• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.48-54
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• 2012

The $[Fe_4S_4]^{2+}$ clusters with 2-, 3-, and 4-pyridinemethanethiolate (S2-Pic, S3-Pic, and S4-Pic, respectively) terminal ligands have been synthesized from the ligand substitution reaction of the $(^nBu_4N)_2[Fe_4S_4Cl_4]$ (I) cluster. The new $(^nBu_4N)_2[Fe_4S_4(SR)_4]$ (R = 2-Pic; II, 3-Pic; III, 4-Pic; IV) clusters were characterized by FTIR and UV-Vis spectroscopy. Cluster II was crystallized in the monoclinic space group C2/c with a = 24.530 (5) $\AA$, b = 24.636(4) $\AA$, c = 21.762(4) $\AA$, ${\beta}=103.253(3)^{\circ}$, and Z = 8. The X-ray structure of II showed two unique 2:2 site-differentiated $[Fe_4S_4]^{2+}$ clusters due to the bidentate-mode coordination by 2-pyridinemethanethiolate ligands. Cluster III was crystallized in the same monoclinic space group C2/c with a = 26.0740(18) $\AA$, b = 23.3195(16) $\AA$, c = 22.3720(15) $\AA$, ${\beta}=100.467(2)^{\circ}$, and Z = 8. The 3-pyridinemethanethiolate ligand of III was coordinated to the $[Fe_4S_4]^{2+}$ core as a terminal mode. Cluster IV with 4-pyridinemethanethiolate ligands was found to have a similar structure to the cluster III. Fully reversible $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ redox waves were observed from all three clusters by cyclic voltammetry measurement. The electrochemical potentials for the $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ transition decreased in the order of II, III and IV, and the reduction potential changes by the ligands were explained based on the structural differences among the complexes. The complex III was reacted with sulfonium salt of $[PhMeSCH_2-p-C_6H_4CN](BF_4)$ in MeCN to test possible radical-involving reaction as a functional model of the [$Fe_4S_4$]-SAM (S-adenosylmethionine) cofactor. However, the isolated reaction products of 3-pyridinemethanethiolate-p-cyanobenzylsulfide and thioanisole suggested that the reaction followed an ionic mechanism and the products formed from the terminal ligand attack to the sulfonium.

• Applied Chemistry for Engineering
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• v.16 no.2
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• pp.243-249
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• 2005

Esterification of lactic acid with alcohols catalyzed by Amberlyst-type ion exchange resins and sulfuric acid was carried out in a batch reactor with total /or partial recycle of distilled condensates, respectively. The esterification of lactic acid in the total-recycling reactor (n-butanol/lactic acid = 4, $100^{\circ}C$) was promoted by decreasing the residual water and increasing the mole ratio of n-butanol/lactic acid. Also, it was confirmed that methanol with simple structure and tert-butanol with superior substitution reactivity were more effective in increasing the conversion of esterification reaction, compared to ethanol, n-butanol, and iso-butanol. In a partial-recycling reactor (n-butanol/ammonium lactate = 4, $115^{\circ}C$), the conversion of ammonium lactate into butyl lactate with 1.0 wt% Amberyst-type resins was higher in comparison to that with 0.2 mol $H_2SO_4$ (per 1.0 mol ammonium lactate). The esterification was gradually occurred during the initial stage of reaction in the presence of solid catalyst, whereas the initial addition of $H_2SO_4$ did not affect the initial rate of esterification reaction because of ammonium sulfate formation by the neutralizing reaction of ammonium lactate with sulfuric acid.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.704-709
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• 1998

Non-linear optical polymer based on poly (${\alpha}$-methylstyrene-co-maleic anhydride) (MSMA) substrate polymer was prepared by polymer reaction method and its thermal and electro-optic properties were examined. In the polymer reaction between MSMA substrate polymer and 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1) chromophore, the degree of substitution of DR1 into MSMA was higher with the 4-dimethylaminopyridine (DMAP) as catalyst and 3-dicyclohexyl carbodiimide (DCC) as dehydrating agent (sample, MSMA-DC) than the one with just 4-dimethylaminopyridine as catalyst (sample, MSMA-D). The synthesized NLO polymer (MSMA-DC) exhibited electro-optic coefficient of 18 pm/V (632.8 nm) and glass transition temperature ($T_g$) of about $175^{\circ}C$.

• Plant Biotechnology Reports
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• v.5 no.2
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• pp.127-134
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• 2011

The biotransformation potential of cell suspension cultures generated from Withania somnifera leaf was investigated, using withanolides, i.e. withanolide A, withaferin A, and withanone as precursor substrates. Interestingly, the cell suspension cultures showed inter-conversion of withanolides, as well converted to some unknown compounds, released to the culture media. The bio-catalyzed withanolide was detected and quantified by TLC and HPLC, respectively. There is noticeable conversion of withanolide A to withanone, and vice versa though at a lower level. The type of reaction of this biotransformation appears to be substitution of 20-OH group to 17-OH in withanolide A. In this paper, we present for the first time the possibility of biotransformation by inter-conversion of withanolides of pharmacological importance through cell suspension culture of W. somnifera. The possible role of putative cytochrome $P_{450}$ hydroxylases is implicated in the conversion.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.663-669
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• 2012

The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1037-1041
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1047-1051
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide with X-pyridines are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The free energy relationships for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ac. Unusual positive $\rho_X$ (= +4.73) and negative ${\beta}_X$ (= -0.75) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=39.3^{\circ}C$. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater magnitudes of selectivity parameters ($\rho_X$ = -6.15 and ${\beta}_X$ = 1.11) with the strongly basic pyridines compared to those ($\rho_X$ = 4.73 and ${\beta}_X$ = -0.75) with the weakly basic pyridines.

• KDI Journal of Economic Policy
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• v.25 no.1
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• pp.3-54
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• 2003

This paper studies the effects of the special surcharge on deposits, proposed as a plan to finance the costs of restructuring Korean corporate and financial sectors. Specifically, the study analyzes the change in the autonomous behavior of economic agents in terms of cost transfer and substitution effects. Given the result that the growth rate of deposits does not respond to the change of interest rates so much as that of loans, financial institutions have more incentive to transfer the costs incurred by the special surcharge to depositors. This paper also reports that the portfolio of households show a noteworthy feature that insured deposits have a relatively small portion in terms of total assets for high-asset class households, whereas most assets for low-asset class households are subject to the special surcharge.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.12 no.2
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• pp.73-79
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• 2002

The polyol process which applies to cobalt, nickel. copper and precious metals is a interesting and unexpected example of such a method for preparing uniform metal powders. The reaction proceeds via dissolution, and the polyol acts simultaneously as a solvent, a reducing agent, and to some extent a protective agent. Submicrometer uniform cobalt particles can be obtained by seeding the reactive medium ($AgNO_3$) to achieve a complete substitution of homogeneous by heterogeneous nucleation. By varying the number of nuclei it is possible to control to some extent the average particle size in the submicrometer (0.5$\mu$m) range.

• Transactions of the Korean hydrogen and new energy society
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• v.8 no.4
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• pp.161-171
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• 1997

$AB_2$ type Zr-based Laves phase alloys have been studied for potential application as negative electrode in Ni/MH batteries. However, They have a serious disadvantage of poor activation behavior in KOH solution. In this work, a new method of alloy design method was tried for improving Zr-based alloy activation. this method has focused on phase controlling to make multi-phase microstructure. In the case of multi-phase Zr-V-Mn-Ni shows good performance in activation, but activation mechanism has not been known. So, we were in search of elucidating this mechanism, Using morphological and electrochemical analysis, we could find that surface morphology and electocatalytic activity of the alloy change during immersion in KOH solution. V-rich second phases are selectively corroded and dissolved and then become Ni-rich phases. Resulting from these surface reaction in KOH solution, self-hydrogen charging occurs through Ni-rich phase. However, the alloy has poor cyclic durability because of such a corrosion mechanism. Therefore, finally we developed durable alloys by substitution of other alloying element.