• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3743-3747
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• 2011

Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${\rho}_Y$ is changed from unusual negative (${\rho}_Y$ < 0) with the weaker electrophiles to positive (${\rho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${\rho}_X$, ${\beta}_X$, and ${\rho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.

• Research in Community and Public Health Nursing
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• v.28 no.2
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• pp.107-117
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• 2017

Purpose: The purpose of this study is to examine the cognitive function in the elderly and to identify the influencing factors. Methods: The design of this study was descriptive research design. A total of 139 elderly people (aged 65 years and over) visiting the electroencephalogram (EEG) center in Seoul, Korea were evaluated. Data were assessed by self-administered questionnaires and CNS Vital Signs (CNSVS). Data were analyzed using SPSS Statistics 23.0 for Windows. Results: There were significant differences in the Korean Mini-Mental State Examination (K-MMSE), executive functions and reasoning according to education level. K-MMSE, visual memory and executive functions were different depending on the jobs. Age was highly correlated with cognitive function. In addition, stepwise multiple regression analyses showed that the factor significantly associated with reaction time and visual memory was depression. Depression and Trait-Anxiety had significant impacts on executive functions and K-MMSE. Conclusion: CNSVS enabled the accurate and objective measurement of cognitive function. Therefore, this study provides useful data to improve cognitive function of the community-dwelling elderly. The results suggested that there is need for comprehensive interventional programs that manage cognitive impairment.

• Journal of Microbiology and Biotechnology
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• v.10 no.5
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• pp.690-693
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• 2000

Efficient intron deletion with the correct splicing of the two exons of the human proinsulin gene was accomplished by a novel stepwise method using genomic DNA [5]. The two exons were separately amplified in two steps, using the second step primers that incorporated additional bases complementary to the other exon. The fragments were combined in a third PCR reaction. Cloning and sequencing of the PCR product demonstrated the correct splicing of the two exons. Expression studies, using the pET9a vector, revealed a protein band with the correct size with respect to human proinsulin as confirmed by SDS-PAGe and Western blot. Proinsulin concentration was estimated to be around 200 mg per liter culture, expressed as inclusion bodies. Protein secretion to the culture medium and periplasmic space was achieved by cloning in the pEZZ18 vector.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3947-3951
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• 2011

The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.201-204
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• 2002

The rates of the aminolysis of S-phenyl substituted-acetate series $(RC(=O)SC_6H_4Z$, with R=Me, Et, i-Pr, t-Bu and Bn) with benzylamines $(XC_6H_4CH_2NH_2)$ are not correlated simply with the Taft's polar $({\sigma}^{\ast})$ and/or steric effect constants $(E_s)$ of the substituents due to abnormally enhanced rate of the substrate with R=Et. Furthermore, the cross-interaction constant, ${\rho}x_z$ , is the largest with R=Et. These anomalous behaviors can only be explained by invoking the vicinal bond $({\sigma})$-antibond $({\sigma}^{\ast})$ charge transfer interaction between C-$C{\alpha}$ and C-S bonds. In the tetrahedral zwitterionic intermediate, $T^{\pm}$ , formed with R=Et the vicinal ${\sigma}_{c-c}-{\sigma}^{\ast}_{c-s}$ delocalization is the strongest with an optimum antiperiplanar arrangement and a narrow energy gap, ${\Delta}{\varepsilon}={\varepsilon}_{{\sigma}^{\ast}}-{\varepsilon}_{\sigma}$. Due to this charge transfer interaction, the stability of the intermediate increases (with the concomitant increase in the equilibrium constant K (= $k_a/k_{-a}$)) and also the leaving ability of the thiophenolate leaving group increases (and hence $k_b$ increases) so that the overall rate, $k_n\;=\;Kk_b$, is strongly enhanced. Theoretical support is provided by the natural bond orbital (NBO) analyses at the B3LYP/6-31+$G^{\ast}$ level. The anomaly exhibited by R=Et attests to the stepwise reaction mechanism in which the leaving group departure is rate limiting.

• 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 environmental and Sanitary engineering
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• v.18 no.3 s.49
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• pp.78-88
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• 2003

This study was conducted to investigate the relation between ozone concentration and the affecting factors in Seosan City of Korea from Jan. 2002 to Dec. 2002. We analyzed the air pollutants such as NO$_2$, PM$_{10} $,SO$_2$, CO and the meteorological factors including solar radiation, air temperature, wind speed and relative humidity. The analytical data were taken statistics by SPSS method. The results were as follows: The seasonal average concentration of ozone were detected 35.0 ppb in Spring, 25.4 ppb in Summer, 23.5 ppb in Autumn and 21.4 ppb in Winter. So the difference of concentrations showed significantly in statistics. The hourly ozone concentration in a day was increased at 7-9 AM, peaked at 3-4 PM. The correlation coefficients was negative to ozone concentration and NO$_2$, SO$_2$, CO, relative humidity, but positive to solar radiation, air temperature, wind speed. With stepwise multiple regression analysis on the 8 factors such as NO$ _2$, PMSO$_{10}$,SO$_2$, CO, solar radiation, air temperature, wind speed and relative humidity, the seasonal primary factors were air temperature in spring, relative humidity in summer and solar radiation in autumn and winter. The above results suggest that ozone is the secondary pollutant by photochemical reaction as the concentration of ozone was increased with the raise of solar radiation.

• Analytical Science and Technology
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• v.7 no.2
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• pp.205-211
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• 1994

Acetic acid and succinic acid bonded polyamine-polyurea(CPPI and SAPPI) resins were synthesized from the reaction of polyethylenimine-polymethylenepolyphenylene isocyanate(PPI) resin as matrix polymer and chloroacetic acid and chlorosuccinic acid respectively. These resins were confirmed with infrared spectrometry and elemental analysis. The adsorption characteristics of the chromium(III) and dichromate(or chromate) ions on the resins were studied by measuring distribution coefficients($K_d$) with changing pH of the solution. It was thought that these ions were adsorbed by ion exchange mechanism. Chromium(III) and dichromate ion could be separated with stepwise elution method by changing pH of the eluent using SAPPI resin packed column($0.6cm(i.\;d.){\times}10cm(L.)$). Also, dichromate ion could be preconecntrated with CPPI resin column by a concentration factor of 50.

• Journal of Korean Society for Atmospheric Environment
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• v.22 no.2
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• pp.249-257
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• 2006

In this work, the adsorptive and desorptive behavior of reduced sulfur compounds (RSC) was investigated using the combination of the Peltier cooling (PC)/thermal desorption (TD) unit with the gas chromatographic (GC) detection technique. To examine the adsorptive characteristics of RSC on clothing materials, a total of nine experiments were conducted in a stepwise manner. Once small towel pieces are exposed to significant quantities of RSC standards with high concentrations (10 ppm), the desoprtion stage was then induced by deloading RSC with ultrapure $N_2$ at three different flow rates (FR) of 20, 40, and 60 mL/min. At each FR, the total deloading volume of 400, 800, and 1,600 mL were maintained. These results were then compared in terms of odoring efficiency by dividing the total amount of desorption with the total amount used for exposition or RSC loading. The results indicated that desorption reaction of certain compounds ($CH_3SH$ and DMS) can be influenced significantly with the reducing FR, while they are not affected directly by the total deloading volume. In addition, when the extent of adsorption was compared for most S compounds by the odoring efficiency term, the extent of absorption generally occurred at approximately 1/1000 level of original exposition.

• Analytical Science and Technology
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• v.9 no.4
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• pp.345-354
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• 1996

Algal(II) Multidentate N, O-Schiff base ligands, such as bis(salicylaldehyde) ethylenediimine(SED), bis(salicylaldehyde) propylenediimine(SPD), bis(salicylaldehyde) diethylenetriimine(SDT), bis (salicylaldehyde) triethylenetetraimine(STT) and bis(salicyl-aldehyde)tetraethylenepentaimine(STP) were prepared. Stepwise proton dissociation constants of the Schiff base were measured potentiometrically in ethanol and a mixture of 70% dioxane and 30% $H_2O$. The stability constants of copper(II)-Schiff base complexes were in the order of Cu(II)-SPD${\leq}$Cu(II)-SED~STT${\leq}$Cu(II)-STP. Oxidation-reduction process of the Cu(II)-Schiff base complexes was involved with one-electron reaction.