• Journal of the Korean Chemical Society
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• v.50 no.4
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• pp.307-314
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• 2006

The redox characteristics of 2-ketohydrazono-3-phenyl-5-substituted-2,3-dihydro-1,3,4-thiadiazoles and its derivatives (1a-h) has been investigated in nonaqueous solvents such as 1,2-dichloroethane (DCE), dichloromethane (DCM), acetonitrile (AN), tetrahydrofuran (THF), and dimethylsulfoxide (DMSO) containing 0.1 mol.dm-3 tetra n-butylammonium perchlorate (TBAP) as supporting electrolyte at platinum ectrode. Through controlled potential electrolysis, the oxidation and reduction products of the investigated compounds can be separated and indentified. The redox mechanism is suggested and proved. It was found that all the investigated compounds are oxidized in two irreversible one-electron processes following the well known pattern of EC-mechanism. On the other hand, these compounds are reduced in a single two electron or in a successive two one electron processes following the well known pattern of EEC-mechanism according to the nature of the substituent

• Journal of the Korean Magnetics Society
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• v.7 no.4
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• pp.196-204
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• 1997

In order to study the effect of substituted $Al^{3+}$ of goethite, which was collected from Shinpyeongli in Cheju Island, we used X-ray diffractometer and Mossbauer spectrometer. In X-ray diffraction analysis, the X-ray diffraction peaks of goethite are not detected due to the high substituted Al contents of goethite. Isomer shifts indicated that the valence of Fe ions is almost oxidized trivalent of high spin state. It is believed that the contents of substituted diamagnetic $Al^{3+}$ for $Fe^{3+}$ is about 15.5 mol%. It seems that Neel temperature and saturated magnetic hyperfine field of the clay goethite are about 250 K and 498 kOe, respectively. For the temperature lower than Neel temperature, quadrupole splittings of the clay goethite are greatly influenced by $Al^{3+}$ substitution. It is believed that the high decrease of Neel temperature and magnetic hyperfine field of the clay goethite results from the magnetic dilution produced by substituting the diamagnetic $Al^{3+}$/TEX> for $Fe^{3+}$.

• YAKHAK HOEJI
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• v.35 no.6
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• pp.497-503
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• 1991

Six novel 5-substituted-1-[2-(3-methoxy-2-hydroxyphenyl)-1-methoxyethyl]uracils 2a-f were prepared by condensation of 2,4-bis(trimethylsilyloxy)-5-substituted uracils with 2,7-dimethoxy-2,3-dihydrobenzofuran (9) in the presence of Lewis acid. The 2,3-dihydrobenzofuran derivative 9 was obtained by intramolecular acetalization of 2-acetoxy-3-methoxyphenyl acetaldehyde (8) which was synthesized by oxidative cleavage of 1-allyl-2-acetoxy-3-methoxybenzene (7) using osmium tetroxide followed by $NaIO_4$. Compounds 2a-f were evaluated for in vitro antiviral activity against HSV-1, HSV-2 and HRV. None of these compounds showed activity with $ID_{50}$ values up to $100\;{\mu}g/ml$ except for 5-chlorouracil derivative 2d which exhibited antiviral activity against HSV-1 with $ED_{50}$ $30\;{\mu}g/ml$. In the antitumor activity against L1210 and P388 leukemia cell lines, 2d showed activity with $ID_{50}$ values of $14\;{\mu}g/ml$ and $11.6\;{\mu}g/ml$, and 2c with $ID_{50}$ values of $22.9\;{\mu}g/ml$ and $8.8\;{\mu}g/ml$, respectively.

• Journal of the Korean Chemical Society
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• v.19 no.3
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• pp.156-162
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• 1975

Rates of reactions of methanesulfonyl chloride with various substituted anilines have been measured in methanol. Substituent effects in aniline are found to be linearly correlated with pKa(Bronsted relation with ${\beta}$ = 0.84) and ${\rho}$(Hammett equation with ${\rho}$ = -2.46) respectively. The results are interpreted in terms of degree of bond-formation at the transition state, which was found to have progressed relatively further. The rates for o-methylaniline deviated from the Bronsted plot established by meta and para substituted anilines because of a steric effect of ortho position in aniline. Activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ have also been determined. The enthalpy of activation showed a regular variation in that electron donating substituents in the p-substituted aniline decrease ${\Delta}H^{\neq}$ and increase the negative value of ${\Delta}S^{\neq}$.

• Bulletin of the Korean Chemical Society
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• v.23 no.8
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• pp.1089-1096
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• 2002

Solvolyses rate constants of trimethylacetyl chloride (2), isobutyryl chloride (3), diphenylacetyl chloride (4) and p-methoxyphenylacetyl chloride (5) in 2,2,2-trifluoroethanol (TFE)-water, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-water and TFE-et hanol solvent systems at $10^{\circ}C$ are determined by a conductimetric method. Kinetic solvent isotope effects (KSIE) are reported from additional kinetic data for methanolyses of various substituted acetylchlorides in methanol According to the results of those reactions analyzed in terms of rate-rate profiles,extended Grunwald-Winstein type correlations, application of a third order reaction model based a general base catalyzed (GBC) and KSIE values. Regardless of the kind of neighboring groups (CH3- or Ph-groups) of reaction center, for aqueous fluorinated alcohol systems, solvolyses of 2, 3, 4, and 5 were exposed to the reaction with the same mechanism (a loose SN2 type mechanism by electrophilic solvation) controlled by a similarity of solvation of the transition sate (TS). Whereas, for TFE-ethanol solvent systems, the reactivity depended on whether substituted acetyl chloride have aromatic rings (Ph-) or alkyl groups (CH3-); the solvations by the predominant stoichiometric effect (third order reaction mechanism by GBC and/or by push-pull type) for Ph- groups (4 and 5) and the same solvation effects as those shown in TFE-water solvent systems for CH3- groups (2 and 3) were exhibited Such phenomena can be interpreted as having relevance to the inductive effect ( $\sigmaI)$ of substituted groups; the plot of log (KSIE) vs. ${\sigma}I$ parameter give an acceptable the linear correlation with r = 0.970 (slope = 0.44 $\pm$ 0.06, n = 5).

• Journal of the Korean Chemical Society
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• v.57 no.2
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• pp.246-251
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• 2013

With -$OCH_2CO$- as a linker, a non ${\beta}$-substituted cationic bisporphyrin (4a) and a ${\beta}$-substituted cationic bisporphyrin (4b) were prepared through methylation of the intermediate which was obtained from ${\beta}$-amino-5,10,15,20-tetra (4-cyanophenyl) porphyrin or 5-hydroxylphenyl-10,15,20-tris(4-cyanophenyl) reacting with 5-hydroxy-10,15,20-trispyridinylporphyrin. Their structures were confirmed by $^1H$ NMR, IR, UV-vis, MS and elemental analysis. DNA photocleavage ability and the singlet oxygen ability of those cationic bisporphyrins were investigated. DNA photocleavage activity of ${\beta}$-substituted cationic bisporphyrin was significantly weaker than that of $H_2TMPyP$, but similar to that of non ${\beta}$-substituted cationic bisporphyrin. While 4a and 4b showed substantial photocleavage activities toward DNA, with 68% and 66% observed at 10 ${\mu}M$. The assessment of indirectly measured $^1O_2$ production rates against $H_2TMPyP$ were described and the relative singlet oxygen production yields were: free cationic bisporphyrins > $H_2TMPyP$. The results showed the cationic bisporphyrins with ${\beta}$-substitution and non ${\beta}$-substitution could be developed as potential photodynamic agents.

• The Journal of Fisheries Business Administration
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• v.42 no.2
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• pp.31-45
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• 2011

Costal fisheries use small boat. The boats are frequently substituted with newly made boat or proper boat. When the boat which is substituted with another one after the fixed date for compensation is estimated for fisheries loss by public project, it is matter that which boat is the object for estimating average catch of fish. There are three ways in practical business. They are based on the date of spot probe, the date of conference for compensation and fixed date for compensation. In case of applying the first and the second ways, as the object of compensation is not fixed, there is problem that estimated result can be changed depending on changing boat tons even after the date of spot probe and the fixed date for compensation. Most of all, these ways are against Attached Form No.4 of the Enforcement Ordinance of Fisheries Law which regulate to calculate average catch of fish applying result of fishery for retroactively counted 3 years from the year before the year in which administrative measure day is. The other side, in applying boat tons based on the fixed date for compensation, estimated result of compensation will not change even boat substituted after the fixed date for compensation. Even though applying tons based on the fixed date for compensation, a problem still remains. If the boat get bigger after the fixed date for compensation, the then boat size must be applied for calculating average catch. But the boat get smaller, the changed boat size must be applied. Because changed small boat would be damaged less than the previous boat. And decrease in catch by changing boat into small one is not due to the project but due to the personal responsibility. This will help to increase objectivity and reliance on the compensation result. As the other objects are fixed based on the fixed date for compensation in the Act on Acquisition and Compensation of Land and Others for Public Project, it can be balanced with other object.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.613-617
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• 2009

3D-QSARs for the inhibition activities against protox by herbicidal 2-N-phenylisoindolin-1-one derivatives were studied quantitatively using CoMFA and CoMSIA methods. The result of the statistical quality of optimized CoMSIA model 2 ($FF:\;{r^2}_{cv.};\;0.973\;&\;{r^2}_{ncv.};\;0.612$) was higher than that of CoMFA model 1 ($AF:\;{r^2}_{cv.};\;0.414\;&\;{r^2}_{ncv.};\;0.909$). Also, the relative contribution of the optimized CoMSIA model 2 showed the steric (24.6%), electrostatic (31.0%), hydrophobic (ClogP, 23.4%) and H-bond acceptor field (21.0%), respectively. From the results of the contour maps, the protox inhibition activities are expected to increase when steric favor and H-bond acceptor favor groups are substituted on $R_2$ position and positive favor group are substituted on $C_2,\;C_3,\;and\;C_5$ atom in phenyl ring of $R_2$ position. And the inhibition activities are expected to increase when hydrophobic favor group is substituted on $C_1,\;C_3$ atom in phenyl ring of $R_2$ position and $C_1$ atom of $R_2$ position and hydrophilic favor groups are substituted on $C_4$ atom in phenyl ring of $R_1$ position and the terminal group of $R_1$ position.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2707-2712
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• 2009

5-$HT_{3}$ receptor;5-$HT_{3A}$ receptor channel activity;Novel 5-$HT_{3}$ receptor channel current blockers;Chlorophenyl substituted piperazinylethylaminomethylpyrazoles; The 5-$HT_{3A}$ receptors are one of ligand-gated ion channels and are known to be involved in visceral pain, anxiety, or anticancer agent-induced nausea and vomiting. In present study, we designed novel skeletons based on the developed 5-$HT_{3}$ receptor antagonists and evaluated their effects on 5-$HT_{3A}$ receptor channel currents ($I_{5-HT}$) of a series of pyrazole derivatives having N-chlorophenylpiperazine functionality (6-9). We found that most of N-p-chlorophenyl substituted piperazinyl-pyrazole derivatives (7b, 7c, 7e and 7h) exhibited the high potency for the inhibition of $I_{5-HT}$, whereas the compound without chloride (6) or with m-chlorophenyl group (a serious of 8 and 9) showed the low potency. These result indicate that p-chlorophenyl group is might play an important role for increasing the inhibitory potency on $I_{5-HT}$.

• Journal of the Korean Ceramic Society
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• v.40 no.11
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• pp.1096-1101
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• 2003

Si -substituted hydroxyapatite has been prepared to obtain biomaterials having an improved biocompatibility. From FT-IR, XRD, and ICP analyses, it was confirmed that the single-phase of hydroxyapatite substituted by Si has formed. Si- substituted hydroxyapatite of up to 2 wt% for Si keeps its original structures intact for the sintering temperatures of up to 1200$^{\circ}C$. However, it is observed that the ion substitutions by the amount higher than the above ratios for the hydroxyapatite leads to destabilize original structures of the hydroxyapatite and to produce tricalcium phosphate and calcium phosphate silicate phases when the samples were sintered at 1l00$^{\circ}C$ or higher.