• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1907-1911
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• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, 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 the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

• Journal of Nutrition and Health
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• v.37 no.4
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• pp.302-309
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• 2004

This study was carried out to investigate the effect of nutrition education program for diabetic patients on the glycemic control at the public health center. The study subjects, aged 61.7 $\pm$ 9.4 years, were 93 sex-and age-matched patients with type 2 diabetes mellitus. They were divided into three groups: nutrition education ＆ diet practice group (EDG), nutrition education-only group (EG), and the control group (CG). Height, weight, and the postprandial 2 hour blood glucose (PP2) were measured at baseline, and 4, 6 and 8 week after the diabetic nutrition education program. At baseline there were no differences in height, weight, and blood glucose levels among the three groups. Nutrition education programs, especially that with group lunch practice sessions were found to be effective in lowering the blood glucose levels in patients with NIDDM patients. At 4 week blood glucose levels were decreased by 40.6% and 19.6% in EDG and EG, respectively, which was further dropped by 50.2% and 35.1% at 8 week, as compared to the CG group. For the EDG group, the total energy intake, which was 162.3% of the prescription before the diet counselling session, was decreased to 113.6% of the prescription after the lunch visit, with most decrease coming from the reduction in carbohydrate and fat intake. Multiple stepwise regression analysis revealed that the total energy intake explained 47.9% and 57% of blood glucose changes for men and women, respectively, and that percent energy intake from protein explained 15.8% for women. These results demonstrate that the public health center nutrition education programs for diabetic patients, especially that with group lunch practice sessions are very effective for the glycemic control in patients with diabetes mellitus.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.93-97
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-2-methylbenzoates (5a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Hammett plots for the aminolysis of 5a-e are nonlinear, e.g., substrates possessing an electron-donating group (EDG) in the benzoyl moiety deviate negatively from the linear line composed of substrates bearing no EDG. In contrast, the Yukawa-Tsuno plots for the same reactions exhibit excellent linear correlations with ${\rho}_X$ = 0.30-0.59 and r = 0.90-1.15, indicating that the nonlinear Hammett plots are caused by stabilization of the substrates possessing an EDG through resonance interactions but are not due to a change in the rate-determining step (RDS). The Br${\phi}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.66-0.82. Thus, the aminolysis of 5a-e has been suggested to proceed through a stepwise mechanism in which departure of the leaving group occurs at the RDS. The ${\rho}_X$ and ${\beta}_{nuc}$ values for the aminolysis of 5a-e increase as the reactivity of the substrates and amines increases, indicating that the reactivity-selectivity principle is not applicable to the current reactions.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.436-440
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• 2014

The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

• Proceedings of the Korean Nuclear Society Conference
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• 2004.10a
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• pp.327-328
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• 2004

• Proceedings of the Korean Society for Noise and Vibration Engineering Conference
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• 2010.05a
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• pp.306-307
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• 2010

• Proceedings of the Korean Nuclear Society Conference
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• 2001.10a
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• pp.340.1-340
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• 2001

• Proceedings of the Korean Nuclear Society Conference
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• 2005.10a
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• pp.642-644
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• 2005

• Proceedings of the Korean Nuclear Society Conference
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• 2005.10a
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• pp.432-433
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• 2005

• Journal of Power System Engineering
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• v.8 no.2
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• pp.5-11
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• 2004

The failure frequency of the Emergency Diesel Generator(EDG) at Nuclear Power Plants(NPPs) is not so much lower than that of the Marine engines, whereas the running hours of the diesel engine at NPPs is much less than those of the engines for commercial service. The primary factor results from the severe surveillance test requirements such as fast start, large number of starting test, fast load-run, high load running, etc. The other factor comes from the excessive maintenance based on the engine maker's instruction manual that did not incorporate the peculiar characteristics of the diesel engines at NPPs. In this paper, the present preventive maintenance program on the basis of the Pielstick diesel engines was reviewed for the purpose of securing the reliability of the emergency diesel generator at NPPs and the ways for its improvement were presented by referring to the overseas cases for their applications.