• Title/Summary/Keyword: K-Plot

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Kinetics and Mechanism of Azidolysis of Y-Substituted Phenyl Benzoates

  • Um, Ik-Hwan;Kim, Eun-Hee;Han, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.29 no.3
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    • pp.580-584
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    • 2008
  • Second-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3) in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (b lg) changes from 0.97 to 0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brnsted curvature) is 4.8, which is practically identical to the pKa of the conjugate acid of N3 ion (4.73). Hammett plots correlated with s o and s constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with r = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brnsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.

Determination of Optimal Application Rates of Phosphorus and Potassium Fertilizers for Paddy Rice (벼에 대한 인산 및 칼리질비료의 적정시비량 결정)

  • Song, Yo-Sung;Jun, Hee-Joong;Park, Woo-Kyun;Jung, Beung-Gan;Jung, Kyu-Seok;Lee, Ki-Sang;Yoon, Young-Sang
    • Korean Journal of Soil Science and Fertilizer
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    • v.41 no.2
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    • pp.75-82
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    • 2008
  • In order to establish environmentally friendly phosphorus(P) and potassium(K) fertilizer application rates for rice cultivation in Korea, a field experiment was conducted in two different characterized paddy soils, higher and lower P and K content in soil from 2005 to 2006 in Suwon, Korea. Chuchong which is typical rice variety in Korea, was selected for experiment. Rice yields in base P-K fertilizer level ($30-30kg\;ha^{-1}$) and no P-K fertilizer level were 97~98% and 93~97% of standard P-K fertilizer level ($45-57kg\;ha^{-1}$), respectively. At the lower content of P and K in immatured paddy soil, the yield of no P plot was decreased by 7% compared to that of standard P-K plot. Significant difference in rice yield and yield characteristics was found neither in standard P-K fertilization plot nor in base P-K fertilization plot. There was no significant difference in P and K uptake at the harvest stage between standard P-K fertilizer plot and base P-K fertilizer plot. Phosphorus and K uptake was slightly decreased in no fertilizer plots compared to standard fertilizer plot. Phosphorus and K use efficiency of rice plant in base fertilizer plot was higher than that in standard fertilizer plot. Available phosphorus and exchangeable potassium content in soil at the harvest stage were increased in both standard and base fertilizer plot. But no significant difference of P and K content in ? was found between standard fertilizer plot and base fertilizer plot. Rice quality characteristics such as proportion of brewers rice, damaged kernel, broken rice, and content of amylose and protein were lowered in the base fertilizer plot than the standard fertilized plot, while the proportion of perfect kernel increased in the base fertilizer plot From the results, we generally recommend the base P-K fertilization ($30-30kg\;ha^{-1}$) instead of standard P-K fertilization ($45-57kg\;ha^{-1}$) for rice cultivation in Korea.

The Effects of Phosphorus Fertilization After Incorporation of Green Manure Crops to Jeju Volcanic Ash Soils on Potato Yields, Available Phosphate Contents in Soil, and Phosphorus Balances

  • Kang, Ho-Jun;Yang, Sang-Ho;Kim, Yu-Kyoung
    • Korean Journal of Soil Science and Fertilizer
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    • v.50 no.3
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    • pp.195-202
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    • 2017
  • The volcanic ash soils from the Jeju province have low available phosphate because of the high phosphate fixing power of the soils. Phosphorus fertilizerwas dressed after cultivating green manure crops and before cultivating potatoes in order to investigate potato yields, the available phosphate contents, and phosphorus balance in the soils. Green manure crops cultivated in this study were hairy vetch alone and hairy vetch and rye. During potato cultivation, four treatments were conducted in the experiments; NF (non fertilizer), P fertilizer ($N-P-K=0-25-0kg\;10a^{-1}$), NK fertilizer ($N-P-K=18-0-19kg\;10a^{-1}$), and NPK fertilizer ($N-P-K=18-25-19kg\;10a^{-1}$). There were no differences in the yields of potato stem and tuber from the cultivation plots of different green manure crops. However, in the plots with single-sown hairy vetch and mixed-sown hairy vetch and rye, the yields of potato stem and tuber were higher in the P fertilizer plot than in NF plot. The yield of tuber among the treatments with mixed-sown hairy vetch and rye was the highest in the NPK fertilizer plot. The available phosphate content in soils initially increased with time in all plots, but began to decrease gradually after Oct. 18. The available phosphate contents were high in the plots for phosphate fertilization, and the difference in available phosphate content between non-phosphorus fertilizer plots and phosphorus fertilizer plots increased with time. In the single-sown hairy vetch and mixed-sown hairy vetch and rye plot, the phosphorus balances in NF plot and NK fertilizer plot were very low, while those in the P fertilizer plot and NPK fertilizer plot were high. In conclusion, available phosphate contents in soil and the potato yields were increased by phosphorus fertilization when potatoes planted after cultivating hairy vetch and rye together, compared to hairy vetch alone.

DNA Sequence Visualization with k-convex Hull (k-convex hull을 이용한 DNA 염기 배열의 가시화)

  • Kim, Min Ah;Lee, Eun Jeong;Cho, Hwan Gyu
    • Journal of the Korea Computer Graphics Society
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    • v.2 no.2
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    • pp.61-68
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    • 1996
  • In this paper we propose a new visualization technique to characterize qualitative information of a large DNA sequence. While a long DNA sequence has huge information, it is not easy to obtain genetic information from the DNA sequence. We transform DNA sequences into a polygon to compute their homology in image domain rather than text domain. Our program visualizes DNA sequences with colored random walk plots and simplify them k-convex hulls. A random walk plot represents DNA sequence as a curve in a plane. A k-convex hull simplifies a random work plot by removing some parts of its insignificant information. This technique gives a biologist an insight to detect and classify DNA sequences with easy. Experiments with real genome data proves our approach gives a good visual forms for long DNA sequences for homology analysis.

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Collapsibility Using Raindrop Plot (RAINDROP PLOT을 이용한 차원축소)

  • Hong C. S.;Kim B. J.;Park J. Y.
    • The Korean Journal of Applied Statistics
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    • v.18 no.2
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    • pp.471-485
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    • 2005
  • For categorical data analysis, the collapsibility were explained with the odds ratio (cross-product ratio). When these theories with these odds ratios are applied to real $2{\times}2{\times}K$ contingency tables, it is impossible to decide whether data are collapsible. Among graphical methods to represent odds ratios, Contour plot which is developed by Doi, Nakamura and Yamamoto (2001) could explain the structure of these data, but cannot decide on the collapsibility. In this paper, by using the Raindrop plot proposed by Barrowman and Myers (2003), we suggest an alternative method which can not only explain the structure of data, but also decide on the collapsibility.

Studies on the Leaching Constituent of Submerged Soil -I. Effects of Potassium Salts on Leaching of Minerals in Submerged Soil (논 토양성분(土壤成分)의 용탈(溶脫)에 관(関)한 연구(硏究) -I. 논 토양성분(土壤成分)의 용탈(容脫)에 미치는 가리염(加里塩)의 영향(影響))

  • Kim, Kwang-Sik;Kim, Yong-Woong
    • Korean Journal of Soil Science and Fertilizer
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    • v.16 no.1
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    • pp.36-41
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    • 1983
  • These studies were carried out to investigate the effects of potassium salts on the changes of chemical properties in submerged soil. Rice plants were cultured in submerged soil using potassium salts. Obtained results were as follows. In the submerged soil cultured with rice plants the value of pH was higher in the potassium chloride plot than in the potassium sulfate plot. The leaching of cations such as calcium, magnesium, potassium and ammonium were higher in the potassium chloride plot than in the potassium sulfate plot. On the other hand, the leaching of phosphate ion was slightly higher in the potassium sulfate plot than in the potassium chloride plot. The leaching of iron was higher in the planted plot than in the non-planted plot, but that of silica was higher in the non-planted plot than in the planted plot. However, the leaching of iron and silica was not affected by potassium salts.

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Wood Quality of Trees Fertilized by Charcoals (목탄시비 수목의 재질)

  • Kim, Byung-Ro;Shin, Chang-Seob
    • Journal of the Korean Wood Science and Technology
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    • v.36 no.3
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    • pp.55-60
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    • 2008
  • This study was carried out to investigate the effect of charcoal meal application on the quality of the wood. As the results, it was observed that annual ring width of seedlings was wider in the plots treated with charcoal meal than the control plots. Depending on the kind of charcoal, annual ring width was widest in the plot treated with Larix kaempferi charcoal, and then was observed in order of Pinus koraiensis > particle board > Quercus acutissima. Latewood percentage and specific gravity were lower in the plots treated with charcoal than the control plots and lowest in Larix kaempferi charcoal plot among the plots treated with charcoal. Tracheid length was longer in the plot treated with powder charcoal than the control plot but tracheid width was not significantly different from the control plot. The cell wall thickness of earlywood was not significantly different between the plot treated with charcoal and the control plot but that of latewood was thicker in the plots treated with charcoal than the control. Microfibril angle was smaller in the plot treated with granulated charcoal than the control plot. However, there was no significant difference between the plot treated with powder charcoal and granulated charcoal.

Kinetic Study on Nucleophilic Substitution Reactions of 4-Chloro-2-nitrophenyl X-Substituted-benzoates with Cyclic Secondary Amines: Effect of Substituent X on Reactivity and Reaction Mechanism

  • Jeon, Seong Hoon;Kim, Hyun Soo;Han, Young Joon;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.2983-2988
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    • 2013
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

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.

Structure-Reactivity Correlations in Nucleophilic Displacement Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Z-Substituted-Phenoxides

  • Son, Yu-Jin;Kim, Eun-Hee;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2455-2460
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    • 2013
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-$ClPhO^-$) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}X=0.89$ and r = 0.58. The Br${\o}$nsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.76$. The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4-$ClPhO^-$) is also linear with ${\beta}_{lg}=-0.72$. The Hammett plot correlated with ${\sigma}^-$ constants for the reactions of 5a-5d results in a much better linear correlation than that correlated with ${\sigma}^o$ constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.