• Journal of Photoscience
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• v.1 no.1
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• pp.31-37
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• 1994

Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.

• Journal of Pharmaceutical Investigation
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• v.36 no.3
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• pp.169-174
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• 2006

The aim of this work was to prepare tenoxicam-ethanolamine salt with improved physicochemical properties for transdermal application. Tenoxicam-ethanolamine salt was prepared in methylene chloride and its physicochemical properties were investigated by DSC and FT-lR. The broad peak of tenoxicam around 3600-3200 $cm^-1$ was shifted to lower wavenumber and more broadened. The characteristic endothermic melting peak of tenoxicam appeared at $223^{\circ}C$. The melting peak of tenoxicam-ethanolamine salt was shifted to $159^{\circ}C$. In contrast to relatively small difference in the partition coefficients of tenoxicam and the tenoxicam-ethanolamine salt, large difference in aqueous solubility was observed. $Crovol^{\circledR}$ PK4O (PEG-12 palm kernel glycerides) provided the highest skin flux for both compounds. The order of the enhancing effect of the various vehicles tested was similar for tenoxicam and tenoxicam-ethanolamine salt, which indicated that their enhancing mechanism for tenoxicam and tenoxicam-ethanolamine salt is similar. Tenoxicam-ethanolamine salt had a higher skin flux than tenoxicam by 1.2- to 31.7-fold, depending on the vehicles used. It is suggested that the vehicles with medium HLB value, 1 double bond, and lower ethylene oxide chain length have a better ability to modify the permeability of the stratum corneum and to promote the effective penetration of tenoxicam and tenoxicam-ethanolamine salt.

• Structural Engineering and Mechanics
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• v.67 no.6
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• pp.579-585
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• 2018

Masonry walls are of a complex (anisotropic) structure in terms of their mechanical properties. The mechanical properties of the walls are affected by the properties of the materials used in wall construction, joint thickness and the type of masonry bond. The carried-out studies, particularly in the seismic zones, have revealed that the most of the conventional masonry walls were constructed without considering any engineering approach. Along with that, large-scale damages were detected on such structural elements after major earthquake(s), and such damages were commonly occurred at the brick-joint interfaces. The aim of this study was to investigate the effect of joint thickness and also type of mortar on the mechanical behavior of the masonry walls. For this aim, the brick masonry walls were constructed through examination of both the literature and the conventional masonry walls. In the construction process, a single-type of brick was combined with two different types of mortar: cement mortar and hydraulic lime mortar. Three different joint thicknesses were used for each mortar type; thus, a total of six masonry walls were constructed in the laboratory. The mechanical properties of brick and mortars, and also of the constructed walls were determined. As a conclusion, it can be stated that the failure mechanism of the brick masonry walls differed due to the mechanical properties of the mortars. The use of bed joint thickness not less than 20 mm is recommended in construction of conventional masonry walls in order to maintain the act of brick in conjunction with mortar under load.

• Journal of the Korean Chemical Society
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• v.18 no.3
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• pp.180-188
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• 1974

Adsorption mechanism of alkyl aldehydes, acetaldehyde, acrolein, and crotonaldehyde on cations supported by layer silicates was studied by means of IR spectroscopy and X-ray. An analysis of four characteristic split bands in the region of $1720∼1580㎝^{-1}$ was made. The carbonyl stretching band which shifted about $130㎝^{-1}$ to lower frequencies was observed only for $Ni^{2+}$ and Al^{3+}$ but slightly with $Ca^{2+}$ at high sample temperature and was attributed to >C=O…M complex formation. A sharp band which appeared as a shoulder at 1722 for acetaldehyde and 1690 for acrolein and crotonaldehyde was responsible for the interaction of carbonyl with surface hydroxyl. The second broad band which appeared at about 1710~1660 was responsible for hydrogen bonding between carbonyl oxygen and cationic hydroxyl group. The third band which appeared at about 1640~1660 was attributed to induced >C=C< double bond due to the strong carbonyl interaction. This was supported by the interlamellar spacings obtained by X-ray diffractometry.

• Korean Journal of Social Welfare
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• v.63 no.2
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• pp.233-260
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• 2011

This study intends to analyze the trend of employment rate of men aged 55~64 in 15 OECD countries from 1980 to 2005. Furthermore, this study means to examine the determinants of men aged 55~64 in 15 OECD countries to support the labor force participation among them. The analysis is based on the data of OECD, ILO and LIS. The analysis method is Arellano and Bond(1981)'s difference GMM which used instrumental variables by dynamic panel model which estimates state dependency of labor market participation and individual panel's heterogeneity. The main results from this analysis are summarized in three points. First, the employment rates of men aged 55~64 had decreased until the middle of the 1990s, while that has been increasing since 1995. Second, the sate dependency strongly worked in the employment rates of 55~64 men and positive period effect was observed for 1980~2005. This study cannot find the pull effect of public pension, while labor market push effect have negatively affected. Third, temporary work rates had contributed to increase the employment rate of men aged 55~64 for 1996~2005. The poverty has become the mechanism of the labor.

• BMB Reports
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• v.31 no.5
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• pp.459-467
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• 1998

A new set of functional group interaction energy descriptors relevant to the ACE (Angiotensin-Converting Enzyme) inhibitory peptide, QSAR (Quantitative Structure Activity Relationships), is presented. The functional group interaction energies approximate the charged interactions and distances between functional groups in molecules. The effective energies of the computationally derived geometries are useful parameters for deriving 3D-QSAR models, especially in the absence of experimentally known active site conformation. ACE is a regulatory zinc protease in the renin-angiotensin system. Therapeutic inhibition of this enzyme has proven to be a very effective treatment for the management of hypertension. The non bond interaction energy values among functional groups of six-feature of ACE inhibitory peptides were used as descriptor terms and analyzed for multivariate correlation with ACE inhibition activity. The functional group interaction energy descriptors used in the regression analysis were obtained by a series of inhibitor structures derived from molecular mechanics and semi-empirical calculations. The descriptors calculated using electrostatic and steric fields from the precisely defined functional group were sufficient to explain the biological activity of inhibitor. Application of the descriptors to the inhibition of ACE indicates that the derived QSAR has good predicting ability and provides insight into the mechanism of enzyme inhibition. The method, functional group interaction energy analysis, is expected to be applicable to predict enzyme inhibitory activity of the rationally designed inhibitors.

• Geomechanics and Engineering
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• v.19 no.6
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• pp.485-498
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• 2019

Pre-tensioned rock bolts can be classified into fully anchored, lengthening anchored and point anchored bolts based on the bond length of the resin or cement mortar inside the borehole. Bolts in varying anchoring methods may significantly affect the supporting effect of surrounding rock around a tunnel. However, thus far, the theoretical basis of selecting a proper anchoring method has not been thoroughly investigated. Based on this problem, 16 schemes were designed while incorporating the effects of anchoring length, pretension, bolt length, and spacing, and a systematic numerical experiment was performed in this paper. The distribution characteristics of the stress field in the surrounding rock, which corresponded to various anchoring scenarios, were obtained. Furthermore, an analytical approach for computing the active and passive strengthening index of the anchored surrounding rock is presented. A new fully anchoring method with pretension and matching technology are also provided. Then, an isolated loading model of the anchored surrounding rock was constructed. The physical simulation test for the bearing capacity of the model was performed with three schemes. Finally, the strengthening mechanism of varying anchoring methods was validated. The research findings in this paper may provide theoretical guidelines for the design and construction of bolting support in tunnels.

• Journal of the Korean Chemical Society
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• v.17 no.3
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• pp.154-162
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• 1973

The rates and activation parameters for the halide $(Cl^{-}, Br^{-}, I^{-})$TeX> exchange reactions of substituted benzenesulfonyl-chloride, $XC_6H_4SO_2Cl$(X:p-MeO, H, p-Cl, p-Br, p-NO$_2l$) in dry acetone at two temperatures have been determined. It was found that the ion-pair of metal halide,$M^{+}X^{-}$, have negligible reactivity compared to free halide ions. It was also found that the nucleophilic order is $Cl^{-}>Br^{-}>I^{-}$for electron-donating substituent, and $Cl^{-}>I^{-}>Br^{-}$ for electron-withdrawing substituents. These results and convex nature of the Hammett plot are interpreted in the light of simple $S_N2$mechanism with the bond breaking becoming important for compounds with the electron withdra-wing substituents.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3495-3501
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• 2014

A novel crystal, the mono-protonated metformin acetate (1), was obtained and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. It was found that one of the imino group in the metformin cation was protonated along with the proton transfer from the secondary amino group to the other imino group. Its crystal structure was then compared with the previously reported diprotonated metformin oxalate (2). The difference between them is that the mono-protonated metformin cations can be linked by hydrogen bonding to form dimers while the diprotonated metformin cations cannot. Both of them are stabilized by intermolecular hydrogen bonds to assemble a 3-D supermolecular structure. The four potential tautomer of the mono-protonated metformin cation (tautomers 1a, 1b, 1c and 1d) were optimized and their single point energies were calculated by Density Functional Theory (DFT) B3LYP method based on the Polarized Continuum Model (PCM) in water, which shows that the most likely existed tautomer in human cells is the same in the crystal structure. Based on the optimized structure, their Wiberg bond orders, Natural Population Analysis (NPA) atomic charges, molecular electrostatic potential (MEP) maps were calculated to analyze their electronic structures, which were then compared with the corresponding values of the diprotonated metformin cation (cation 2) and the neutral metformin (compound 3). Finally, the possible tautomeric mechanism of the mono-protonated metformin cation was discussed based on the observed phenomena.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2494-2504
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• 2014

P38 mitogen activated protein (MAP) kinase is an important anti-inflammatory drug target, which can be activated by responding to various stimuli such as stress and immune response. Based on the conformation of the conserved DFG loop (in or out), binding inhibitors are termed as type-I and II. Type-I inhibitors are ATP competitive, whereas type-II inhibitors bind in DFG-out conformation of allosteric pocket. It remains unclear that how these allosteric inhibitors stabilize the DFG-out conformation and interact. Organosilicon compounds provide unusual opportunity to enhance potency and diversity of drug molecules due to their low toxicity. However, very few examples have been reported to utilize this property. In this regard, we performed docking of an inhibitor (BIRB) and its silicon analog (Si-BIRB) in an allosteric binding pocket of p38. Further, molecular dynamics (MD) simulations were performed to study the dynamic behavior of the simulated complexes. The difference in the biological activity and mechanism of action of the simulated inhibitors could be explained based on the molecular mechanics/generalized Born surface area (MM/GBSA) binding free energy per residue decomposition. MM/GBSA showed that biological activities were related with calculated binding free energy of inhibitors. Analyses of the per-residue decomposed energy indicated that van der Waals and non-polar interactions were predominant in the ligand-protein interactions. Further, crucial residues identified for hydrogen bond, salt bridge and hydrophobic interactions were Tyr35, Lys53, Glu71, Leu74, Leu75, Ile84, Met109, Leu167, Asp168 and Phe169. Our results indicate that stronger hydrophobic interaction of Si-BIRB with the binding site residues could be responsible for its greater binding affinity compared with BIRB.