• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2955-2959
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• 2011

Second-order rate constants for nucleophilic substitution reactions of 2,4-dinitrophenyl benzenesulfonate 1a with a series of alicyclic secondary amines in MeCN have been measured spectrophotometrically and compared with those reported previously for the corresponding reactions performed in aqueous medium to investigate the effect of medium on reactivity and reaction mechanism. The amines employed in this study are found to be more reactive in the aprotic solvent than in $H_2O$. The reactions of 1a in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.58, which contrasts to the curved Br${\o}$nsted-type plot reported previously for the corresponding reactions performed in the aqueous medium (i.e., ${\beta}_2$ = 0.86 and ${\beta}_1$ = 0.38). Accordingly, it has been concluded that the reaction mechanism changes from a stepwise mechanism to a concerted pathway upon changing the medium from $H_2O$ to MeCN. Reactions of Y-substituted phenyl benzenesulfonates 1a-c with piperidine in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{lg}$ = -1.31, indicating that expulsion of the leaving group is significantly more advanced than bond formation in the transition state. The trigonal bipyramidal intermediate ($TBPy^{\pm}$) proposed previously for the reactions in $H_2O$ would be highly unstable in MeCN due to strong repulsion between the negative charge in $TBPy^{\pm}$ and the negative dipole end of MeCN. Thus, destabilization of $TBPy^{\pm}$ in MeCN has been concluded to change the reaction mechanism from a stepwise mechanism to a concerted pathway.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3253-3257
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• 2012

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2719-2723
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• 2012

A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1915-1919
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• 2010

Second-order rate constants $(k_N)$ have been measured for reactions of 2,4-dinitrophenyl phenyl carbonate (2) with a series of pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ and compared with the $k_N$ values reported for the corresponding reactions of 2,4-dinitrophenyl benzoate (1) to investigate the effect of nonleaving group on reactivity and mechanism. The reactions of 2 result in larger $k_N$ values than those of 1. The Br${\o}$nsted-type plot for the reactions of 2 exhibits a downward curvature (i.e., ${\beta}2$ = 0.84 and ${\beta}1$ = 0.16), which is typical for reactions reported to proceed through a stepwise mechanism with a change in rate-determining step. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a{^{\circ}}$, has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of $k_N$ into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1}$ ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the $k_2/k_{-1}$ ratio has been found to be independent of the electronic nature of Ph and PhO.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2023-2028
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• 2013

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

• Journal of Digital Convergence
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• v.16 no.5
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• pp.351-359
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• 2018

The purpose of this study was to investigate the levels of emotional intelligence, and convergent nurses' work environment and to identify the effects of emotional intelligence and convergent nurses' work environment on nursing performance among clinical nurses as career-beginners. The study subject was a total of 95 clinical nurses as career-beginners that were recruited from three hospitals. Descriptive statistics, t-test, ANOVA, Pearson correlation coefficient and stepwise multiple regression with SPSS 21.0 program were used to analyze the data. The study results had shown significant correlations of emotional intelligence, and convergent nurses' work environment and regulator of emotional and leadership had explanation power 28.0% of nursing performance. We should consider the methods to enhance regulator of personal emotional and improve leadership of administrators for nursing performance. Therefore, the results can be used as basic data to develop nursing performance improvement program and the strategies for clinical nurses as career-beginners.

• Journal of Digital Convergence
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• v.16 no.9
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• pp.309-317
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• 2018

The purpose of this study was to examine influences on grit in the nursing student. The data were collected from 146 nursing students in the H university located Y city and April 16 2018 to April 20 2018. The data were analyzed by descriptive statistics, T-test, ANOVA, Pearson's correlation coefficient, and stepwise multiple regression. Grit was found to be in a significant positive correlation with positive psychological capital and academic achievement. The result of the stepwise multiple regression indicates the positive psychological capital predict 21.1% of grit. Therefore, it is necessary to develop an education program to strengthen the positive psychological capital of nursing students.

• Asian Pacific Journal of Cancer Prevention
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• v.16 no.16
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• pp.7321-7326
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• 2015

As the essence of health in humans, spiritual health is a fundamental concept for discussing chronic diseases such as cancer and a major approach for improving quality of life in patients is through creating meaningfulness and purpose. The present descriptive analytical study was conducted to assess the relationship between spiritual health and quality of life in 210 patients with cancer admitted to the Cancer Institute of Iran, selected through convenience sampling in 2014. Data were collected using Spiritual Health Questionnaire and the European Organization for Research and Treatment of Cancer Quality of Life Questionnaire (EORTC-QLQ). Patients' performance was assessed through the Karnofsky Performance Status Indicator and their cognitive status through the Mini-Mental State Examination (MMSE). Data were analyzed in SPSS-16 using descriptive statistics and stepwise linear regression. The results obtained reported the mean and standard deviation of the patients' spiritual health scoreas $78.4{\pm}16.1$ and the mean and standard deviation of their quality of life score as $58.1{\pm}18.7$. The stepwise linear regression analysis confirmed a positive and significant relationship between spiritual health and quality of life in patients with cancer (${\beta}$=0.688 and r=0.00). The results of the study show that spiritual health should be more emphasized and reinforced as a factor involved in improving quality of life in patients with cancer. Designing care therapies and spiritual interventions is a priority in the treatment of these patients.

• Asian Pacific Journal of Cancer Prevention
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• v.13 no.11
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• pp.5483-5488
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• 2012

Background: Although nicotine dependence plays a role as a main barrier for smoking cessation, there is still a lack of solid evidence on the validity of biomarkers to determine nicotine dependence in clinical settings. This study aimed to investigate whether urinary cotinine levels could reflect the severity of nicotine dependence in active smokers. Materials and Methods: Data regarding general characteristics and smoking status was collected using a self-administered smoking questionnaire. The Fagerstr$\ddot{o}$m test for nicotine dependence (FTND) was used to determine nicotine dependence of the participants, and a total of 381 participants were classified into 3 groups of nicotine dependence: low (n=205, 53.8%), moderate (n=127, 33.3%), and high dependence groups (n=49, 12.9%). Stepwise multiple linear regression model and receiver operating characteristic (ROC) curves analyses were used to determine the validity of urinary cotinine for high nicotine dependence. Results: In correlation analysis, urinary cotinine levels increased with FTND score (r=0.567, P<0.001). ROC curves analysis showed that urinary cotinine levels predicted the high-dependence group with reasonable accuracy (optimal cut-off value=1,000 ng/mL; AUC=0.82; P<0.001; sensitivity=71.4%; specificity=74.4%). In stepwise multiple regression analysis, the total smoking period (${\beta}$=0.042, P=0.001) and urinary cotinine levels (${\beta}$=0.234, P<0.001) were positively associated with nicotine dependence, whereas an inverse association was observed between highest education levels (>16 years) and nicotine dependence (${\beta}$=-0.573, P=0.034). Conclusions: The results of this study support the validity of using urinary cotinine levels for assessment of nicotine dependence in active smokers.

• Journal of Digital Convergence
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• v.14 no.10
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• pp.107-117
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• 2016

This study examines information efficiency of financial information on the firm value for the listed manufacturing companies in Korea stock market in terms of timing pattern of information. We set 3 different test periods based on the financial statement released years - the current year, 90 days before financial statement announcement and the next year. We introduce using the stepwise regression method to examine the effect of financial variables on the stock returns. The financial variables include profitability ratio, growth ratio, stability ratio, activity ratio and market valuation ratio. The results of the study showed that both growth and profitability ratio affected the current year stock returns, while stability and activity ratio affected the next year stock returns. Growth rate of total asset affects both current year and next year stock returns. Our findings imply that the period in which financial information is reflected in the firm value, could vary with the characteristics of financial information.