• Bulletin of the Korean Chemical Society
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• 제23권11호
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• pp.1595-1603
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• 2002

In this paper we have presented the results of diffusion behavior of model systems for eight liquid n-alkanes ($C_{12}$-$C_{44}$) in a canonical (NVT) ensemble at several temperatures using molecular dynamics simulations. For these n-alkanes of small chain length n, the chains are clearly <$R_{ee}^2$>/6<$R_g^2$>>1 and non-Gaussian. This result implies that the liquid n-alkanes over the whole temperatures considered are far away from the Rouse regime, though the ratio becomes close to the unity as n increases. Calculated self-diffusion constants $D_{self}$ are comparable with experimental results and the Arrhenius plot of self-diffusion constants versus inverse temperature shows a different temperature dependence of diffusion on the chain length. The global rotational motion of n-alkanes is examined by characterizing the orientation relaxation of the end-to-end vector and it is found that the ratio ${\tau}1/{\tau}2$ is less than 3, the value expected for a isotropically diffusive rotational process. The friction constants ${\xi}$of the whole molecules of n-alkanes are calculated directly from the force auto-correlation (FAC) functions and compared with the monomeric friction constants ${\xi}_D$ extracted from $D_{self}$. Both the friction constants give a correct qualitative trends: decrease with increasing temperature and increase with increasing chain length. The friction constant calculated from the FAC's decreases very slowly with increasing temperature, while the monomeric friction constant varies rapidly with temperature. By considering the orientation relaxation of local vectors and diffusion of each site, it is found that rotational and translational diffusions of the ends are faster than those of the center.

• Journal of the Korean Society for Industrial and Applied Mathematics
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• 제16권3호
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• pp.181-192
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• 2012

Here in this paper, the steady paint film flow on a vertical wall of a non-Newtonian pseudo plastic fluid for drainage problem has been investigated. The exact solution of the nonlinear problem is obtained for the velocity profile. Also the average velocity, volume flux, shear stress on the wall, force to hold the wall in position and normal stress difference have been derived. We retrieve Newtonian case, when material constant ${\mu}_1$ and relaxation time ${\lambda}_1$ equal zero. The results for co-rotational Maxwell fluid is also obtained by taking material constant ${\mu}_1$ = 0. The effect of the zero shear viscosity ${\eta}_0$, the material constant ${\mu}_1$, the relaxation time ${\lambda}_1$ and gravitational force on the velocity profile for drainage problem are discussed and plotted.

• Bulletin of the Korean Chemical Society
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• 제19권12호
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• pp.1326-1333
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• 1998

The study of coupled relaxation for methyl spin system in 2,6-dichlorotoluene was performed on the basis of the magnetization mode formalism. Using five initial perturbing pulse sequences, eight experimntal data sets were obtained, which were fitted with theoretical expressions with nine spectral density parameters. The same experiment was carried out at both 50.3 MHz and 125.6 MHz in carbon frequency. The measured spectral densities at both fields are similar in the exception of that related with carbon random field term. Furthermore, from the dipolar spectral density, the physical values may be extracted depending on the model of molecular reorientation. For example, it was assumed that the molecular framework undergoes asymmetric diffusive rotational process and methyl group reorients by either diffusive rotation about its symmetry axis or jump among internal rotational potential minima.

• 한국자기공명학회논문지
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• 제4권1호
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• pp.29-40
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• 2000

Coupled carbon-13 relaxation study of 1,1,1-trichloroethane dissolved in DMSO has been performed to gain some crucial insight into the dynamics of methyl group in this compound. For this purpose the relaxation behaviors of several observable magnetization modes for CH3 spin system generated by various perturbing pulse sequences have been carefully investigated and various dipolar spectral densities were estimated by nonlinear numerical fittings of the observed data with the relaxation curves, which were then employed to determine the three principal values for the diffusion tensor for end-over-end molecular rotation as well as internal rotational parameters of methyl group. In this process we could uniquely determine two correlation times $\tau$int(1) and $\tau$int(2) which give valuable information on internal rotor dynamics and thus obtained data were interpreted on the basis of various proposed models for internal rotation. compound undergoes three-fold jumps at 25$^{\circ}$. The fact that the ratio $\tau$int(1) / $\tau$int(2) is close to 1.0 may be interpreted as indicating that methyl group in this C.

• 한국음향학회:학술대회논문집
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• 한국음향학회 1999년도 학술발표대회 논문집 제18권 1호
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• pp.171-174
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• 1999

Methyl acetate의 초음파 흡수측정을 0.2-10MHz의 주파수 범위, 은도 5-30에 걸쳐 광회절 초음파 공명법을 사용하여 행하였다. 그 결과, cis와 trans에 의한 완화는 단일 완화현상을 보였고 그 스책트럼으로 부터 완화 주파수와 완화강도를 결정하였다. 완화 주파수의 온도 의존성으로부터 활성화 에너지(${\Delta}H^{#}$)=6.6 kcal/mol을, 완화강도의 온도 의존성에서 엔탈피차(${\Delta}H$)=3.4 kcal/mol을 각각 구하였다.

• Bulletin of the Korean Chemical Society
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• 제4권1호
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• pp.25-28
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• 1983

The effect of internal rotation of methyl group in liquid perdeuterotoluene on nuclear quadrupole relaxation of methyl deuterons is investigated. A model of a spherical diffusor undergoing rotational diffusion is extended to include the extended diffusion of internal rotation. The overall reorientational correlation time in the presence of internal rotation is explicitly given as an analytical function of the angular momentum correlation time. Also, the degree of inertial effect in the internal rotation is evaluated.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.975-979
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• 2012

Structure and Dynamics of dilute two-dimensional (2D) ring polymer solutions are investigated by using discontinuous molecular dynamics simulations. A ring polymer and solvent molecules are modeled as a tangent-hard disc chain and hard discs, respectively. Some of solvent molecules are confined inside the 2D ring polymer unlike in 2D linear polymer solutions or three-dimensional polymer solutions. The structure and the dynamics of the 2D ring polymers change significantly with the number ($N_{in}$) of such solvent molecules inside the 2D ring polymers. The mean-squared radius of gyration ($R^2$) increases with $N_{in}$ and scales as $R{\sim}N^{\nu}$ with the scaling exponent $\nu$ that depends on $N_{in}$. When $N_{in}$ is large enough, ${\nu}{\approx}1$, which is consistent with experiments. Meanwhile, for a small $N_{in}{\approx}0.66$ and the 2D ring polymers show unexpected structure. The diffusion coefficient (D) and the rotational relaxation time ($\tau_{rot}$) are also sensitive to $N_{in}$: D decreases and $\tau$ increases sharply with $N_{in}$. D of 2D ring polymers shows a strong size-dependency, i.e., D ~ ln(L), where L is the simulation cell dimension. But the rotational diffusion and its relaxation time ($\tau_{rot}$) are not-size dependent. More interestingly, the scaling behavior of $\tau_{rot}$ also changes with $N_{in}$; for a large $N_{in}$ $\tau_{rot}{\sim}N^{2.46}$ but for a small $N_{in}$ $\tau_{rot}{\sim}N^{1.43}$.

• 한국인쇄학회지
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• 제23권2호
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• pp.1-14
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• 2005

Generally, printing inks are composed of pigment, vehicle and additive. Among others, the vehicle transfers the pigment to substrate and then binds it on the surface. So, rheological properties of the vehicle are an important factor which has influence on printability. Thus, in this study, rheology of the vehicle was investigated by using rotational rheometer according to molecular weight of resin. Also, emlusion rheology of water in oil type and its microstructure were examined with increasing the shear rate. Consequently, the following results were obtained: (1) By viscometric flow test, zero shear viscosity and shear thinning index of vehicle increased with increasing the molecular weight of resin. (2) By relaxation and creep test, relaxation time and retardation time of vehicle increased with increasing the molecular weight of resin. (3) By frequency sweep test, crossover point of vehicle increased with increasing the molecular weight of resin. (4) G' and G" of emlusions increased with increasing the molecular weight by amplitude sweep test. (5) The shape of water drop in emlusions was changed to the capillary tube.

• Archives of Pharmacal Research
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• 제15권3호
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• pp.196-203
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• 1992

Intramolecular excimer formation of 1, 3-di(1-pyrenyl)propane (Py-3-Py) and fluorescence polarization of 1, 6-diphenyl-1, 3, 5-hexatriene (DPH) were used to investigate the effects of barbiturates on the fluidity of model membranes of phosphatidycholine (SPMVPC), phosphatidylserine (SPMVPS), and phosphatidylinositol (SPMVPI) fractions of synaptosomal plasma membrane vesicles (SPMV) isolated from bovine cerebral cortex. In a dose-dependent manner, barbiturates decreased the excimer to monomer fluorescence intensity ratio (I'/I) of Py-3-Py and increased the anisotropy(r), rotational relaxation time (P), limiting anisotropy $(r_infty)$, and order parameter (S) of DPH in SPMVPC, SPMVPS and SPMVPI. This indicates that barbiturates decreased both the lateral and rotational diffusion of the probes in SPMVPC, SPMVPS and SPMVPI. The relative potencies of barbiturates in ordering the membranes were in the order: pentobarbital > hexobarbital > amobarbital > phenobarbital. This order correlates well with the anesthetic potencies of barbiturates and the potencies for enhancement of $\gamma$-aminobutyric acid-stimulated chloride uptake. Thus, it is strongly suggested that a close relationship might exist between the membrane ordering effects of barbiturates and the chloride fluxes across SPMV.

• Bulletin of the Korean Chemical Society
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• 제35권6호
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• pp.1706-1712
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• 2014

The OH($X^2{\Pi}$, ${\upsilon}^{\prime\prime}=0,1$) internal state distribution following the reaction of electronically excited oxygen atom ($O(^1D_2)$) with cyclo-$C_3H_6$ has been measured using laser-induced fluorescence, and compared with that following the reaction of $O(^1D_2)$ with $C_3H_8$. The overall characteristics of the OH internal energy distributions for both reactions were qualitatively similar. The population propensity of the ${\Pi}(A^{\prime})$ ${\Lambda}$-doublet sub-level suggested that both reactions proceeded via an insertion/elimination mechanism. Bimodal rotational population distributions supported the existence of two parallel mechanisms for OH production, i.e., statistical insertion and nonstatistical insertion. However, detailed analysis revealed that, despite the higher exoergicity of the reaction, the rotational distribution of the OH following the reaction of $O(^1D_2)$ with $C_3H_8$ was significantly cooler than that with cyclo-$C_3H_6$, especially in the vibrational ground state. This observation was interpreted as the effect of the flexibility of the insertion complex and faster intramolecular vibrational relaxation (IVR).