The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.
In this study, we analyzed the explanations and examples of Brønsted-Lowry model in Chemistry I and Chemistry II textbooks of the 2009 revised curriculum. In particular, the definition of the Brønsted-Lowry model, the examples, and the content of experiments were analyzed by the process perspective of chemical equilibrium, emergent process. The analyzed textbooks were 4 kinds of Chemistry I textbooks and 4 kinds of Chemistry II textbooks in 2009 revision curriculum. As a result, Chemical I textbooks did not adequately show the chemical equilibrium viewpoint when explaining the Brønsted-Lowry model. In the Chemistry II textbooks, the examples of Brønsted-Lowry model were not present emergent process viewpoint, and those were described as sequential viewpoint of Arrhenius model. In addition, examples of experiments to demonstrate the Brønsted-Lowry model of Chemistry II textbooks were insufficient. The experimental examples related to the definition of acid bases were at the level of classification by the color change of indicators. The experimental examples for explaining the strength of acid and base were to compare current intensity or amount of hydrogen gas generated from the reaction with metal. In addition, all textbooks presented the state of aqueous solution when describing the Brønsted-Lowry model, causing problems with differentiation from the Arrhenius model. Therefore, it is necessary to develop examples of experiments to help students understand Brønsted-Lowry model by presenting acid and base reaction in the non-aqueous solution state.
Kim, Soo-Hyun;Yim, Sung-Soo;Lee, Do-Joong;Kim, Ki-Su;Kim, Hyun-Mi;Kim, Ki-Bum;Sohn, Hyun-Chul
Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
/
2008.06a
/
pp.239-240
/
2008
As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.
Tooth loss in elderly is mainly caused by alveolar bone loss via severe periodontitis. Although the severity of periodontitis is known to be affected by age, the aging process or the genetic changes during the aging of periodontal tissue cells are not well characterized. In this study, we investigated the effect of in vitro aging on the change of gene expression pattern in periodontal fibroblasts. Gingival fibroblasts (GF) and periodontal ligament fibroblasts (PDL) were obtained from two young patients and replicative senescence was induced by sequential subcultivation. When more than 90% cells were positively stained with senescence-associated ${\beta},-galactosidase$, those cells were regarded as aged cells. In aged GF and PDL, the level of phosphorylated retinoblastoma (RB) and $p16^{INK4A}$ protein was significantly decreased and increased, respectively. However, the protein level of p53 and p21, well known senescence-inducing genes, did not increase in aged GF and PDL. Although $p27^{Kip1}$ and $p15^{INK4B}$, another cyclin-dependent kinase inhibitors, were reported to be involved in replicative senescence of human cells, they were decreased in aged GF and PDL. Because senescent cells showed flattened and enlarged cell shape and are known to have increased focal adhesion, we examined the protein level of several integrins. Aged GF and PDL showed increased protein level of integrin ${\alpha}2$, ${\alpha}v$, and ${\beta}1$. When the gene expression profiles of actively proliferating young cells and aged cells were compared by cDNA microarray of 3,063 genes and were confirmed by reverse transcription-polymerase chain reaction, 7 genes and 15 genes were significantly and commonly increased and decreased, respectively, in aged GF and PDL. Among them, included are the genes that were known to be involved in the regulation of cell cycle, gene transcription, or integrin signaling. The change of gene expression pattern in GF and PDL was minimally similar to that of oral keratinocyte. These results suggest that $p16^{INK4A}/RB$ might be involved in replicative senescence of periodontal fibroblasts and the change of gene expression profile during aging process is cell type specific.
The inhibition characteristics of chlorsulfuron [CHL, 2-chloro-N-[{ (4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino}carbonyl]benzenesulfonamide] and imazaquin [IMA, 2-{4,5-dihydro-4-methyl-4-(1-methy-lethyl)-5-oxo-1H-imidazol-2-yl}-3-quinolinecarboxylic acid] on acetolactate synthase(ALS) activity of corn plants were investigated. CHL and IMA rapidly inhibited ALS activity of corn plants in vitro. Their $I_{50}$ values for ALS activity were 100nM and $5{\mu}M$, respectively, indicating that CHL had 50 times more inhibitory effect on ALS activity than IMA. The first applied herbicide had a dominant inhibitory effect on ALS activity when the two herbicides were applied sequentially. Branched-chain amino acids, valine(Val), leucine(Leu), and isoleucine(Ile) showed a feedback inhibition on ALS activity ; Val or Leu had a more inhibitory effect on ALS activity than Ile. Branchedchain amino acids and CHL or IMA exhibited an additive effect on inhibiting ALS activity. This suggests that branched-chain amino acids inhibit ALS activity by a different mechanisms) from that of CHL or IMA. Apparent ALS activity, which was measured on the basis of the conversion of pyruvate to acetolactate, was decreased by the addition of 2-ketobutyrate into the ALS reaction mixture in a concentration-dependent manner. In addition, kinetic studies revealed that CHL acts as a noncompetitive inhibitor, while IMA acts as an uncompetitive inhibitor to ALS with respect to pyruvate.
Inorganic/organic composite particles were also synthesized by changing an initiator an it's concentration, concentration of an adsorbed surfactant, reaction temperature, and agitation speed in the presence of $CaCO_3$ adsorbed SDBS. The polymerization conditions were optimized according to the conversion of the core-shell composite particles. In the inorganic/organic core-shell composite particle polymerization, $CaCO_3$ absorbed surfactant SDBS of 0.5 wt % was prepared first and then core $CaCO_3$ was encapsulated by sequential emulsion polymerization using MMA, concentration of APS $3.16{\times}10^{-3}mol/L$ to minimize the formation of new PMMA particle during MMA shell polymerization. The structure characterization of the inorganic/organic core-shell particles was verified by measuring the decomposition degree of $CaCO_3$ using HCl solution. It was found that $CaCO_3$ was encapsulated by shell PMMA due to having excellent dispersion in the epoxy resin, smooth surface distinctly from spindle shape, and broad particle distribution after the capsulation.
Journal of the Korean Society of Food Science and Nutrition
/
v.21
no.6
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pp.693-700
/
1992
As an approach to study a new natural antioxidant for edible fats and oils, antioxidative fractions from acorn powder were characterized. The oxidative stabilities of soybean, palm, beef tallow, and lard oil containing the acorn active fraction extracted with various organic solvents were studied by determining the peroxide value during the storage at $60^{\circ}C.$ And this effective antioxidative components were isolated and identified by thin layer chromatography and high performance liquid chromatography. The proximate compositions of acorn powder were water 11.9~12.0%, protein 7.1~7.4%, starch 65.5~69.4%, fat 2.1~2.6%, fiber 2.1~3.6%, ash 2.4~2.6%, and total tannin 4.6~6.8%, respectively. The final yield of fraction extracted by sequential order of acetone : $H_2O$(1 : 1) and ethylacetate was 2.8~3.1%. Gallic acid, digallic acid and gallotannin were contained this final fraction. The main antioxidative activity was speculated due to the presence of gallic acid in acorn powder extract. The antioxidative activity was more effective in fat water emulsion than just fat system. Antioxidative activities measured by peroxide value were quite high in beef tallow and soybean emulsion, but low in lard and palm oil emulsion in the concentration of 200ppm acorn extract. Therefore, the addition of 200ppm acorn extract was suggested to expect effective antioxidation concentration in the reaction system.
Core-shell polymers of methyl methacrylate/styrene pair were prepared by sequential emulsion polymerization in the presence of sodium dodecyl benzene sulfonate(SDBS) as an emulsifier using ammonium persulfate(APS) as an initiator. The characteristics of these core-shell polymers were evaluated. Core-shell composite latex has the both properties of core and shell components in a particle, where as polymer blonds or copolymers show a combined properties from the physical properties or two homopolymers. This unique behavior of core-shell composite latex can be used in many industrial fields. However, in preparation of core-shell composite latex, several unexpected phenomina are observed, such as, particle coagulation, low degree of polymerization, and formation of new particles during shell polymerization. To solve the disadvantages, we studied the effects of surfactant concentrations, initiator concentrations, and reaction temperature on the tore-shell structure or PMMA/PSt and PSt/PMMA. Particle size and particle size distribution were measured by using particle size analyzer, and the morphology of the core-shell composite latex was observed by using transmission electron microscope. Glass transition temperature($T_g$) was also measured by using differential scanning calorimeter. To identify the core-shell structure, pH of the composite latex solutions were measured.
This study elucidated the biological activities and structural characteristics of polysaccharides isolated from ginseng leaves fermented using Cordyceps sinensis (GLF). GLF comprised at least 18 glycosyl linkages, including 4-linked glucose residues (24.0%). To characterize the neutral polysaccharides in GLF, it was further fractionated by anion exchange chromatography, and the unabsorbed fraction (GLF1) was isolated. Peritoneal macrophages stimulated with GLF1 produced various cytokines in a dose-dependent manner. The properties and activities of the four subfractions (PHI, PHIA1-PHIA3) obtained after sequential enzymatic digestion were examined. PHI and PHIA3 primarily comprised glucose, whereas PHI exhibited an iodine-color reaction. Furthermore, the PHIA1-3 fractions indicated that cytokine production was completely inhibited. These results suggest at the immune activities of GLF1 may be due to the α-(1→4)-glucan branched at the C(O)6 position, which was produced by C. sinensis.
Kim, Dong-Min;Ju, Hong-Guang;Kang, Ju-Won;Han, Seong Sook;Ahn, Sang-Nag
Korean Journal of Breeding Science
/
v.43
no.6
/
pp.620-624
/
2011
'Hwaweon 4' was developed from a cross between the African upland cultivar, 'Moroberekan' and 'Ilpumbyeo' based on marker-aided backcross selection. The recurrent parent 'Ilpumbyeo' is a high grain quality cultivar with medium to late maturity. 'Hwaweon 4' is nearly isogenic to 'Ilpumbyeo' except a small Moroberekan introgressed segment on chromosome 4 harboring the resistance gene for blast. The preliminary and replicated yield trial was conducted at Chungnam National University in 2006 and 2007. The local adaptability test was carried out by the National Seed Management Office (NSMO) from 2008 to 2009. This cultivar was registered to NSMO with a cultivar designated as 'Hwaweon 4'. This cultivar averaged 76 cm in culm length and has medium growth duration. Milled rice of 'Hwaweon 4' is translucent and the grain quality traits are comparable to those of the recurrent parent. It has low protein content. The yield potential of 'Hwaweon 4' in grain was about 6.31 MT/ha at the ordinary fertilizer level for two years. This variety showed highly resistance reaction at the blast nursery test at four locations and also at the sequential planting method. This resistance is due to the resistance gene designated as Pi45(t) on chromosome 4 introgressed from the donor parent, 'Moroberekan'. The Pi45(t) gene would be useful inenhancing resistance to blast in rice breeding program.
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