• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.168-170
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• 1987

The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.500-505
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• 2010

Two different dyes containing the same molecular weight but different chemical structure have been utilized for the study of thermodynamic parameters. In this study, {3-(4-(diethylamino)phenyl)-3-(1-ethyl-2-methyl-1H-indol-3-yl)isobenzofuran-1(3H)-one} (Blue 502) and {3-(4-(diethylamino)-2-methylphenyl)-3-(1,2-dimethyl-1H-indol-3-yl)isobenzofuran-1(3H)-one} (Blue 402) were used. It has been performed by measuring UV spectra of the two dyes. In general, the blue shift has been observed from both dyes in higher carbon number alcohol solvents. Interestingly, Blue 502 showed higher stability than Blue 402 in the same conditions used in this study. And, the equilibrium constants (0.9~1.0) of the dyes depending upon temperature change were also calculated using UV absorbance. The standard enthalpy calculated from equilibrium constants and molar absorptivity($\varepsilon$) are 10.94 kJ/mol in Blue 402 and 9.010 kJ/mol in Blue 502, respectively.

• Korean Journal of Food Science and Technology
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• v.24 no.4
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• pp.335-340
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• 1992

The amounts of salt diffused into radish after immersing in various concentrations of salt solution at different temperatures were measured and the changes of radish texture by the salt diffusion were estimated with the viscoelastic constants of a 3 element solid model determined by a stress relaxation test. The amount of salt diffused through radish was increased with increasing the salt concentration and soaking temperature. While the instantaneous stress, equilibrium elastic solid content and viscoelastic constants of radish were decreased as salt concentration and soaking temperature increased, the stress relaxed fast. Viscoelastic constants as well as the diffusivity were influenced by salt concentration more than by soaking temperature. The rheological equations for the predictable stress changes of radish after immersed in the salt solution at various conditions (temperature, salt concentration and impure salt) were suggested as a function of time.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.607-613
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• 1989

The chemical equilibria of Ni(II)-tetraamine (tetraamine = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene) complex ion in water, acetonitrile, acetone and nitromethane were investigated using spectrophotometric method, respectively. The equilibria between low-spin ($D_{4h}$) and high-spin ($O_h$) structures of Ni-tetraamine complex ion were presented in water, acetonitrile and acetone, but not in nitromethane. The eqilibrium constants, the reaction enthalpies and the reaction entropies were determined from analysis of the temperature dependence of the electronic spectra. The formation of the triplet species ($O_h$) was found to be exothermic. The solvent and electrolyte effects on the equilibrium constants could be explained by the dielectric constants of solvents and the reaction entropies.

• Analytical Science and Technology
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• v.8 no.1
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• pp.33-40
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• 1995

Only trace amounts of hydroxide ion can be extracted from aqueous phase into organic phase by Tetra-n-Butyl Ammonium Chloride(TBAC). Addition of small amounts of primary alcohols, particularly certain dials, dramatically changes the behavior of Phase Transfer Catalysis systems, and surprising amounts of base can be found in the organic phase. Quantitative measurements were carried out for the extraction amounts of primary alkoxides, secondary alkoxides, and diol anions into organic phase. On the other hand, the selectivity constants for extraction of primary alcohols and benzylalcohol could be separated to the equilibrium constants of the ion pairs such as $Q^+RO^-$ and $Q^+Cl^-$ in the aqueous and organic phases and this distribution coefficients between phases on anions respectively. In a word, the colligated property for the selectivity of $Q^+RO^-$ in which $Q^+$ is quaternary cation and $RO^-$ alkoxide ion could be discussed in more detail by using of the corresponding free energies to the various constants mentioned.

• Applied Chemistry for Engineering
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• v.1 no.2
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• pp.182-189
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• 1990

Various crosslinked poly(4-vinylpyridines) having different degrees of crosslinking were prepared by radical copolymerizations of 4-vinylpyridine with N, N'-2, 6-pyridinebisacrylamide as a crosslinker. The abilities of these crosslinked polymers to bind methyl orange and butyl orange were investigated at various temperatures in a buffer solution of pH 7. The first binding constants were evaluated from the equilibrium binding amounts. The first binding constants against the temperatures showed bell-shaped curves. Also, the first binding constants against the degree of crosslinking showed bell-shaped curves. When the temperature and the degree of crosslinking of maximum binding in the curves of these binding systems were compared with those of previous systems containing crosslinked poly(4-vinylpyridines) prepared by using N, N'-methylenebisacrylamide, N, N'-tetramethy-lenebisacryamide and divinylbenzene as crosslinkers, respectively, they were varied with the crosslinked poly(4-vinyl pyridines) containing different crosslinkers. These results were discussed in terms of the properties of the crosslinkers.

• Journal of the Korean Chemical Society
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• v.46 no.4
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• pp.323-330
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• 2002

The protonation equilibrium of 5-substituted 2-furaldehydes is investigated spectrophotometrically in aqueous sulfuric acid at $25^{\circ}C$ and the basicity constants(p$K_{BH+}$) of the substrates is calculated by means of the excess acidity method. The basicity constant of 5-metyl-2-furaldehyde having electron donating group is larger than that of 5- nitro-2-furaldehyde having electron withdrawing group. Difference between the basicity constants(p$K_{BH+}$) of these two compounds was about 3.25 pK unit. The m value which is the degree of solvation of the protonated substrate is similar to that of acetophenone having same protonation site. The dependence of p$K_{BH+}$ on m value shows good linear cor-relation.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2595-2602
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• 2009

Hexamer cluster of N,N-dimethylformamide(DMF) based on the crystal structure was investigated for the equilibrium structure, the stabilization energies, and the vibrational properties in the density functional force field. The geometry (point group $C_i$) of fully optimized hexamer clustered DMF shows quite close similarity to the crystal structure weakly intermolecular hydrogen bonded each other. Stretching force constants for intermolecular hydrogen bonded methyl and formyl hydrogen atoms with nearby oxygen atom, methyl C–H${\cdots}$O and formyl C–H${\cdots}$O, were obtained in 0.055 $\sim$ 0.11 and $\sim$ 0.081 mdyn/$\AA$, respectively. In-plane bending force constants for hydrogen bonded methyl hydrogen atoms were in 0.25 $\sim$ 0.33, and for formyl hydrogen $\sim$ 0.55 mdynÅ. Torsion force constants through hydrogen bonding for methyl hydrogen atoms were in 0.038 $\sim$ 0.089, and for formyl hydrogen atom $\sim$ 0.095 mdynÅ. Calculated Raman and infrared spectral features of single and hexamer cluster represent well the experimental spectra of DMF obtained in the liquid state. Noncoincidence between IR and Raman frequency positions of stretching C=O, formyl C–H and other several modes was interpreted in terms of the intermolecular vibrational coupling in the condensed phase.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.26 no.1
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• pp.11-36
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• 2021

The solar annual (Sa) and semiannual (Ssa) tides account for much of the non-uniform annual and seasonal variability observed in sea levels. These non-equilibrium tides depend on atmospheric variations, forced by changes in the Sun's distance and declination, as well as on hydrographic conditions. Here we employ tidal harmonic analyses to calculate Sa and Ssa harmonic constants for 21 Korean coastal tidal stations (TS), operated by the Korea Hydrographic and Oceanographic Agency. We used 19 year-long (1999 to 2017) 1 hr-interval sea level records from each site, and used two conventional harmonic analysis (HA) programs (Task2K and UTide). The stability of Sa harmonic constants was estimated with respect to starting date and record length of the data, and we examined the spatial distribution of the calculated Sa and Ssa harmonic constants. HA was performed on Incheon TS (ITS) records using 369-day subsets; the first start date was January 1, 1999, the subsequent data subset starting 24 hours later, and so on up until the final start date was December 27, 2017. Variations in the Sa constants produced by the two HA packages had similar magnitudes and start date sensitivity. Results from the two HA packages had a large difference in phase lag (about 78°) but relatively small amplitude (<1 cm) difference. The phase lag difference occurred in large part since Task2K excludes the perihelion astronomical variable. Sensitivity of the ITS Sa constants to data record length (i.e., 1, 2, 3, 5, 9, and 19 years) was also tested to determine the data length needed to yield stable Sa results. HA results revealed that 5 to 9 year sea level records could estimate Sa harmonic constants with relatively small error, while the best results are produced using 19 year-long records. As noted earlier, Sa amplitudes vary with regional hydrographic and atmospheric conditions. Sa amplitudes at the twenty one TS ranged from 15.0 to 18.6 cm, 10.7 to 17.5 cm, and 10.5 to 13.0 cm, along the west coast, south coast including Jejudo, and east coast including Ulleungdo, respectively. Except at Ulleungdo, it was found that the Ssa constituent contributes to produce asymmetric seasonal sea level variation and it delays (hastens) the highest (lowest) sea levels. Comparisons between monthly mean, air-pressure adjusted, and steric sea level variations revealed that year-to-year and asymmetric seasonal variations in sea levels were largely produced by steric sea level variation and inverted barometer effect.

• Journal of Microbiology and Biotechnology
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• v.11 no.4
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• pp.649-655
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• 2001

The kinetics of the thermolysin-catalyzed synthesis of N-(benzyloxycarbonyl)-L-phenylalanyl-L-leucine ethyl ester (Z-Phe-LeuOEt) from N-(benzyloxycarbonyl)-L-phyenylalanine (Z-Phe) and L-leucine ethyl ester (LeuOEt) in an ethyl acetate saturated aqueous system in a batch operation were studied. The kinetics for the synthesis of Z-Phe-LeuOEt were expressed using a rate equation for the rapid equilibrium random bireactant mechanism. The four kinetic constants involved in the rate equation were determined numerically by the quasi-Newton method so as to fit the calculated results with the experimental data. Within the pH and temperature range examined, the $K_{cat}$ value for the synthesis of Z-Phe-LeuOEt reached a maximum at pH 7.0 and $45^{\circ}C$, whereas the affinity between Z-Phe and thermolysin reached a maximum at pH 6.0 adn $40^{\circ}C$. The inhibitory effect of Z-Phe on the condensation reaction decreased as the pH and temperature decreased. In contrast, they affinity between LeuOEt and thermolysin remained unchanged within the pH and temperature range examined. Therefore, it was concluded that the protonation state of the carboxyl groups. of Z-Phe was more imprtant than that of the amono groups of LeuOEt for the synthesis of Z-Phe-LeuOEt in the present solvent system. The equilibrium yield at pH 6.0 and $30^{\circ}C$ was 8% higher than that at pH 7.0 and $40^{\circ}C$, although the rate was much slower. This result suggested that the affinity between the enzyme and the substrate rather than the overall rate was a more important factor affecting the equilibrium yield, when the peptide synthesis was carried out in a product-precipitation system.