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Kinetic Study on Aminolysis of 4-Chloro-2-Nitrophenyl X-Substituted-Benzoates in Acetonitrile and in 80 mol % H2O/20 mol % DMSO: Effect of Medium on Reactivity and Reaction Mechanism

  • Kim, Ha-Ram;Um, Tae-Il;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.4
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    • pp.1128-1132
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    • 2014
  • A kinetic study on aminolysis of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-i) in MeCN is reported. The Hammett plot for the reactions of 6a-i with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X$ = 1.03 and r = 0.78. The nonlinear Hammett plot is not due to a change in rate-determining step (RDS) but is caused by the resonance stabilization of substrates possessing an electron-donating group in the benzoyl moiety. The Br${\phi}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (6e) with a series of cyclic secondary amines is linear with ${\beta}_{nuc}$ = 0.69, an upper limit for reactions reported to proceed through a concerted mechanism. The aminolysis of 6e in aqueous medium has previously been reported to proceed through a stepwise mechanism with a change in RDS on the basis of a curved Br${\phi}$nsted-type plot. It has been concluded that instability of the zwitterionic tetrahedral intermediate ($T^{\pm}$) in MeCN forces the reaction to proceed through a concerted mechanism. This is further supported by the kinetic result that the amines used in this study are less reactive in MeCN than in $H_2O$, although they are more basic in MeCN over 7 $pK_a$ units.

Effects of Slow-Release Nitrogen Fertilizers, Latex Coated Urea and Meister10, on Direct Seeded Rice in Dry Soil (벼 건답직파재배시 완효성질소비료의 시용 효과)

  • Back, Jun-Ho;Jang, Myung-Hwan;Lee, Seung-Ho;Lee, Sang-Jo;Lim, Jun-Young;Kim, Bok-Jin
    • Korean Journal of Soil Science and Fertilizer
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    • v.34 no.6
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    • pp.407-412
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    • 2001
  • This study was conducted to find out the effect of slow-release nitrogen fertilizer, such as latex coated urea(LCU) and Meister10(MS10) on direct seeded rice in dry soil(DS). Junghwabyeo, and early maturity rice cultivar was grown on the plots which were treated with None-nitrogen. urea. LCU and MS10 plot. Growth characteristic, yield and yield components were investigated. Nitrogen uptake-efficiency and physico-chemical properties of soil before-after experiment were analyzed. Plant height and number of tillers $m^{-2}$ in LCU and MS10 plot at early grow stages were higher than those in urea plot. Plant height and number of tillers $m^{-2}$ grown on the plot of Ms10 plot were higher than those of LCU plot. The number of seedling $m^{-2}$ were no significant differences among None-N, urea, and MS10 plot in DS. Heading date and leaf color were higher with Urea than LCU and MS10 plot. Culm length in LCU and MS10 plot were longer compared with urea plot, but panicle length was similar among with Urea, LCU and MS10 plot. Number of panicles $m^{-2}$ was greater in order of MS10 > LCU > Urea plot. Yield were greater in order of MS10 > LCU > Urea plot. Nitrogen uptake and nitrogen efficiency were greater in order of MS10 > LCU > urea plot. After the experiment, total content of nitrogen in soil was not changed at all treatments, but pH, P and Si of soil were lower than those of before experiment at all treatments.

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Effect of Continuous Application of Organic Farming Materials on the Soil Physicochemistry Property and Plant Growth, Yield and Components of Tomato (유기농 자재의 연용이 토양의 이화학적 성질과 토마토의 생육, 수량 및 체내성분에 미치는 영향)

  • 오주성;이종성;강경희;김회태;정원복;정순재
    • Korean Journal of Organic Agriculture
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    • v.9 no.1
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    • pp.75-89
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    • 2001
  • This study the effects of the application of organic farming materials on the soil Physicochemistry property and plant growth, yield and components of Tomato were compared with conventional culture. The results obtained from the experiment are summarized as follows : 1. The effect of soil chemical properties after application organic farming materials, The amounts of pH and O.M. in N, P, K treated plot were few of change, To the contrary, fermentation compost and microorganisms fermentation compost treated plot were some increase, Amount of $P_2$$O_{5}$, Ca and K increase in comparison with the N, P, K treated plot. 2. Changes of soil microbial after application organic farming materials, The number of bacteria, actinomycetes and fungi in N, P, K treated plot were appeared definite direction. to the contrary, The number of bacteria and actimycetes in fermentation compost and microorganisms fermentation compost treated plot showed the increased tendency, The number of fungi showed the decreased tendency. 3. Effect of organic farming materials application on the growth and yield of tomato was superior in order of microorganisms fermentation compost plot〉 chemical fertilizers plot〉 fermentation compost plot. especially, chicken manure + microorganisms fermentation compost treated plot was the highest. 4. Effect of organic farming materials application on the components of tomato were not different.

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DEVELOPMENT OF A POST-PROCESSING PROGRAM FOR VISUALIZATION OF MRI DATA (MRI Data 가시화용 후처리 프로그램 개발)

  • Myong, H.K.;Choi, H.H.
    • 한국전산유체공학회:학술대회논문집
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    • 2007.10a
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    • pp.67-72
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    • 2007
  • A post-processing program based on the OOP(Object-Oriented Programming) concept has been developed for visualization of MRI. User-friendly GUl(Graphic User Interface) has been built on the base of MFC(Microsoft Foundation Class). The program is organized as modules by classes based on VTK-library, and these classes are made to function through inheritance and cooperation which are an important and valuable concept of object-oriented programming. The major functions of this post-processor program are introduced and demonstrated, which include contour plot, surface plots, cut plot and clip plot as well as view manipulation (translation, rotation, scaling etc).

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Kinetics and Mechanism of Alkaline Hydrolysis of [(Methoxy)(p-substituted styryl)-carbene] Pentacarbonyl Chromium(0) Complexes in Aqueous Acetonitrile

  • Shin, Gap-Cheol;Hwang, Jae-Young;Yang, Ki-Yull;Koo, In-Sun;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.12
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    • pp.1981-1985
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    • 2005
  • Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

Effects of Sulphur Bentonite Mixture Fertilizer for the Growth of Young Radish (Raphanus sativus L.) (열무 생육을 통한 유황벤토나이트 혼합 비료의 효과)

  • Nam, Ki-Woong;Yoon, Deok-Hoon
    • Korean Journal of Plant Resources
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    • v.27 no.4
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    • pp.354-358
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    • 2014
  • Field study was conducted to evaluate the agronomic effectiveness of sulphur-bentonite fertilizer. Soil pH was slightly lower tendency to the increase of sulphur-bentonite fertilization, but did not indicate a sharp decline in soil pH. The T-N contents in the $6kg/1000m^2$ plot was higher to 700 mg/kg and the organic matter content was 1.29% in the $3kg/1000m^2$ plot. The content of available-P was also increased to 289 mg/kg in the $6kg/1000m^2$ plot. The growth characteristics of the young radish (Raphanus sativus L.) has significantly more in $3kg/1000m^2$ plot on upper part, and more on under part in $6kg/1000m^2$ plot. Therefore, it is concluded that the application of sulphur-bentonite fertilizer was thought to be effective for the chemical characteristics of soil and crop growth enhancement.

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.

Effects of Liming and Nitrogen Sources on the Yield and Quality of Burley Tobacco II. Effects of Chemical Constituents of tobacco leaves (석회의 질소원이 버어리종 담배의 수량과 품질에 미치는 영향 II. 잎담배의 화학성분에 미치는 영향)

  • 김상범;한철수;김용규
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.32 no.4
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    • pp.379-385
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    • 1987
  • A field experiment was conducted to find out the effects of liming (soil pH) and sources of N on the chemical constituents of soil and leaf lamina of burley tobacco. Treatments consisted of liming (nonliming, liming to soil pH 5.5 and 6.5) as the main plot and N sources[compound fertilizer of containing 3.9% $NH_4-N$ and 6.1% $NH_2-N,\;NaNO_3,\;(NH_2)_2CO\;and\;(NH_4)_2SO_4$]as the sub-plot. The soil pH was high in $NaNO_2$ plot, while low in $(NH_4)_2SO_4$. But the differences of Ca concentration in top soil among N sources were not detected. The $NO_3-N$ concentration in top soil was high in high limed and $NaNO_3$ plot. The $NO_3-N$ content of leaf (lamina) at 75 days after transplanting was high in $NaNO_3$ plot and CaO con-tent of leaf at 45 days after transplanting was high in high limed plot. But neither liming nor N source had effect on the contents of total nitrogen, $P_2-O_{5}\;and\;K_2O$ of leaf during growing season. There was no significant differences in total alkaloid and total nitrogen contents of cured leaf (lamina) to liming and N source. But when the source of N was $NaNO_3$, the content of total alkaloid was increased by adding lime. When the source of N was $(NH_4$)_2SO_4$, the content of $K_2O$ in cured leaf was high while CaO was low. But neither liming nor N source had effect on the contents of $P_2-O_{5}$ and MgO in cured leaf.

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Effects of Forest Practices on the Changes of Characteristics of Forest Stand, Mesopore Ratio and Soil Water Contents in Pinus koraiensis Stands (산림시업이 잣나무림의 생장, 토양조공극 및 토양함수능에 미치는 영향)

  • Jun, Jaehong;Jeong, Yongho;Choi, Hyung Tae;Yoo, Jae-Yun
    • Journal of the Korean Society of Environmental Restoration Technology
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    • v.11 no.3
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    • pp.20-27
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    • 2008
  • This study was conducted to investigate the influence of thinning and pruning on characteristics of forest stand, mesopore ratio and soil water content at the Pinus koraiensis stands in Gwangneung, Gyeonggido. The Pinus koraiensis had been planted in 1976 and thinning and pruning were carried out in 1996. A sample area survey was conducted at experimental plots (thinned and unthinned) in 1998 and 2005, and mesopore ratio and soil water content have been monitored from 2000 to present. Average tree height of the thinned plot increased from 10.9m to 13.2m and from 10.3m to 12.8m for the unthinned plot. Average D.B.H of the thinned plot increased from 15.9cm to 21.1cm and from 14.5cm to 16.7cm for the unthinned plot during the period 1998-2005. Crown density at the thinned plot increased from 81.5% to 95.0% and from 89.5% to 95.0% for the unthinned plot during the period 1998-2005. Mesopore ratio (pF2.7) of A layer soil at the thinned plot was 40.1% while that of the unthinned plot was 37.3%. Changes of mesopore ratio at unthinned plot were not associated with stand age, but those at thinned plot had increased and then decreased, showing declining of the practice effect. Average soil water content at the thinned plot were 23.7% and 22.4% for the unthinned plot. Soil watercontents at both plots have been increased with increase in stand age. But the difference of soil watercontent at each plot has been decreased, especially at the depth of 10cm.

A Kinetic Study on Michael-type Reactions of 1-(X-Substituted Phenyl)-2-propyn-1-ones with Amines: Effect of Amine Nature on Reactivity and Mechanism

  • Um, Ik-Hwan;Hwang, So-Jeong;Lee, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.29 no.4
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    • pp.767-771
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    • 2008
  • Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.