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