• Journal of the Korean Chemical Society
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• v.43 no.3
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• pp.251-256
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• 1999

Viscosities of toluene were experimentally determined by the falling-ball method at several temperatures and pressures to investigate the pressure and temperature dependence of the viscosity of toluene. With the shear stress of the viscous flow of toluene, the shear free energy, the shear entropy, and the shear enthalpy were defined to discuss the variations of the shear thermodynamic properties with pressure. The effect of temperature and pressure on the shear thermodynamic properties obtained experimentally can be explained by means of the molecular thermal agitation due to temperature incleasing and the steric effect of the closed molecules of to Iuene due to pressure elevation.

• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.71-75
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• 1995

Tricarbonyl(2-methyl-1-phenylpentadienyl)iron(+1) hexafluorophosphate cation was prepared by the protonation of tricarbonyl(4-methyl-5-hexadien-1-ol)iron wit hexafluorophosphoric acid. Reaction of the cation with water, dimethyl cuprate, diphenylacetylenyl cuprate, and enolate of cyclohexanone gave the corresponding (η4-1,3-diene)Fe(CO)3. The regioselectivity for the nucleophilic attack appears to the predominantly the result of steric effect.

• Journal of the Korean Chemical Society
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• v.20 no.4
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• pp.295-298
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• 1976

The fact that a reaction between organothioenamine phosphonate and styrene oxide produces a derivative of cyclopropane has been proved by structural identification. This suggests that an anionic oxygen atom from the ring opening of the styrene oxide by nucleophilic attack of thioenamine phosphonate links to the phosphorous atom to from a betaine as an intermediate which is followed by cleavage of the weak P-C bond. The dextrorotatory optical activity of the product showed that the reaction was under the control of steric stability of the benzyl carbon in styrene which leads to the product through a sterically stable pathway.

• Journal of the Korean Chemical Society
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• v.29 no.3
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• pp.205-212
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• 1985

By using the Mass-Weighted-Cartesian coordinate method, the allosteric effect of 2,2'-bipyridyl crown(4) ether is studied. The vibrational modes of 235, 234, 188, and 178cm$^{-1}$ belong to the pore opening motion of crown ether and those of 168, 104, and 67cm$^{-1}$ belong to the rotational vibration motion of bipyridyl. Especially the mode appearing at 178cm$^{-1}$ shows a large allosteric effect by activation of the allosteric site.

• Journal of the Korean Chemical Society
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• v.29 no.3
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• pp.247-251
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• 1985

Dichloro cobalt(III) complex of a flexible tetradentate ligand of ethylenediamine-N,N'-di-S-${\alpha}$-propionic acid (eddp) has been prepared via the air-oxidation technique. Only ${\Delta}$-cis isomer has been yielded showing high stereoselectivity of the eddp ligand. Elemental analysis, ir, nmr and electronic absorption spectra have been used to characterize the complex and the absolute configuration of the complex is assigned by means of the nmr spectroscopy.

• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.465-470
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• 1997

A chiral pentadentate ligand, 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triaza-nonane, (S,S-prochen) which shows the stereospecific reaction was synthesized from the reaction of S-proline and diethylenetriamine (dien). The red-violet $[Co(SS-prodien)H_2O]ClO_4$ was prepared by the oxidation of the aqueous solution dissolving $CoCl_2{\cdot}6H_2O$ and S,S-prodien. Elemental analysis, electronic absorption spectroscopy, and $^{13}C-NMR$ spectroscopy suggest that the geometrical structure of the Co(III) complex to be an ${\alpha}{\beta}$ (ffm) form, where the dien moiety of the ligand chelates the metal center to comprise a facial isomer, and an aqua ligand coordinates a cis site to the secondary nitrogens of the dien. Based upon the CD spectroscopic analysis, it seems that the absolute configuration of the ${\alpha}{\beta}$(ffm)-$[Co(SS-prodien)H_2O]ClO_4$ has the ${\Lambda}$-form.

• Journal of the Korean Chemical Society
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• v.58 no.6
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• pp.560-568
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• 2014

The contribution of electrostatic interactions to protein folding reaction was studied by using mutant ubiquitin with lysine to alanine mutation at residue position 29. Based on the three dimensional structure of ubiquitin, lysine 29 is located close to negatively charged glutamate 16 and aspartate 21 and considered to stabilize the native state of ubiquitin by electrostatic interactions between these residues. The equilibrium unfolding experiment showed that the native stability was decreased by about ~20% upon mutation. This observation indicates lysine 29 indeed forms electrostatic interactions with nearby residues. Folding kinetics measurements using stopped-flow device and quantitative analysis of kinetics data indicate that ubiquitin folds from unfolded state to native state via intermediate state as observed previously. This intermediate state was observed to form immediately after the initiation of folding reaction. The folding intermediate was shown to be destabilized considerably upon lysine to alanine mutation. These observations indicate that electrostatic interactions can form early stage of protein folding and hence lead the folding reaction.

• Journal of the Korean Chemical Society
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• v.34 no.3
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• pp.239-247
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• 1990

The gas-phase S_N2$ reactions can be classified into neutral bimolecular, solvated, and ionic reactions; the neutral bimolecular reaction proceeds via retention mechanism whereas the ionic reaction produces inversion products. In the reaction of solvated nucleophile with one solvent molecule, a six-center transition state (TS) is formed and the two processes i.e., retention and inversion, are found to compete with a favored path depending on the electronic effect of the nucleophile and substituents in the substrate and on the steric requirement. In the ionic reaction, the difference in the energy barrier between the two processes reduces to a small value when the substrate methyl group is made bulky, leaving ability of the leaving group is improved and at the same time the negative charge of the nucleophile is dispersed. When the reaction center atom in the $S_N2$ reaction is changed to a larger sized second row elements, the activation barrier decreases since the steric crowding in the penta-coordinated TS is relieved. However within the same row, the barrier was found to increase as the atomic size decreased. For the boron, B, the barrier height was the least since in addition to the relatively large atomic size compared to C and N, it forms tetra-coordinated TS so that the steric crowding becomes nearly negligible.

• Journal of the Korean Chemical Society
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• v.40 no.11
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• pp.692-698
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• 1996

A synthesis of the oxazole skeleton of discokiolide B, represented by discokiic acid 1, is described. Aldol condensation of 2[2'-(4-phenyl-3-butenyl)]-1,3-oxazole 4-carboxaldehyde(4a) with lithium enolate of methyl propionate provided the discokiic acid methyl ester. The key intermediate 2[2'-(4-phenyl-3-butenyl)]-1,3-oxazole-4-carboxaldehyde (4a) has been synthesized from the rhodium-catalyzed cycloaddition of diazomalonaldehyde with nitrile. The relative stereochemistry of the 3-hydroxy-2-methylpropanoate unit of discokiic acid was assigned on the basis of $^1H$ and $^{13}C$ NMR data.

• Korean Journal of Environmental Agriculture
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• v.13 no.2
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• pp.191-198
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• 1994

2-Thiophenyltriisopropoxytitanium was prepared in situ by trans-metallization of 2-thiophenyllithium and chlorotitaniumtriisopropoxide. It could be isolated at room temperature and preserved at $-10{\circ}C$ for weeks. The reactivity of 2-thiophenyltriisopropoxytitanium to carbonyl compounds proved to be high. Complete aldehyde-selectivity was observed in competition reactions of 2-thiophenyl-triiso-propoxytitanium with a 1 : 1 mixture of aldehyde and ketone. In the competitive reaction of 2-thiophenyl-triisopropoxytitanium to ketone-ester function, ketone adduct was perfectly obtained.