• Bulletin of the Korean Chemical Society
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• v.28 no.6
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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.

• Journal of the Korean Chemical Society
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• v.63 no.1
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• pp.29-36
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• 2019

A potentially tetradentate Schiff base ligand, 2-((2-((pyridin-2-ylmethylene)amino)ethyl)amino)ethan-1-ol (PMAE), and its cadmium(II) complex, [$Cd(PMAE)I_2$] (1), were prepared and characterized by elemental analysis, FT-IR, Raman, $^1H$ and $^{13}C$ NMR spectroscopies and single-crystal X-ray diffraction. In the crystal structure of 1, the cadmium atom has a slightly distorted square-pyramidal geometry and a $CdN_3I_2$ environment in which the PMAE acts as an $N_3$-donor. In the crystal packing of the complex, the alcohol and amine groups of the coordinated ligands participate in hydrogen bonding with iodide ions and form $R^2{_2}(14)$ and $R^2{_2}(8)$ hydrogen bond motifs, respectively. In addition to the hydrogen bonds, the crystal network is stabilized by ${\pi}-{\pi}$ stacking interactions between pyridine rings. The thermodynamic stability of the isolated ligand and its cadmium complex along with their charge distribution patterns were studied by DFT and NBO analysis.

• Journal of the Korean Ceramic Society
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• v.39 no.3
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• pp.265-271
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• 2002

Density, water resistance, Raman and infrared spectroscopy were used to investigate the change of structural characteristics with the composition of phosphate galss samples made by melting method. The structural abnormality of the density and water resistance were rapidly increased and shown near the 60mol% of $P_2O_5$. This result could be explained by the structural changes owing to the strong shrinkage of glass network by the coordination of DBO(Double-Bonded Oxygen) around $Mg^{2+}$ cations. In addition, it seems that the DBOs coordinating $Mg^{2+}$ cations lose its characteristics of double bonding and resonate with other NBOs(Non-Bonding Oxygen).

• Journal of Applied Biological Chemistry
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• v.51 no.1
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• pp.28-35
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• 2008

The physico-chemical properties of kapok fibers were altered via the combination processes of chlorite-periodate oxidation, in order to assess their efficacy as a heavy metal adsorbent. The chemically-oxidized kapok fibers were found to harbor a certain amount of polysaccharides, together with lowered lignin content. This alteration in lignin characteristics was clearly confirmed via FTIR and NBO yield. Moreover, chemically oxidized kapok fibers retained their hollow tube shape, although some changes were noted. The chemically oxidized kapok fibers evidenced elevated ability to adsorb heavy metal ions with the best fit for the Langmuir adsorption isotherm model. Three cycles of adsorption-desorption were conducted with in-between regeneration steps. Our experimental results indicated that chemically oxidized kapok fibers possessed excellent adsorption characteristics, and the modified kapok fibers could be completely regenerated with almost equimolar diluted sodium hydroxide. Pb, Cu, Cd and Zn ions evidenced adsorption rates of 93.55%, 91.83%, 89.75%, and 92.85% on the chemically oxidized kapok fibers. The regeneration efficiency showed 73.58% of Pb, 71.55% of Cu, 66.87% of Cd, and 75.00% of Zn for 3rd cycle with 0.0125N NaOH.

• Journal of the Korean Ceramic Society
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• v.31 no.7
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• pp.695-702
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• 1994

Current study was undertaken to explain the structural evolution and corresponding changes in the properties of calcium aluminate glasses with the variation of SiO2 doping concentration. Calcium aluminate glasses in the compositional ranges of (100-x)(0.6CaO+0.4Al2O3)+xSiO2(where x=0~60) were fabricated. DTA analysis confirmed an anomalous behavior in glass transition temperature (Tg) with the maximum of 887$^{\circ}C$ and minimum of 859$^{\circ}C$ when x=5 and 50, respectively. densities and refractive indices monotonically decreased with increasing SiO2 content and IR transmitting cutoff shifted to shorter wavelength side when the amount of added SiO2 exceeded 5 mole%. IR fundamental vibration absorption peaks showed the change that NBOs were inclined to SiO4 tetrahedron in the low-silica region and NBO per SiO4 tetrahedra changed from 2 to 0 with increasing silica content. Based on the analysis of IR fundamental vibration absorption peaks, the model of the structural change can be proposed in three step: 1) SiO4 scavenged the NBOs located at AlO4-tetrahedra, which resulted in the increased of Tg values, 2) NBOs located in the main network again with a decrease in Tg, and 3) dominated by the decrease in the relative amount of NBOs in the glass system, where Tg re-increased.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2358-2368
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• 2011

Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, employing the B3LYP method and the LANL2DZ, 6-31G$^*$(LANL2DZ for Tc), 6-31G$^*$(cc-pVDZ-pp for Tc) and DGDZVP basis sets, have been performed to investigate the electronic structures and absorption spectra of the technetium-99m-labeled methylenediphosphonate ($^{99m}Tc$-MDP) complex of the simplest diphosphonate ligand. The bonding situations and natural bond orbital compositions were studied by the Mulliken population analysis (MPA) and natural bond orbital (NBO) analysis. The results indicate that the ${\sigma}$ and ${\pi}$ contributions to the Tc-O bonds are strongly polarized towards the oxygen atoms and the ionic contribution to the Tc-O bonding is larger than the covalent contribution. The electronic transitions investigated by TDDFT calculations and molecular orbital analyses show that the origin of all absorption bands is ascribed to the ligand-to-metal charge transfer (LMCT) character. The solvent effect on the electronic structures and absorption spectra has also been studied by performing DFT and TDDFT calculations at the B3LYP/6-31G$^*$(cc-pVDZ-pp for Tc) level with the integral equation formalism polarized continuum model (IEFPCM) in different media. It is found that the absorption spectra display blue shift in different extents with the increase of solvent polarity.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2086-2092
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• 2014

Two novel coordination compounds $[Cu_2(pypya)_3(H_2O)_2]{\cdot}Cl{\cdot}(H_2O)_5$ (1) and $\{[Cd(pypya)(ta)_{1/2}]{\cdot}H_2O\}_n$ (2) (Hpypya=2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid, $H_2ta$=terephthalic acid) were synthesized and characterized by single X-ray diffraction. Structure determination reveals that complex 1 and complex 2 crystallize in the triclinic system, with the P-1 space group. The asymmetric unit of 1 contains two Cu(II) ions, and their coordination modes are different. These units of complex 1 are linked together via hydrogen bonds and ${\pi}-{\pi}$ interactions, and the 3D structure of complex 1 was formed. Complex 2, a mononuclear Cd(II) coordination compound, has a 2D structure which was constructed via coordination bonds. TGA and fluorescence spectra analysis of complex 1 and complex 2 have also been studied. In addition, the geometry parameters of complex 1 have been optimized with the B3LYP method of density functional theory (DFT) to explain its coordination behavior. The electronic properties of the complex 1 and ligand Hpypya have been investigated based on the nature bond orbital (NBO) analysis at the B3LYP level of theory. The result verifies that the synergistic effect have occurred in the compound.

• Transactions of the Society of Information Storage Systems
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• v.2 no.1
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• pp.43-49
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• 2006

Fractal/angle multiplexing is a $LiNBO_3$ crystal using a X-Y Galvano mirror, and the random access concept in fractal/angle multiplexing are discussed in this paper. First, the brief introduction of the designed holographic digital data storage system is presented. Then, the average access time concept for the storage system is newly defined, and the comparison of the average access time between the holographic storage and a conventional optical disk is performed. Second, the basic simulation and experiment to find the X-Y Galvano mirror dynamics are conducted. From this analysis, we find that the average access time in our HDDS which has 6 degree scan angle is about 5 msec. This result is very high performance when it compared with the average access time of a conventional optical disk. Finally, some recording results using fractal/angle multiplexing are presented, then, the relationship between bit error rate and angle mismatch for the each multiplexing are discussed.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.882-890
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• 2000

Ab initio calculations are carried out on protonation equilibria of 5-memberedheteroaromatic aldehydes (5MHAs;heteroatom Y = NH, O, PH,and S and substituentZ = NH2, OCH3, SCH3, CH3, H, Cl, CHO, CN,NO2) at the $MP2}6-31G*$ level. Naturalbond orbital (NBO) analyses show that the optimal localized natural Lewis structures of the protonated aldehydes,(P), are ortho (C3) protonated (for Y = O, PH and S) and N-pro-tonated (for Y = NH) forms in contrast to the standard structural Lewis formula for aldehydes, (R). The delo-calizability of ${\pilone}-pairon$ the heteroatom $(n{\pi}(Y))$ is in the order Y = NH > O > S > PH. The transmission efficiency of (Z) substituent effects to the carbonyl moiety run parallel to the delocalizability of $n{\pi}(Y)$ for R,but is dominantly influenced by the cationic charge on $C{\alpha}(C{\alpha}+)$ for P, which is in the reverse order of thede-localizability of $n{\pi}(Y).$ The Hammett ${\rho}values$ for variation of Z in the protonation are determined by the dif-ference in the transmission efficiencies between Pand R stateat simple interpretation of their magnitude is not warranted. However,the magnitude of the gas-phase ${\rho}z+$ values decreases as the level ofcomputation is raised from RHF/3-21G* to RHF/6-31G* and to $MP2}6-31G*$ but increases again at the MP4SDQ/6-31G* level. Further decrease occurs when solvent effect (water) is accounted for by the SCRF method. Comparison of the SCRF ${\rho}z+values$ with those determined in the aqueous acid solution for Y = S and CHCH shows inadequacy of accounting for the solvent effects on the ${\rho}values$ by a continuum model. It is noteworthy that semiempirical calculations, especially theAM1 method, give even lower magnitude of the gas-phase ${\rho}values.

• Korean Journal of Materials Research
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• v.18 no.11
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• pp.617-622
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• 2008

In this study, the additivity factors of compositions to density and glass transition point ($T_g$) in a $xLi_2O-(1-x)[(1-y)TeO_2-yZnO]$ (0$T_g$ was discussed. As a method for predicting the relation between glass structure and ionic conductivity, density was measured by the Archimedes method. The glass transition point was analyzed to predict the relation between ionic conductivity and the bonding energy between alkali ions and non-bridge oxygen (NBO). The relation equations showing the additivity factor of each composition to the two properties are as follows: Density(g/$cm^3$) = $2.441x_1\;＋\;5.559x_2\;＋\;4.863x_3\;T_g(^{\circ}C)$ = $319x_1\;＋\;247x_2\;＋\;609x_3\;－\;1950x_1x_3$ ($x_1$ : fraction of $Li_2O$, $x_2$ : fraction of $TeO_2$, $x_3$ : fraction of ZnO) The density decreased as $Li_2O$ content increased. This was attributed to change of the $TeO_2$ structure. From this structural result, the electric conductivity of the glass samples was predicted following the ionic conduction mechanism. Finally, it is expected that electric conductivity will increase as the activation energy for ion movement decreases.