• Title/Summary/Keyword: Correlation 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.

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.

A Graphical Method for Evaluating the Effect of Outliers in One- and Two-Variate Data (일변량 및 이변량 자료에 대하여 특이값의 영향을 평가하기 위한 그래픽 방법)

  • Jang, Dae-Heung
    • The Korean Journal of Applied Statistics
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    • v.20 no.2
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    • pp.395-407
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    • 2007
  • Outliers distort many measures for data analysis. We can propose dandelion seed plot as a graphical tool for evaluating the effect of outliers in one-and two-variate data. We can draw mean-variance dandelion seed plots using linked curves which are made by changing weights from 1 to 0 for each datum. Similarly we can also draw covariance-correlation-coefficient dandelion seed plots. This graphical method can be a useful tool for elementary statistics education in college.

Biological Control of Aphids on Pepper in Greenhouses Using Aphidius gifuensis (싸리진디벌을 이용한 하우스고추에서 발생하는 진딧물의 생물적 방제)

  • Chang, Young-Duck;Jeon, Heuong-Yong
    • Korean Journal of Agricultural Science
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    • v.30 no.1
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    • pp.11-19
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    • 2003
  • The life-cycle of the aphid-parasite, Aphidius gifuensis, took 11.9 days at $25^{\circ}C$ and 12.1 days at $30^{\circ}C$. The female appearance rate of A. gifuensis was the best at $20{\sim}25^{\circ}C$ compared to the other temperatures. Optimum rearing temperature of Aphidius gifuensis was $20{\sim}25^{\circ}C$ Optimum temperatures for A. gifuensis emergence were $20^{\circ}C$ and $25^{\circ}C$ with 99.1% and 98.2%, respectively. However the emergence rate of Aphidius gifuensis was 58.8% at $10^{\circ}C$. There was a positive correlation between A. gifuensis adult activity and temperature, but there was a negative correlation between developmental period of Myzus persicae nymph and temperature. Among the pests occurring in pepper greenhouse, dominant species was M. persicae and its density was 6~1,024 per plant. The damaged fruit rate by Helicoverpa assulta was 3.3~53.3%. The number of aphid and mummy in the A. gifuensis released plot were 173.5 and 10 in June, 1.8 and 17 in July, 2000, respectively. The numbers of Aphidius gifuensis were 7.5 and 0.4 in May, 27.1 and 2.1 in June, 2001, respectively. The suppressive effects on M. persicae in A. gifuensis released plot was better than the control plot, but there was no significant difference compared to the pesticide-sprayed plot. The first leaf length and the stem width in the A. gifuensis released plot, the control plot, and the pesticide-sprayed plot were not significantly different, but the A. gifuensis released plot showed the highest yield among the plots.

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Correlation Analysis on the Runoff Pollutants from a Small Plot Unit in an Agricultural Area

  • Kang, Meea;Choi, Byoung-Woo;Lee, Jae-Kwan
    • Environmental Engineering Research
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    • v.15 no.4
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    • pp.191-195
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    • 2010
  • This study was carried out to investigate the important factors relating to runoff and pollutant loads in a plot unit located in an agricultural area. Of the precipitation parameters, such as total precipitation, days since last rainfall (ADD, the rainfall was more than 10mm) and average rainfall intensity on runoff, the strongest effect was obtained due to total precipitation, but the rainfall intensity showed a slightly positive correlation. It was expected that both variables, i.e. total precipitation and rainfall intensity, would lead to the generation of greater runoff. In contrast, runoff was negatively correlated with ADD, which is understandable because more infiltration and less runoff would be expected after a long dry period. The TSS load varied greatly, between 75.6 and $5.18{\times}10^4g$, per event. With the exception of TN, the TSS, BOD, COD and TP loads were affected by runoff. The correlations of these items were proportional to the runoff volume, with correlation coefficients (r) greater than 0.70, which are suitable for use as NPS model data. The TSS load showed very good relationships with organics (BOD & COD) and nutrients (TN & TP), with correlation coefficients greater than 0.79. Therefore, the removal of TSS is a promising factor for protecting water basins.

A Comparative Study on Measurement of Physical Activity between Smartphone App and Self-Reported Questionnaire (스마트폰 앱과 자가보고식 설문지의 신체활동 측정 비교)

  • Suh, Minhee;Seo, Kyoungsan
    • Journal of muscle and joint health
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    • v.29 no.2
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    • pp.91-99
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    • 2022
  • Purpose: The purpose of this study was to examine the level of agreement between smartphone apps and self-reported physical activity questionnaires. Methods: Quantitative methods were used to assess the correlation and agreement between the number of steps counted by a smartphone app and the amount of walking reported in a survey. A total of 29 adults who used smartphones were recruited from a university, and their step counts from their smartphone pedometers and responses to the international physical activity questionnaire (IPAQ) were collected over a 10-week period. Results: An analysis of 170 data pairs with Spearman's rho correlation and a Bland-Altman plot revealed a positive correlation between step counts from the smartphone app and walking activity from the IPAQ. The Bland-Altman plot also demonstrated the agreement to be improved among female participants. Conclusion: In assessing walking activity, smartphone pedometer apps showed good correlation with the IPAQ and improved agreement with the IPAQ among women. Therefore, it is suggested that the participants' gender and activity intensity, as well as the accuracy of measurement tools, should be considered in an evaluation of the delivery of physical activity promotion programs through smartphone apps.

Kinetic Study on Aminolysis of Y-Substituted-Phenyl X-Substituted-Benzoates: Effects of Substituents X and Y 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.35 no.2
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    • pp.471-476
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    • 2014
  • A kinetic study on aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (2a-k) in 80 mol % $H_2O/_20mol%$ DMSO at $25.0^{\circ}C$ is reported. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (2g) with a series of cyclic secondary amines curves downward (e.g., ${\beta}_1=0.25$, ${\beta}_2=0.85$ and $pK_a^o=10.3$), which is typical of reactions reported to proceed through a stepwise mechanism with a change in ratedetermining step (RDS). The Hammett plot for the reactions of 2a-k with piperidine consists of two intersecting straight lines, while the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X=1.15$ and r = 0.59. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in RDS but is caused by stabilization of substrates through resonance interactions between the electron-donating substituent and the C=O bond. Substrates possessing a substituent at the 2-position of the leaving aryloxide deviate negatively from the curved Br${\emptyset}$nsted-type plot for the reactions of Y-substituted-phenyl benzoates (3a-i), implying that the steric hindrance exerted by the substituent at the 2-position is an important factor which governs the reactivity of Y-substituted-phenyl benzoates.

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.

Bradykinin Antagonistic Activities of Antihistamine Agents Containing Piperazine Moiety (피페라진계 항히스타민제들의 브라디키닌 길항작용)

  • 정성현;이소영;윤혜숙
    • YAKHAK HOEJI
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    • v.37 no.6
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    • pp.625-630
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    • 1993
  • Among the six antihistamine agents tested in this study, homochlorcyclizine showed the highest bradykinin antagonistic activity in the receptor binding assay as well as the isolated rat ileum assay. Schild plot analysis of bradykinin-induced ileal contraction in the presence of three different concentrations of homochlorcyclizine revealed a pA$_{2}$=6.26, and a correlation coefficient of 0.984. Homochlorcyclizine of (100 $\mu{M}$ final concentration) also showed 25% antagonistic activity in the receptor binding assay.

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Effect of Dry Matter Production and Growth Construction of Zoysia japonica on a photoperiod (일조시간 조절이 잔디(Zoysia japonica)의 물질생산과 생장에 미치는 영향)

  • 도봉현
    • Asian Journal of Turfgrass Science
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    • v.15 no.2
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    • pp.65-76
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    • 2001
  • This study was designed to estimate on the interaction of the first productivity, light condition and to examine the ecophysiological characteristics of Zoysia japonica. rtificial community of Zoysia japonica was analyzed effect of matter production and growth construction under various shading condition. The results summarized this experiment were as follows; 1. The relative growth rate (RGR) in all experimental plots was high during the growth stage of 20 days after transplanting, and then decreased. The maxium RGR value appeared in the control plot (2.13g/g. 10days) during the growth stage from 10 to 20 days after transplating. RGR value in server shading of short day condition was remarkably decreased from the early growth stage. The main factor to lower RGR value considered as a short day condition than that of shading. 2. The net assimilation rate (NAR) in all experimental plots except 3hour photoperiod plot was high during the early growth stage after transplanting, and then decreased early growth stage after transplanting, and then decreased as the growth proceeded. The maxium value appeared in the control plot (35g/g. 10days). NAR value in the severe shading of short day condition plots was low. Especially, NAR value in the three hours photoperiod plot was remarkably low from the early growth, there was no great difference by growth stage. NAR had negative correlation with LAI and positive correlation with RGR. 3. The increasing rate of leaf area ratio(LAR) was high during the early growth stage after transplanting in the control plot and in the photoperiod plot, the shorter the exposure time to sunlight, the higher the LAR value from the early growth stage. Especially, its value in the 3 hour photoperiod plot was remarkably high but its increasing rate was lower as the growth proceeded. LAR hade negative correlation on RGR and NAR. 4. The crop growth rate(CGR) in each experimental plot was increased until 50 days after transplanting, and then decreased. After that time, the maxium CGR value appeared in the control plot (1.56g/$\textrm{cm}^2$. 10-days), 60 days after transplanting, CGR had positive correlation with LAI. The optimum LAI in the control, 9 hour, 7 hour, 5 hour, and 3 hour photoperiod plots appeared as 1.87, 1.12, 0.83, and 0.18.

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