• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2608-2612
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• 2009

The unequivocal solid-state structure and stereochemistry of the hetaryl leuco-TAM dye, 2,2’-(2-phenyl propane- 1,3-diylidene) bis(1,3,3- trimethylindoline) derivatives were established using X-ray single crystal analysis. The X-ray crystal analysis showed that the (Z, E)-isomers only formed stereoselectively, with a so-called “threebladed propeller” conformation, from the reaction of a Fischer base and benzaldehyde derivatives. These isomers were stacked in a juxtaposition to form a dimer or a double dimer, adopting either a triclinic, with P-1, or monoclinic crystal system with a space group P21/n in the unit cell of the crystal.

• 대한화학회지
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• 제57권6호
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• pp.684-690
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• 2013

Since a glycerol molecule has three active sites, two ${\alpha}$ and one ${\beta}$ hydroxyl groups; it undergoes condensation by releasing water molecules to produce linear, nonlinear and heterocyclic oligomers. The Gibbs free energy (G), enthalpy (H) and internal energy (E) of 7 diglycerol, 15 triglycerol and 23 tetraglycerol isomers were calculated at B3LYP level of theory using 6-311++G(d, p) basis set, in both gas and aqueous phases. Linear oligomers, ${\alpha}{\alpha}$-diglycerol, ${\alpha}{\alpha}$, ${\alpha}{\alpha}$-triglycerol and ${\alpha}{\alpha}$, ${\alpha}{\alpha}$, ${\alpha}{\alpha}$-tetraglycerol, were found to be the most stable oligomers in aqueous phase. It was found that the stability of cyclic oligomers decreases as the size of their rings increases. Cyclic oligomers are produced by dehydration of the acyclic ones which is an endothermic reaction while its ${\Delta}G$ is negative. The dehydration reaction is less endothermic in aqueous phase.

• 약학회지
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• 제30권1호
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• pp.47-50
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• 1986

The enantiomers of five amino acids (alanine, valine, threonine, leucine and phenylalanine) could be separated by gas chromatography with optically active (S)-5-isopropyll-$N^3$-phenyl-2-thiohydantoinic stationary phase, which prepared from L-valine and phenylisothiocyanate. Gas chromatographic separations on methylesterificated and N-trifluoroacetylated amino acids have been conducted in isothermal at several column temperatures (180~190, 200, $210^{\circ}C$). The separation factors were 1.29 (alanine, $190^{\circ}C$), 1.35 (valine, $190^{\circ}C$), 1.33 (threonine, $190^{\circ}C$), 1.17 (leucine, $190^{\circ}C$) and 1.05 (phenylalanine, $190^{\circ}C$) and D-isomers eluted prior to L-isomers in every instance. The result of this experiment shows that this stationary phase can be used for the separation of the other amino acids enantiomers.

• 한국연초학회지
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• 제6권1호
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• pp.25-31
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• 1984

The volatile aroma components were isolated from Korean flue-cured tobacco (N.C. 2326) by using a vacuum steam distillation method. Individual aroma components were identified by GCIMS and comparison of gas chromatowaphic retention time with those of the authentic samples. Sensory analysis showed that a vacuum steam-distilled product of Flue-cured tobacco had a typical haylike, floral and fruity aroma. Among 62 compounds identified, major compounds included neophytadiene, benzyl alcohol, ethyl acetate, phenyl ethyl alcohol, ethyl alcohol, ethyl formate, acetic acid, solanone, 2-acetyl pyrrole, $\beta$-ionone epoxide, 2, 4-heptadienal (2 isomers), megastigmatrienone (4 isomers), furfural and total amounts of 13 compounds were about 80%.

• Bulletin of the Korean Chemical Society
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• 제18권1호
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• pp.27-32
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• 1997

The geometries and energies of the isomers in alkyne complexes MCl(PH3)2(η2-C2H2), M=Rh and Ir, are theoretically investigated using ab initio methods at the Hartree-Fock and up to MP4 level of theory and relativistic effective core potentials for Rh and Ir metals. The optimized structures of Rh complexes, 1-3 at MP2/ECP1 level are in good agreement with the related experimental data. The binding energies of C2H2 to d8-metal fragments are computed to be ∼55 kcal/mol. The vinylidene complexes for Rh and Ir metals are calculated to be much lower in energy than the alkyne complexes. The alkyne-vinylidene rearrangement is possible to proceed exothermically through the intermediate hydrido-alkynyl complexes, 2 or 9. Detailed comparison is given about the geometries and relative energies on Rh and Ir isomers at the various level ab initio calculations with orbital analysis.

• Bulletin of the Korean Chemical Society
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• 제12권1호
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• pp.31-35
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• 1991

Three isomers of damascenone, odorous terpenic ketones, have been synthesized conveniently from a same starting material, ethyl 2,6,6-trimethyl-4-oxo-2-cyclohexene-1-carboxylate(1), which was easily available by the acid-catalyzed condensation of mesityl oxide or acetone with ethyl acetoacetate. ${\alpha}$-Damascenone(7) was prepared by converting the enone ester 1 into the corresponding tosylhydrazone(4), followed by treating with 4 molar equiv of allyllithium. ${\beta}$-Damascenone(12) was synthesized by chemoselective reduction of 1 with sodium borohydride/cerium chloride to give corresponding allylic alcohol 8, conversion of 8 into acetate 9, and thermal decomposition of 9 with DBU to afford ethyl ${\beta}$-safranate(10), followed by reaction with an excess amount of allyllithium. ${\gamma}$-Damascenone(15) was obtained by dehydration of 8 with boric acid to furnish ${\gamma}$-safranate(13), followed by treatment with 2 molar equiv of allyllithium.

• Bulletin of the Korean Chemical Society
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• 제7권1호
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• pp.45-50
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• 1986

Separation of optical isomers of some derivatives of amino acids by reversed-phase HPLC has been accomplished by adding a chelate of an optically active amino acid to copper(Ⅱ) to the mobile phase. Cu(Ⅱ) complexes of L-proline and L-hydroxyproline in the mobile phase showed different degrees of separation. Optical isomers of DNS derivatives of amino acids are selectively separated, but those of several other derivatives are not at all. The kinds of buffer agents, the pH, and the concentrations of acetonitrile and the Cu(Ⅱ) ligand all affect the separations. The elution behavior between D and L DNS-amino acids appears to depend on the alkyl side chain of the amino acids. A chromatographic mechanism is proposed that is based on a stereospecificity of the formation of ternary complexes by the D, L-DNS-amino acids and the chiral additive associated with the stationary phase. The steric effects of the ligand exchange reactions are related with the feasibility of cis and/or trans attack of the amino acids to the binary chiral chelate retained on the stationary phase.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.693-698
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• 2001

Ab initio density functional calculations on the structural isomers, the hydration energies, and the hydrogen bond many-body interactions for gauche-, trans-protonated ethylenediamine-(water)3 complexes (g-enH+(H2O)3, t-enH+(H2O)3) have been performed. The structures and relative stabilities of three representative isomers (cyclic, tripod, open) between g-enH+(H2O)3 and t-enH+(H2O)3 are predicted to be quite different due to the strong interference between intramolecular hydrogen bonding and water hydrogen bond networks in g-enH+(H2O)3. Many-body analyses revealed that the combined repulsive relaxation energy and repulsive nonadditive interactions for the mono-cyclic tripod isomer, not the hydrogen bond cooperativity, are mainly responsible for the greater stability of the bi-cyclic isomer.

• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.491-498
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• 1992

Chelating triphosphines were applied to freeze the fluxionality and to minimize the number of isomers found in the monophosphine analogues and this technique was proved to be useful. RuH(NO)$P_3$($P_3$; Cyttp, ttp and etp) complexes were characterized to have similar trigonal bipyramidal structures with linear NO groups. Cyttp prefers to have a meridional geometry while etp prefers a facial one and ttp complexes are mixture of these two isomers. The crystal structure of RuH(NO)(Cyttp) has been determined to have a distorted trigonal bipyramidal structure with a linear NO in the equatorial plane. The crystals are orthorhombic, space group $P_{nma}$, with unit cell dimensions a = 16.356(2), b = 20.474(2), c = 10.915(l) ${\AA}$, V = 3655 ${\AA}^3$, Z = 4, R = 0.035 and $R_w$ = 0.034 for the 2900 intensities with $F_o^2 >3{\sigma}(F_o^2)$ and the 208 variables.

• Bulletin of the Korean Chemical Society
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• 제20권12호
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• pp.1483-1486
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• 1999

The contents of pentachlorophenol (PCP) and 2,3,5,6-tetrachlorophenol (TeCP) in textile products are regulated for safety. Since an organic solvent such as 2-methoxyethanol is needed to extract chlorinated phenols from textile samples, nonaqueous capillary electrophoresis has been applied to achieve the separation of PCP and isomers of TeCP. The run buffer was 100 mM Tris/acetate in methanol whose pH was adjusted to 8.0. All of the analytes were negatively charged at pH 8.0 and their electrophoretic velocities were higher than the electroosmotic flow of the methanol buffer. A reverse voltage of -20 kV was applied along a 27-cm fused silica capillary with ID of 50 μm, and PCP and 3 TeCP isomers were separated based on the difference in $pK_a$ values in less than 4 min. The limits of detection (S/N = 3) were about 0.02 μM. By varying pH of the methanol run buffer, $pK_a$ values of the 4 chlorinated phenols were also estimated.