• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.504-511
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• 2008

Two kinds of nitroazobenzene derivatives: 4-{4'-(nitrophenylazo)phenoxy}alkanoic acids (NAAn, n = 2~8, 10, number of methylene units in the alkyl chain) and 4-{4'-(nitrophenylazo)phenoxy}alkanoyl chlorides (NACn, n = 2~8, 10) were synthesized, and their thermotropic liquid crystalline behaviors were investigated. NAA6 formed an enantiotropic nematic phase, while the remainders, except NAA2, showed monotropic nematic phases. Isotropic-nematic transition temperature ($T_{iN}$) and change of entropy (${\Delta}S$) at $T_{iN}$ for both of NAAn and NACn varied by the change of n, and pronounced odd-even effects of n were also observed. However, the $T_{iN}$ and ${\Delta}S$ values of NAAn were much higher than those of NACn. This fact may be attributed to the hydrogen bonding between carboxyl groups. Thermal properties and degree of order in the mesophase and the magnitude of the odd-even effects of both NAAn and NACn were significantly different from those reported for 4-(alkoxy)-4'-nitroazobenzenes. It was discussed in terms of the differences in the molecular anisotropy and the temperature-dependent flexibility of the substituted groups.

• Korean Journal of Environmental Biology
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• v.17 no.2
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• pp.129-138
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• 1999

Chlorinated aromatic compounds are one of the largest groups of environmental pollutants as a result of world-wide distribution by using them as herbicides, insecticides, fungicides, solvents, hydraulic and heat transfer fluids, plasticizers, and intermediates for chemical synthesis. Because of their toxicity, persistence, and bioaccumulation, the compounds contaminated ubiquitously in the biosphere has attracted public concerns in terms of serious influences to wild lives and a human being, such as carcinogenicity, mutagenicity, and disturbance in endocrine systems. The biological recalcitrance of the compounds is caused by the number, type, and position of the chlorine substituents as well as by their aromatic structures. In general, the carbon-halogen bonds increase the recalcitrance by increasing electronegativity of the substituent, so that the dechlorination of the compounds is focused as an important mechanism for biodegradation of chlorinated aromatics, along with the cleavage of aromatic rings. The removal of the chlorine substituents has been known as a key step for degradation of chlorinated aromatic compounds under aerobic condition. This can occur as an initial step via oxygenolytic, reductive, and hydrolytic mechanisms. The studies on the biochemistry and genetics about microbial dechlorination give us the potential informations for microbial degradation of xenobiotics contaminated in natural microcosms. Such investigations might provide biotechnological approaches to solve the environmental contamination, such as designing effective bioremediation systems using genetically engineered microorganisms.

• Journal of the Korean Chemical Society
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• v.32 no.2
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• pp.135-143
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• 1988

The correlations between chromatographic parameters of monosubstituted benzenes and several physical parameters in reversed phase liquid chromatography were studied. The relationships between retention data and polarity index were investigated by plotting $log(log k'_S/k'_B)$ vs. $P'_S/P'_B$ which were relative retention and relative polarity index of monosubstituted benzenes with respect to benzene, respectively. The linear relationship between relative retention and polarity index was observed for the monosubstituted benzenes having polar group, while in case of those having nonpolar group, the good linearity was observed by combination with relative molecular weight i.e. $(P'_S/P'_B)/(MW_S/MW_B)$. Multivariant regression analysis, $a(P'_S/P'_B)+b(MW_S/MW_B)$+c did not give significantly better correlations compared to single variant analysis, $a[(P'_S/P'_B)/(MW_S/MW_B)]$+c, but multiple stepwise regression analysis was recommended when several physical parameters simultaneously were chosen. The best correlation between retention data for monosubstituted benzenes taken from the literature and substituent constant(${\pi}$), derived from hydrophobic parameter and the first order molecular connectivity index$(^1{\chi}^{\nu})$, was established for methanol/water mobile phase system. The larger the surface coverage of the stationary phase, the higher was the correlation coefficient between these two parameters and retention data.

• Polymer(Korea)
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• v.35 no.1
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• pp.77-86
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• 2011

Polymerization properties of six dinuclear constrained geometry catalysts (DCGC) were investigated. The different length bridges of three catalysts were para-phenyl (Catalyst 1), para-xylyl (Catalyst 2), and para-diethylene phenyl (Catalyst 6). The other three DCGC have the same para-xylyl bridge with the different substituents at the phenyl ring of the bridge. The selected substituents were isopropyl (Catalyst 3), n-hexyl (Cataylst 4), and n-octyl (Catalyst 5), It was found that the longer catalyst not only exhibited a greater activity but also prepared a higher molecular weight copolymer. The catalyst 3 having a bulky isopropyl substituent revealed the lower activity but formed the highest molecular weight polymer comparing with the other alkyl substituted DCGCs. These results were able to be understood on the basis of the electronic and steric characteristics of the bridge. This study confirms that the control of the bridge structure of DCGC may contribute to control the microstructure of polymers.

• Applied Biological Chemistry
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• v.38 no.5
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• pp.455-462
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• 1995

The new six herbicidal N-[(pyrimidin-2-yl)aminocarbonyl]-2-substituted-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide derivatives(S) were synthesized and rate constants for the hydrolysis of thier in the range of pH $1.0{\sim}10.0$ have been studied in 15%(v/v) aqueous acetonitrile solution at $45^{\circ}C$. From the basis of the results, pH-effect, solvent effect, ortho-substituent effect, thermodynamic parameters(${\Delta}H^{\neq}$ & ${\Delta}S^{\neq}$), pKa constant(4.80), rate equation, analysis of hydrolysis products(2-(1-hydroxy-2-fluoroethyl)benzenesulfonamide & 4,6-dimethoxyaminopyrimidine), it may be concluded that the general acid catalyzed hydrolysis through $A-S_E2$ mechanism and specific acid catalyzed hydrolysis through A-2 type(or $A_{AC}2$) mechanism proceeds via conjugate acid($SH^+$) and tetrahedral intermediate(I) below pH 8.0, whereas, above pH 9.0, the general base catalyzed hydrolysis by water molecules(B) through $(E_1)_{anion}$ mechanism proceeds via conjugate base(CB). In the range between $pH\;7.0{\sim}pH\;9.0$, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.40 no.3
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• pp.161-166
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• 1996

6-ethyl-5,6-dihydrouracil($C_6H_10N_2O_2$) is monoclinic, space group $$P2_{1}c}$$ with a=10.302(2), b=10.419(3), $c=7.095(1)\AA$, $\beta=106.6(0)$, Z=4, $V=729.7(3)\AA$^3$$, $D_c=1.29 g/cm^3,\;{\lambda}(MoK\alpha)=0.71073\AA$, $\mu=0.010cm^{-1}$, F(000)=304, and R=0.054 for 1070 unique observed reflection with F>4.0 $\sigma(F).$ The structure was solved by direct methods and refined by full-matrix least-squares refinement with the fixed C-H bond length at $0.96\AA.$ The hydrouracil molecule makes an envelope conformation with the ethyl substituent oriented to an axial position attainable to a varying degree of steric strain. There are two intermolecular hydrogen-bondings via N-H---O interactions, being nearly parallel to the 100 plane. The shortest distance between molecules is $3.187\AA$ of C(4) and O(8) (-x,-y, 1-z).

• Proceedings of the Korea Concrete Institute Conference
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• 2008.04a
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• pp.769-772
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• 2008

The problem of disposing construction waste materials has become a national and social problem. Recycled powder generated in the process of making aggregate, and the recycled powder is land-filled in its entirety. Results of toxicity testing of recycled power show that it contains base-pair substituent mutagenicity. As recycled powder is disposed of as landfill, it can cause secondary contamination such as soil and underground water contamination. There has been very little research made on recycled powder. This study has examined the utilization of concrete mixture by using recycled powder in a mixture instead of cement and compared and analyzed the characteristics of dynamics and workability. This study has examined the application of recycled powder in concrete. Depending on the replacement rate and workability, test piece was manufactured using different mixing rate by CP, WCP, PCP. The CP was used to examine the physical property of concrete and characteristics its dynamics. The letters W of WCP and P of PCP are the initials of water and mixture. They were made using the standard mixing ratiosemphasizing the workability to determine the characteristic of dynamics of concrete based on the mixing ratio of recycled powder. With the increase in the replacement rate, CP had very little change in the strength. But with the decline of slump, the workability was not good. The result of manufacturing WCP and PCP using the standard mixing ratio showed that WCP had a drop in strength compared to the plain. PCP had almost the same value as the plain only when the replacement rate was 10%. When it was higher than that, a reduction in strength was observed.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3588-3592
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

• Nuclear Engineering and Technology
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• v.13 no.3
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• pp.145-152
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• 1981

Even though a lately reported method of high temperature exchange labelling of o-iodo-hippuric acid (Hippuran) in the absence of oxidizing agent was considered to be an attractive one, the exchange mechanism was somewhat unclear. In this study iodine isotope exchanges between o-iodohippuric acid (OIH) and radioiodide ($^{125}$ $I^{ }$) or between OIH and molecular radioiodine ($^{125}$ $I_2$) were carried out at two different temperatures. Rate constants and activation parameters were measured by applying a radio-paper chromatography technique. Since o-iodobenzoic acid is known as a by-product in the exchange labelling of OIH, data were also obtained for the OIB-iodide systems for comparison. The rate constant was increased in the order of OIB...$^{125}$ $I^{[-10]}$ >OIB...$^{125}$ $I_2$>OIH..$^{125}$ $I^{[-10]}$ >OIH...$^{125}$ $I_2$ and the activation parameters for OIH were generally larger than those for OIB :$\Delta$H$\neq$$_{OIH}$>$\Delta$H$\neq$$_{OIB}$, $\Delta$S$\neq$$_{OIH}$>$\Delta$S$\neq$$_{OIB}$. These results suggest that the mechanism of the high temperature exchange is predominantly nucleophilic even though some electrophilic character can also be involved depending upon reaction conditions. Such a fact may well be caused by a feasible formation of hydrogen bonding type transition state due probably to the ortho substituent effect of-CONHC $H_2$COOH. Thus, the high temperature exchange method is estimated to be quite effective for labelling Hippuran especially at a small research center where reducing agent-free $^{131}$ I is unavailable.ailable..

• The Korean Journal of Pesticide Science
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• v.9 no.4
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• pp.279-286
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• 2005

The herbicidal activities against pre-emergence barnyard grass (Echinochloa crus-galli) by a series of new 2-(4-(6-chloro-2-benzoxazolyloxy)phenoxy)-N-phenylpopionamide derivatives as substrate molecule were studied using molecular holographic (H) quantitative structure activity relationships (HQSAR) methodology. From the based on the findings, the higher herbicidal active compounds are predicted by the derived HQSAR model. The best HQSAR model (VI-1) was derived from fragment distinction combination of atoms/bonds in fragment size, $7{\sim}10$bin. The herbicidal activities from atomic contribution maps showed that the activity will be able to increased according to the R-substituents variation of the N-phenyl ring and change of 6-chloro-2-benzoxazolyloxy group. Based on the results, the statistical results of the best HQSAR model (VI-1) exhibited the best pedictability and fitness for the herbicidal activities based on the cross-validated value ($q^2=0.646$) and non cross-validated value ($r^2_{ncv.}=0.917$), respectively. From the graphical analyses of atomic contribution maps, it was revealed that the lowest herbicidal activitics depends upon the 4-(6-chloro-2-benzoxazolyloxy)phenoxy group ($pred.pI_{50}=-3.20$). Particularly, the R=4-fluoro, X=isobutoxy substituent (P2) of (X)-phenoxy-N-(R)-phenylpropionamide derivative is predicted as the highest active compound ($pred.pI_{50}=9.12$).