• Journal of Photoscience
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• v.4 no.2
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• pp.61-67
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• 1997

The model based on the idea that the p$_y$-orbital of the carbonyl oxygen is responsible to receiving hydrogen was devised for simulation of intramolecular hydrogen transfer. A Monte Carlo method was applied to free rotation of a molecular chain performed by changing the dihedral angles, and a "hit" was defined as the case when the migrating hydrogen comes within the region defined as the p$_y$-orbital and satisfies all the geometrical requirements for abstraction. A set of parameters was employed for defining the region and the requirements; $\tau$ was defined as the angle formed between O...H vector and its projection on the mean plane of the carbonyl group (- 43$\circ$ < $\tau$ < + 43$\circ$), $\Delta$ as the C=O...H angle (90 -15$\circ$ < $\Delta$ < 90 + 15$\circ$), $\theta$ as the O...H - C angle ( 180 - 80$\circ$< 0 < 180 + 80$\circ$), d as the distance from the center of the lobe of the p$_y$-orbital to hydrogen (0 < d < 1.04 ${\AA}$). The minimum value for the distance between carbonyl oxygen (O$_1$) and the migrating hydrogen (H$_i$) and for that between non-bonded atoms except the pair of O$_1$ and H$_i$ were assumed to be 0.52 ${\AA}$ and 1.54 ${\AA}$, respectively. The apphcation of this model to intramolecular $\beta$-, $\gamma$-, $\delta$-, $\epsilon$-, and $\zeta$-hydrogen abstraction in ketones and $\eta$- and $\theta$- proton transfer in oxoesters gave good results reflecting their photochemical behavior. The model was also used for prediction of photoreactivities of 2-(N,N-dibenzylamino)ethyl 2-, 3- and 4-benzoylbenzoate (1a - c). (1a - c).

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.457-460
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• 2005

• Polymer(Korea)
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• v.29 no.1
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• pp.74-80
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• 2005

To use the filter materials for reduction of carbonyl compounds in cigarette mainstream smoke, the bead type cation and anion exchangers were synthesized by the suspension polymerization of GMA and DVB followed by the subsequent functionalization with sodium sulfite and diethylamine, respectively. FT-IR/ATR was used to characterize functionalized copolymer formation by sulfonation and amination, and the morphology change of ion exchangers according to the adsorption of cigarette mainstream smoke were observed by SEM. Ion exchange capacity, functionalization yield and adsorption properties of carbonyl compounds in cigarette mainstream smoke were investigated. The highest functionalization yields and ion exchange capacity were obtained at 5 wt% DVB content in co-monomer. The adsorption amount of carbonyl compounds in cigarette mainstream smoke of anion exchanger was higher than that of cation exchanger because of its electron delocalization in carbonyl group. The adsorption efficiency was increased in the presence of moisture. This results indicated that the anion exchanger was applicable for cigarette filter material because of its large ion exchange capacity and rapid ion exchange reaction.

• Carbon letters
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• v.20
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• pp.19-25
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• 2016

Activated carbon fiber (ACF) surfaces are modified using an electron beam under different aqueous solutions to improve the NO gas sensitivity of a gas sensor based on ACFs. The oxygen functional group on the ACF surface is changed, resulting in an increase of the number of non-carbonyl (-C-O-C-) groups from 32.5% for pristine ACFs to 39.53% and 41.75% for ACFs treated with hydrogen peroxide and potassium hydroxide solutions, respectively. We discover that the NO gas sensitivity of the gas sensor fabricated using the modified ACFs as an electrode material is increased, although the specific surface area of the ACFs is decreased because of the recovery of their crystal structure. This is attributed to the static electric interaction between NO gas and the non-carbonyl groups introduced onto the ACF surfaces.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.162-168
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• 2011

Many ligands have been experimentally designed and tested for their activities as inhibitors against bacterial enoyl-ACP reductase (FabI), ENR. Here the binding energies of the reported ligands with the E. coli ENR-$NAD^+$ were calculated, analyzed and compared, and their molecular dynamics (MD) simulation study was performed. IDN, ZAM and AYM ligands were calculated to have larger binding energies than TCL and IDN has the largest binding energy among the considered ligands (TCL, S54, E26, ZAM, AYM and IDN). The contribution of residues to the ligand binding energy is larger in E. coli ENR-NAD+-IDN than in E. coli ENR-$NAD^+$-TCL, while the contribution of $NAD^+$ is smaller for IDN than for TCL. The large-size ligands having considerable interactions with residues and $NAD^+$ have many effective functional groups such as aromatic $\pi$ rings, acidic hydroxyl groups, and polarizable amide carbonyl groups in common. The cation-$\pi$ interactions have large binding energies, positively charged residues strongly interact with polarisable amide carbonyl group, and the acidic phenoxyl group has strong H-bond interactions. The residues which have strong interactions with the ligands in common are Y146, Y156, M159 and K163. This study of the reported inhibitor candidates is expected to assist the design of feasible ENR inhibitors.

• Bulletin of the Korean Chemical Society
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• v.28 no.1
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• pp.17-28
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• 2007

Indium and gallium have emerged as useful metals in organic synthesis as a result of its intriguing chemical properties of reactivity, selectivity, and low toxicity. Although indium belongs to a main metal in group 13, its first ionization potential energy is very low and stable in H2O and O2. Therefore, indium-mediated organic reactions are of our current interest. On the basis of these properties of indium, many efficient indium-mediated organic reactions have been recently developed, such as the addition reactions of allylindium to carbonyl and iminium groups, the indium-mediated synthesis of 2-(2-hydroxyethyl)homoallenylsilanes, the indiummediated allylation of keto esters with allyl halides, sonochemical Reformatsky reaction using indium, the indium-mediated selective introduction of allenyl and propargyl groups at C-4 position of 2-azetidinones, the indium-mediated Michael addition and Hosomi-Sakurai reactions, the indium-mediated β-allylation, β- propargylation and β-allenylation onto α,β-unsaturated ketones, the highly efficient 1,4-addition of 1,3-diesters to conjugated enones by indium and TMSCl, and the intramolecular carboindation reactions. Also, we found gallium-mediated organic reactions such as addition reactions of propargylgallium to carbonyl group and regioselective allylgallation of terminal alkynes.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.491-496
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• 1993

A class A ${\beta}$-lactamase from Staphylococcus aureus PC1 complexed with 3R,5R-clavulanate is studied. The starting geometry for the computation is the crystal structure of the ${\beta}$-lactamase. Docking of the clavulanate to the enzyme is done exploiting the requirements of electrostatic and shape complementarity between the enzyme and clavulanate. This structure is then hydrated by water molecules and refined by energy minimization and short molecular dynamics simulation. In the energy refined structure of this complex, the carboxyl group of the clavulanate is hydrogen bonded to Lys-234, and the the carbonyl carbon atom of the clavulanate is adjacent to the $O_{\gamma}$ of Ser-70. It is found that a crystallographic water molecule initially located at the oxyanion hole, which is formed by the two -NH group of Ser-70 and Gln-237, is replaced by the carbonyl oxygen atom of the 3R,5R-clavulanate after docking and energy reginement. The crystallographic water molecules are proved to be important in ligand binding. Glu-166 residue is found to be repulsive to the binding of clavulanate, which is in agreement with experimental observation. Arg-244 residue is found to be important to the binding of clavulanate as well as to interaction with C2 side chain of the clavulanate. The electron density redistribution of the clavulanate on binding to the ${\beta}$-lactamase in studied by an ab initio quantum-mechanical calculation. A significant redistribution of electron density of the clavulanate is induced by the enzyme, toward the enzyme, toward the transition state of the enzymatic reaction.

• Bulletin of the Korean Chemical Society
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• v.19 no.5
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• pp.527-530
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• 1998

This paper presents the electrochemistry and molecular orbital (MO) picture of a series of conformationally-restricted thioxantone derivatives. A series of $C_2-substituted$ thioxanthones were examined to probe the electronic influence of the substituent on the electrooxidation and electroreduction sites (i.e., on the electron densities at the 10-and 9-positions), respectively. In the presence of "electrophoric" groups such as C=O and S, characteristic electrochemical reduction and oxidation responses are observed. The electrochemical reaction was diffusion-controlled, because the $I_p/{\upsilon}^{1/2}$ ratio was constant for the anodic and cathodic wave of thioxantone derivatives. These substituent effects are presented in terms of correlations of oxidation (or reduction) potentials with the highest occupied molecular orbital (HOMO), or lowest unoccupied molecular orbital (LUMO) energies, respectively. There is good correlation between energies of the HOMO vs. $E_{pa}^{(+)}$ and energies of the LUMO vs. $E_{pc}^{(-)}$. Frontier Molecular Orbital (FMO) is changed by the functional group of thioxanthones. FMO energy level was offered us the information about the electron transfer direction, and the coefficient of FMO was offered the information about the electron transfer position. Sulfur atom has an important effect on oxidation potential, $E_{pa}^{(+)}$ and the carbonyl carbon has an important effect on reduction potential, $E_{pc}^{(-)}$. Therefore we were appreciated that the contribution of sulfur atom for the $E_{pa}^{(+)}$ and HOMO energies is larger than the contribution of carbonyl group for the $E_{pc}^{(-)}$ and LUMO energies.

• Polymer(Korea)
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• v.34 no.4
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• pp.381-385
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• 2010

Aiphatic diester monomer, 3-[(benzyloxycarbonylamino)butyl]-1,4-dioxane-2,5-dione (BABD), was synthesized with the N-$\varepsilon$-benzyloxy-carbonyl-L-lysine as starting material. This monomer was synthesized to add the functionality to poly(lactic acid)s. BABD unit was successfully incorporated into the PLLA chain which was confirmed by $^1H$ NMR. The copolymer composition could be controlled by the feed ratios of monomer. The $M_n$ of this resultant polymer is expected to reach high molecular weight after the purification of monomer and optimization of polymerization time, though the polymer showed relatively low degree of polymerization ($M_n$＝3300). The copolymer is expected to possess the enhanced hydrophilicity and the possibility of chemical modification on amino group.

• Journal of the Korean Society of Clothing and Textiles
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• v.18 no.1
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• pp.15-22
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• 1994

The formation of carbonyl group was dominant to other functional groups. Concentrations of both carboxyl and peroxide groups were found to rapidly reach low steady state values that increased slightly with increa-sing temperature and relatice humidity. Since the deg-radation of cellulose samples was in the initial stage and the conversion of glycosidic bonds and hydroxyl groups were very small, it was found that changes in the physical and chemical properties could be fitted to a first-order reaction model.