• 대한화장품학회지
• /
• 제40권4호
• /
• pp.383-390
• /
• 2014

기질 분자로서 2-[(2,6-dioxocyclohexyl)methyl]cyclohexane-1,3-dione 유도체(1-23)들의 분자 내 치환기($R_1$ 및 $R_2$)가 변화함에 따른 tyrosinase 수용체의 저해활성에 관한 2D-QSAR 모델로부터 다음과 같은 결론을 얻었다. 유도된 최적의 2D-QSAR 모델은 $Obs.pI_{50}=-0.295({\pm}0.031)TDM$ $-0.120({\pm}0.014)DMZ+0.135({\pm}0.050)DMX$. $R_2+6.382({\pm}0.17)$이었으며, 예측성($q^2=0.843$)보다는 상관성($r^2=0.905$)이 큰 모델이었다. Tyrosinase 저해활성은 TDM > $DMX.R_2{\geq}DMZ$ 순으로 영향을 미치었으며, 기질분자의 소수성(ClogP > 0)이 크고, $R_1$-치환기의 입체적 크기가 클수록 더욱 증가하는 경향을 나타내었다. 모델을 분석한 결과, 분자 내 $R_2$-치환기 상 X-축 성분의 쌍극자능률($DMX.R_2$)이 클수록, 그리고 분자 전체의 쌍극자능률(TDM; Total Dipole Moment)과 Z-성분의 쌍극자능률(DMZ; Dipole Moment of Z-Component)이 작을수록 기질분자의 tyrosinase 저해활성이 높아짐을 암시하였다. 따라서 tyrosinase 저해활성은 기질분자 및 $R_2$-치환기의 전자 친화력에 기인한 것으로 예상되었다. 그러므로 저해활성을 증가시키려면 분자 내 극성 그룹을 소수성에 기여하는 비극성 작용기로 대체함이 바람직할 것으로 예측되었다.

• 천문학논총
• /
• 제30권2호
• /
• pp.309-313
• /
• 2015

If the present universe is slightly open then pre-inflation curvature would appear as a cosmic dark-flow component of the CMB dipole moment. We summarize current cosmological constraints on this cosmic dark flow and analyze the possible constraints on parameters characterizing the pre-inflating universe in an inflation model with a present-day very slightly open ${\Lambda}CDM$ cosmology. We employ an analytic model to show that for a broad class of inflation-generating effective potentials, the simple requirement that the observed dipole moment represents the pre-inflation curvature as it enters the horizon allows one to set upper and lower limits on the magnitude and wavelength scale of pre-inflation fluctuations in the inflaton field and the curvature parameter of the pre-inflation universe, as a function of the fraction of the total initial energy density in the inflaton field. We estimate that if the current CMB dipole is a universal dark flow (or if it is near the upper limit set by the Planck Collaboration) then the present constraints on ${\Lambda}CDM$ cosmological parameters imply rather small curvature ${\Omega}_k{\sim}0.1$ for the pre-inflating universe for a broad range of the fraction of the total energy in the inflaton field at the onset of inflation. Such small pre-inflation curvature might be indicative of open-inflation models in which there are two epochs of inflation.

• Bulletin of the Korean Chemical Society
• /
• 제22권9호
• /
• pp.969-974
• /
• 2001

Model calculations for small molecules Li2, F2, LiF and BF have been performed at the Dirac-Fock level of theory using Dirac-Coulomb and Dirac-Coulomb-Magnetic Hamiltonians with various basis sets. In order to understand what may happen when the relativity becomes significant, the value of c, speed of light, is varied from the true value of 137.036 a.u. to 105 (nonrelativistic case) and also to 50 and 20 a.u. (exaggerated relativistic cases). Qualitative trends are discussed with special emphasis on the effect of the magnetic part of the Breit interaction term. The known relativistic effects on bonding such as the bond length contraction or expansion are demonstrated in this model study. Total energy, $\pi-orbital$ splitting, bond length, bond dissociation energy and dipole moment are calculated, and shown to be modified in a uniform direction by the effect of the magnetic term. Inclusion of the magnetic term raises the total energy, increases the bond length, reduces the $\pi-orbital$ splitting, increases the bond dissociation energy, and mitigates the changes in dipole moment caused by the Dirac term.

• 대한화학회지
• /
• 제57권4호
• /
• pp.461-471
• /
• 2013

Optimized geometrical structure, atomic charges, molecular electrostatic potential, nonlinear optical (NLO) effects and thermodynamic properties of the title compound N-(2,5-methylphenyl)salicylaldimine (I) have been investigated by using ab initio quantum chemical computational studies. Calculated results showed that the enol form of (I) is more stable than keto form. The solvent effect was investigated for obtained molecular energies, hardneses and the atomic charge distributions of (I). Natural bond orbital and frontier molecular orbital analysis of the title compound were also performed. The total molecular dipole moment (${\mu}$), linear polarizability (${\alpha}$), and first-order hyperpolarizability (${\beta}$) were calculated by B3LYP method with 6-31G(d), 6-31+G(d,p), 6-31++G(d,p), 6-311+G(d) and 6-311++G(d,p) basis sets to investigate the NLO properties of the compound (I). The standard thermodynamic functions were obtained for the title compound with the temperature ranging from 200 to 450 K.

• Bulletin of the Korean Chemical Society
• /
• 제20권5호
• /
• pp.587-591
• /
• 1999

A molecular dynamics simulation study on the structure and dynamics of Na+ ions in non-rigid dehydrated Na12-A zeolite framework at 298.15 K was conducted using the same method reported in previous studies on rigid and non-rigid Na12-A zeolite frameworks. The agreement between the experimental and calculated results for the zeolite-A framework atoms of structural parameters for non-rigid dehydrated Na12-A zeolite is generally quite good, and for the adsorbed Na+ions the agreement is acceptable. The calculated bond lengths are generally in good agreement with the experimental results and other theoretical data. The calculated IR spectrum by Fourier transform of the total dipole moment autocorrelation function shows two major peaks around 2700 cm-1 and 7000 cm-1. The former appeared in the calculated IR spectra of non-rigid zeolite-A framework only system and the latter remains unexplained except, perhaps, indicating a new formation of a vibrational mode of the framework due to the adsorption of Na+ ions. The peaks above 6200-6800 cm-1 in non-rigid dehydrated Nal2-A zeolite are much larger than those in non-rigid dehydrated H12-A zeolite.

• Bulletin of the Korean Chemical Society
• /
• 제27권2호
• /
• pp.211-218
• /
• 2006

This work deals with 24 substances composed of nitrogen-containing heterocycles. The relationships between the chromatographic retention factor (k) and those physicochemical properties which are relevant in quantitative structure-properties relationship (QSPR) studies, such as the polarizability $(\alpha)$, molar refractivity (MR), lipophilicity (logP), dipole moment $(\mu)$, total energy $(E_{tot})$, heat of formation $(\Delta H_f)$, molecular surface area $(S_M)$, and binding energy $(E_b)$, were investigated. The accuracy of the simple linear regressions between the chromatographic retention and the descriptors for all of the compounds was satisfactory (correlation coefficient, $0.8 \leq r \leq 1.0$). The QSPR models of these nitrogen-containing heterocyclic compounds could be predicted with a multiple linear regression equation having the statistical index, r = 1.000. This work demonstrated the successful application of the multiple linear approaches through the development of accurate predictive equations for retention factors in liquid chromatography.

• Bulletin of the Korean Chemical Society
• /
• 제28권9호
• /
• pp.1472-1476
• /
• 2007

Artificial neural networks (ANNs) are successfully developed for the modeling and prediction of normalized polarity parameter (ETN) of 216 various solvents with diverse chemical structures using a quantitative-structure property relationship. ANN with architecture 5-9-1 is generated using five molecular descriptors appearing in the multi-parameter linear regression (MLR) model. The most positive charge of a hydrogen atom (q+), total charge in molecule (qt), molecular volume of solvent (Vm), dipole moment (μ) and polarizability term (πI) are input descriptors and its output is ETN. It is found that properly selected and trained neural network with 192 solvents could fairly represent the dependence of normalized polarity parameter on molecular descriptors. For evaluation of the predictive power of the generated ANN, an optimized network is applied for prediction of the ETN values of 24 solvents in the prediction set, which are not used in the optimization procedure. Correlation coefficient (R) and root mean square error (RMSE) of 0.903 and 0.0887 for prediction set by MLR model should be compared with the values of 0.985 and 0.0375 by ANN model. These improvements are due to the fact that the ETN of solvents shows non-linear correlations with the molecular descriptors.

• Bulletin of the Korean Chemical Society
• /
• 제26권1호
• /
• pp.139-145
• /
• 2005

Artificial neural networks (ANNs), for a first time, were successfully developed for the modeling and prediction of solvent effects on rate constant of [2+2] cycloaddition reaction of diethyl azodicarboxylate with ethyl vinyl ether in various solvents with diverse chemical structures using quantitative structure-activity relationship. The most positive charge of hydrogen atom (q$^+$), dipole moment ($\mu$), the Hildebrand solubility parameter (${\delta}_H^2$) and total charges in molecule (q$_t$) are inputs and output of ANN is log k$_2$ . For evaluation of the predictive power of the generated ANN, the optimized network with 68 various solvents as training set was used to predict log k$_2$ of the reaction in 16 solvents in the prediction set. The results obtained using ANN was compared with the experimental values as well as with those obtained using multi-parameter linear regression (MLR) model and showed superiority of the ANN model over the regression model. Mean square error (MSE) of 0.0806 for the prediction set by MLR model should be compared with the value of 0.0275 for ANN model. These improvements are due to the fact that the reaction rate constant shows non-linear correlations with the descriptors.

• 대한화학회지
• /
• 제57권5호
• /
• pp.574-590
• /
• 2013

A new solid complexes of Ti(IV), Y(III) and Ce(IV) have been synthesized with ofloxacin. The formulae and structure of the complexes have been proposed in the light of analytical, spectral ($^1H$ NMR, IR and UV-Visible), magnetic, molar conductivities and thermal studies. The complexes are soluble in DMSO-$d_6$ and DMF. The measured molar conductance values indicate that, the three complexes are electrolyte in nature. The results support the formation of the complexes and indicated that ofloxacin reacts as a bidentate ligand chelate to the metal ion through the pyridone oxygen and one carboxylato oxygen. The kinetic parameters of thermogravimetric and its differential have been evaluated by using Coats Redfern (CR) and Horowitz-Metzeger (HM) methods. The thermodynamic data reflect the thermal stability for all complexes. The metal- ligand binding of the Ti(IV), Y(III) and Ce(IV) complexes is predicted using density funcational theory at the B3LYP-CEP-31G level of theory and total energy, dipole moment estimation of different Ti(IV), Y(III) and Ce(IV) ofloxacin structures. The biological activities of the ofloxacin, inorganic salts and their metal complexes were assayed against different bacterial species.

• Bulletin of the Korean Chemical Society
• /
• 제20권3호
• /
• pp.285-290
• /
• 1999

In the present paper, we report a molecular dynamics (MD) simulation study for the structure and dynamics of H+ ions in non-rigid dehydrated H12-A zeolite framework at 298.15 K, using the same method we used in our previous studies of rigid and non-rigid zeolite-A frameworks. It is found that two different structures appear, depending on the choice of the Lennard-Jones parameter (σ) for the H+ ion, as is also observed in the study of rigid dehydrated H12-A zeolite framework, but the ranges of σ are different for the two structures. It is also found that some of the H+ ions exchanged their sites without changing the number of H+ ions at each site. The agreement between experimental and calculated structural parameters for non-rigid dehydrated H12-A zeolite is generally quite good. The calculated IR spectrum by Fourier transform of the total dipole moment auto-correlation function shows two major peaks, one around 2700 cm-1 and the other around 7000 cm-1. The former appears in the calculated IR spectra of non-rigid zeolite-A framework only system and the latter remains unexplained except, perhaps, as an indication of a new formation of a vibrational mode of the framework due to the adsorption of the H+ ions.