• Bulletin of the Korean Chemical Society
• /
• v.30 no.10
• /
• pp.2403-2407
• /
• 2009

Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 1998.06a
• /
• pp.239-242
• /
• 1998

Ca $F_2$ films have superior gate insulator properties than conventional gate insulator such as $SiO_2$, Si $N_{x}$, $SiO_{x}$, and T $a_2$ $O_{5}$ to the side of lattice mismatch between Si substrate and interface trap charge density( $D_{it}$). Therefore, this material is enable to apply Thin Film Transistor(TFT) gate insulator. Most of gate oxide film have exhibited problems on high trap charge density, interface state in corporation with O-H bond created by mobile hydrogen and oxygen atom. This paper performed Ca $F_2$ property evaluation as MIM, MIS device fabrication. Ca $F_2$ films were deposited at the various substrate temperature using a thermal evaporation. Ca $F_2$ films was grown as polycrystalline film and showed grain size variation as a function of substrate temperature and RTA post-annealing treatment. C-V, I-V results exhibit almost low $D_{it}$(1.8$\times$10$^{11}$ $cm^{-1}$ /le $V^{-1}$ ) and higher $E_{br}$ (>0.87MV/cm) than reported that formerly. Structural analysis indicate that low $D_{it}$ and high $E_{br}$ were caused by low lattice mismatch(6%) and crystal growth direction. Ca $F_2$ as a gate insulator of TFT are presented in this paper paperaper

• Bulletin of the Korean Chemical Society
• /
• v.27 no.9
• /
• pp.1405-1417
• /
• 2006

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

• Korean Journal of Crystallography
• /
• v.4 no.1
• /
• pp.6-10
• /
• 1993

11 β ,17 β -dihydroxy-9a-fluoro-l7a-methyl androst-4-en-3-one (Fluoxymesterone), CgoH29 FO,, orthorhombic, P2,2,2,, a=13.468(5) A, b= 19.554 (2)A, c=6.578(9)A, a=b=r=90˚, A (CuKa)=1.5406 A , Dm=1.289cm-3, Dc=1.299cm-3 and Z=4 at T=298k. The structure was solved by direct method using seminvariants of ggg Parity group and refined by the full-matrix least-square method, resulting model with reliability factor R=0.069 for 1098 unique reflection over 3σ . Ring A is an 1β-2a-half chair, 5 ring has a highly symmetrical chair conformation, C ring is in a distorted chair conformation and D ring is a 13aenveLope conformation. In the crystal structure, the molecules are packed with a hydrogen bond of 011-H23‥‥03(0.5+x, 1.5-y, 1.0-z) [1.94(9) A of H‥‥0.2.786(9)A of 0‥‥0 and 165(8) ˚ of

• Transactions of the Korean hydrogen and new energy society
• /
• v.23 no.3
• /
• pp.199-206
• /
• 2012

HC-SCR was conducted over Co-Pt/ZSM5 catalyst coated over 200 cpsi cordierite in the condition of atomspheric pressure and $200^{\circ}C-500^{\circ}C$. Weight ratio of Co/Pt determined from EDX analysis was 8/2, which was almost equal to the weight ratio at preparation step. XPS showed that nitrates within cobalt precursor and chlorine withn Pt precursor were removed. TEM result demonstrated that crystallite size of cobalt and Pt was under 5nm. Among these tested hydrocarbon reductants, isobutane ($i-C_4H_{10}$) showed the highest de-$NO_x$ yield of 80% under the condition of the mole ratio of reductant/NOx=1.0 at $180^{\circ}C$. De-$NO_x$ yield from HC-SCR was increased as the carbon number of hydrocarbon reductant was increased. The decrease of bonding energy between C and H of HC reductant played a role to increase of de-$NO_x$ yield, which indicated that the dissociation step of C-H bond of hydrocarbon molecule might be the rate determining step of HC-SCR. The increase of oxygen concentration in the feed resulted in the decrease of de-$NO_x$ yield but the increase of CO and $N_2O$ yield.

• Journal of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.1-9
• /
• 1990

Cholesteryl pentanoate $(C_{32}O_2H_{54})$ is orthorhombic, space group $P2_12_12_1$, with a = 21.930(3), b = 21.404(3), c = 6.419(5) $\AA$, Z = 4, V = 3012.8(5)$\AA$$^3$, $D_c$ = 1.04 g$cm^{-3}$, ${\lambda}(Mo\; K{\alpha}$ = 0.71069 $\AA$, $\mu$ = 0.58 $cm^{-1}$, F(000) = 1048, T = 298, R = 0.086 for 1502 unique observed reflections with I > 1.0 $\sigma$ (I). The structure was solved by direct methods and refined by cascade diagonal least-squares refinement. The C-H bond lengths and the methyl groups are fixed and refined as their ideal geometry. A comparison with other cholesteryl esters gives normal structure for the tetracyclic ring, while the tail regions of the side chain and the ester group which stands on end, show a variation from their normal values, presumably due to thermal effects. The molecules are stacked together by non-bonded van der Waals forces with the shortest intermolecular distance of 3.529 $\AA$.

• Journal of Ginseng Research
• /
• v.31 no.1
• /
• pp.34-43
• /
• 2007

Background: Previous research has suggested that single doses of a standardised Panax ginseng extract can decrease fasted blood-glucose levels and modulate cognitive performance in healthy young volunteers. The latter has generally been seen in terms of improved secondary memory performance. However, both the cognitive effects of chronic administration of ginseng and the potential modulation of working memory have received comparatively little research attention. Aims: The current double-blind, placebo-controlled, balanced cross-over study investigated the effects of 8-weeks administration of Korean ginseng extract (200 mg) on cognitive performance, gluco-regulatory parameters and ratings of subjective mood and 'quality of life'. Methods: 'Eighteen healthy young participants were assessed pre-dose and 3 hours post-dose on the mornings of Day 1, Day 29 and Day 57 of 8 week treatment regimens of both placebo and ginseng. A four-week placebo wash-out separated the treatment phases. Each assessment included the Cognitive Drug Research battery, computerised working memory tasks, and Bond-Lader mood scales. The WHO Quality of Life scale (WHOQOL-BREF) was completed once per visit. Gluco-regulatory parameters were assessed with assays of blood glucose, insulin and HbA1c. Results: Data from the 16 participants that completed the study showed that there were no significant, acute treatment related differences on Day 1 of treatment, or in gluco-regulatory parameters throughout the study. However, time related performance improvements were evident following chronic administration of ginseng on the '3-Back' and 'Corsi-block' computerised working memory tasks. Ginseng was also associated with an improved score on the 'social relations' subscale of the WHOQOL-100, and a significant shift on the 'calm' factor of the Bond-Lader mood scales (from calm/relaxed towards excited/tense). Conclusion: The results of the current study suggest that Korean ginseng extract can modulate working memory performance and subjective ratings of 'quality of life' and mood. Replication with a larger sample size may further elucidate the actions of this product.

• Korean Journal of Materials Research
• /
• v.20 no.2
• /
• pp.78-81
• /
• 2010

Surface modification of silica nanoparticles was investigated using an aerosol self assembly. Stearic acid was used as surface treating agent. A two-fluid jet nozzle was employed to generate an aerosol of the colloidal suspension, which contained 20 nm of silica nanoparticles, surface modifier, and ethyl alcohol. Powder properties such as morphology, specific surface area and pore size distribution were analyzed by SEM, BET and BJH methods, respectively. Surface properties of the silica power were analyzed by FT-IR. The OH bond of the $SiO_2$ surface was converted to a C-H bond. It was revealed that the hydrophilic surface changed to a hydrophobic one due to the aerosol self assembly. Morphology of the surface treated powder was nanostructured with lots of pores having an average diameter of around $2\;{\mu}m$. Depending on the stearic acid concentration (0.25 to 1.0 wt%), the pore size distribution of the particles and the degree of hydrophobicity ranged from 1.5 nm to 180 nm and 29.6% to 50.2%, respectively.

• Journal of the Korean Chemical Society
• /
• v.40 no.7
• /
• pp.483-491
• /
• 1996

Dieis-Alder reaction between cyclopentadiene and 5-membered ring compounds which have exo-cyclic double bond has been studied using the PM3 method. Transition states do not show large geometrical change with the variation of dienophiles. Two isomers are possible due to the rotation of the exo-cyclic double bond of a dienophile. The reactivity for the formation of different products are explained using the FMO energy gap. The exo and endo selectivity of the reaction has been also studied from the correlation between the deformation energy and the activation barrier. Minimum energy reaction path is discussed using the Curtin-Hammett principle.

• Resources Recycling
• /
• v.18 no.6
• /
• pp.30-37
• /
• 2009

Silica sol was prepared from the mixture of sodium silicate solution and oxidized silicate solution in which sodium had been removed by sol-gel process. The properties of sodium silicate solution and silicate solution thus prepared were characterized by yellow silicomolydate method. Moreover, the formation and growth of silica sol from sodium silicate solution was investigated. Sodium silicate solution with 2% of $SiO_2$ contains 95% of reactive silicate, and 50% of reactive silicate participates sol-gel reaction. From the results of FT-IR analysis, it was found that the intensity of silanol bond decreased and the intensity of siloxane bond increased with increasing reaction temperature. Zeta potential of silica sol prepared at each condition was -40~-60 mV and it could be known that silica sol in this study was well dispersed. The silica sol with 5~10 nm size could be prepared by heating the mixed solution of sodium silicate and silicate solution. And the silica sol grew into about 20 nm as silicate solution was added to silica sol solution.