• Bulletin of the Korean Chemical Society
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• 제23권1호
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• pp.65-70
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• 2002

We have evaluated the specific hydroxyl group-solvent and carbonyl group-solvent interactions by using an Alltima C18 stationary phase and by measuring the retention data of carefully selected solutes in 60/40, 70/30, and 80/20(v/v%) acetonitrile/water eluents at 25, 30, 35, 40, 45, and 50 oC. The selected solutes are phenol, acetophenone, alkylbenznes(benzene to hexylbenznene), 4 positional isomers of phenylbutanol, 5-phenyl-1-pentanol, 3 positional isomers of alkylarylketone derived from butylbenzene, and 1-phenyl-2-hexanone. The magnitudes of hydroxyl group-acetonitrile/water specific interaction enthalpies are larger than those of carbonyl group-acetonitrile/water specific interaction enthalpies in general while the magnitudes of carbonyl group-methanol/water specific interaction enthalpies are larger than those of hydroxyl group-methanol/water specific interactions. We observed clear discrepancies in functional group-solvent specific interaction among positional isomers. The variation trends of solute transfer enthalpies and entropies with mobile phase composition in the acetonitrile/water system are much different from those in the methanol/water system. The well-known pocket formation of acetonitrile in aqueous acetonitrile mixtures has proven to be useful to explain such phenomena.

• 대한화학회지
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• 제58권6호
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• pp.528-534
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• 2014

어떤 이성분계용액에서는 상한임계용액온도와 하한임계용액온도가 동시에 나타나는 원형모양의 온도-조성 상도를 보인다. 이러한 현상은 분자간 특정상호작용이 존재하는 경우 나타나는 것으로 알려져 있다. 특정상호작용을 묘사하는 방법에는 여러 가지가 있다. 본 연구에서는 특정상호작용의 총수가 이항분포에 따라 분포한다고 가정하였다. 이 경우 특정상호작용을 Regular 용액이론, Quasichemical 이론 그리고 Flory-Huggins 격자이론에 적용하였을 때 원형모양의 온도-조성 상도를 보이는 경우에 대한 정확한 수학적인 조건을 유도하였다. 그리고 매개변수들이 온도-조성상도에 미치는 영향을 조사하였고, 물-니코틴에 대한 온도-조성상도를 계산하여 실험값과 비교하여 보았다.

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.959-964
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• 2007

The benzene complexes with dimethyl sulfur (DMS) and fluorinated DMS (FDMS) have been investigated using ab initio calculations. The natural bond orbital (NBO) charge population on S atom varies remarkably for different conformations of DMS and FDMS, which determines the possible binding modes for their benzene complexes. The electronegative substituent at the methyl group of DMS causes a significant change in the molecular electrostatic potential around the sulfur atom and changes the interaction mode with aromatic ring. It was found that the sulfur…π interaction mode does not occur in the DMS-benzene complex, while it does in the FDMS-benzene complex. Both B3LYP and MP2 methods provide reliable structures, while the interaction energy obtained by B3LYP is unreliable.

• Bulletin of the Korean Chemical Society
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• 제25권1호
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• pp.85-89
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• 2004

Geometrical structures of [Pd(L)$Cl_2$] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)$Cl_2$ complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (Pd${\cdots}$O) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial ($Pd{\cdots}$O) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via ${\pi}$-acceptors of the empty d-orbitals.

• 대한화학회지
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• 제52권2호
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• pp.118-123
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• 2008

항암제인 독소루비신과 아데닌과의 상호작용을 알아보기 위하여 10-3~10-4의 수용액상 농도 범위에 서 1 : 2의 부피비로 혼합하여 조사하였다. 자외선 공명라만 분광법과 표면증강 라만 분광법을 이용하여 수용 액상에서 독소루비신 분자의 아데닌 분자에 대한 결합 자리를 알아 본 결과 독소루비신 분자는 아데닌 분자 의 7번 위치의 질소와 상호작용 가능성을 확인할 수 있었다.

• 대한화학회지
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• 제22권6호
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• pp.403-411
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• 1978

Collagen의 model compound인 poly(Gly-Pro-Pro)의 수화에 관해서 empirical ppotential energy 함수를 사용하여 이론적으로 연구하였다. 물 분자와 model compound 간의 상호작용 energy를 최소화시켜서 물 분자들의 위치와 결합 energies를 계산하였다. 다음에는 일차수화층에 물이 붙음으로써 생기는 안정화 energy를 계산하고, 전체 안정화에 기여하는 여러 energy components의 기여도에 대해 논의하였다.

• Bulletin of the Korean Chemical Society
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• 제7권2호
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• pp.124-129
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• 1986

The effects of molecular attraction and orientations for the energy mismatch variance, vibrational energy level and double-quantum transition, in the vibration-vibration energy exchange, have been considered. The contribution of molecular attraction increases the exchange rate of the purely repulsive interaction, in general, significantly, but which becomes smaller as the temperature is increased. As the energy mismatch is increased, its contribution is also increased, but which is small. However, its contribution for the double-quantum transition is very paramount. At each orientation, the exchange rate constants have been calculated and compared with the results for rotational average, and it is found that the exchange rate is a strong function of the orientation angles of colliding molecules. We have also discussed about the system having the strong interaction such as the hydrogen bond, and it is found that for this system the preferred orientation should be considered in order to calculate the exchange rates.

• Bulletin of the Korean Chemical Society
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• 제18권4호
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• pp.424-427
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• 1997

To study the NMR chemical shift arising from the 5f-electron orbital angular momentum and the 5f-electron spin dipolar-nuclear spin angular momentum interactions, the evaluation of the hyperfine integrals has been extended to any pairs of SCF type 5f orbitals adopting a general method which is applicable to a general vector R, pointing in any direction in space. From the electronic wavefunctions for 5f orbitals expressed in common coordinate system, the radial part of the hyperfine interaction integrals are derived by translating the exponential part, r2 exp(-2βr), in terms of R, rN and the modified Bessel functions. The radial integals for 5f orbitals are tabulated in analytical forms. When two of the hyperfine integrals along the (100), (010), (001), (110), and (111) axes are calculated using the derived radial integrals, the calculated values for the 5f system change sign for R-values larger than R　0.35 nm. But the calculated values for the 4f systems change sign for R-values larger than R　0.20 nm.

• Macromolecular Research
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• 제11권5호
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• pp.303-310
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• 2003

The phase behavior of binary blends of dimethylpolycarbonate-tetramethyl polycarbonate (DMPCTMPC) copolycarbonates and styrene-acrylonitrile (SAN) copolymers has been examined and then compared with that of DMPC/TMPC/SAN ternary blends having the same chemical components and compositions except that the DMPC and TMPC were present in the form of homopolymers. Both binary and ternary blends were miscible at certain blends compositions, and the miscible blends showed the LCST-type phase behavior or did not phase separated until thermal degradation temperature. The miscible region of binary blends is wider than that of the corresponding ternary blends. Furthermore, the phase-separation temperatures of miscible binary blends are higher than those of miscible ternary blends at the same chemical compositions. To explain the destabilization of polymer mixture with the increase of the number of component, interaction energies of binary pairs involved in these blends were calculated from the phase separation temperatures using lattice-fluid theory and then the phase stability conditions for the polymer mixture was analyzed with volume fluctuation thermodynamics.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3448-3450
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• 2012