• Title/Summary/Keyword: Steric Hindrance

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Inactivation of Brain Glutamate Dehydrogenase Isoproteins by MDL 29951

  • Lee, Eun-Young;Yoon, Hye-Young;Kim, Tae-Ue;Choi, Soo-Young;Won, Moo-Ho;Cho, Sung-Woo
    • BMB Reports
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    • v.34 no.3
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    • pp.268-273
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    • 2001
  • In addition to the recognition site for glutamate, the N-methyl-D-aspartate (NMDA)-preferring glutamate receptor subtype shows a binding site for glycine. In this paper, we present the effects of 3-(4,6-dichloro-2-carboxymethylamino-5,7-dichloroquinoline-2-carboxylic acid (MDL 29951), a potent inhibitor of glycine binding to the NMDA receptor, on glutamate dehydrogenase (GDH) from bovine brains. The incubation of GDH isoproteins from bovine brains with MDL 29951 resulted in a dose-dependent loss of enzyme activity Separately or together, 2-oxoglutarate and NADH did not give an efficient protection against the inhibition, indicating that GDH isoproteins saturated with NADH or 2-oxoglutarate are still open to attack by MDL 29951. MDL 29951 was an uncompetitive inhibitor with respect to both 2-oxoglutarate and NADH for GDH isoproteins. These results suggest that the binding site of MDL 29951 is not directly located at the catalytic site, and the inhibition of GDH isoproteins by MDL 29951 is probably due to a steric hindrance, or a conformational change altered upon the interaction of the enzyme with its inhibitor. The inhibitory effects of MDL 29951 on GDH isoproteins were significantly diminished in the presence of ADP. GDH I reacted more sensitively with ADP than GDH II on the inhibition by MDL 29951. Our results suggest a possibility that the two types of GDHs are differently regulated by MDL 29951, depending on the physiological concentrations of ADP.

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Origin of Decreasing the Dielectric Constant and the Effect of Ionic Polarization (유전상수가 낮아지는 원인과 이온 분극의 효과)

  • Oh, Teresa
    • Journal of the Korean Vacuum Society
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    • v.18 no.6
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    • pp.453-458
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    • 2009
  • SiOC film was deposited by the chemical vapor deposition using BTMSM and oxygen mixed precursor. The characteristic of SiOC film varied with increasing of the gas flow rate ratios. The dielectric constant was obtained by C-V measurement using the structure of metal/SiOC film/Si. The space effect due to the steric hindrance between alkyl group at terminal bond of Si-$CH_3$ made the pores, and increased the thickness. However, the SiOC film due to the lowering of the polarization decreased the thickness and then decreased the dielectric constant. After annealing process, the dielectric constant decreased because of the evaporation of the OH or $H_2O$ sites. The thickness was related to the lowering of the dielectric constant by the reduction of the polarization and the thickness decreased with the decrease of the dielectric constant. The refractive index was in inverse proportion to thickness. The trends of the thickness and refractive index did not change after annealing.

The Control of Side Reactions in Bunsen Reaction Section of Sulfur-Iodine Hydrogen Production Process (황-요오드 수소 생산 공정의 분젠 반응 부분에서 부반응 제어)

  • Lee, Kwang-Jin;Hong, Dong-Woo;Kim, Young-Ho;Park, Chu-Sik;Bae, Ki-Kwang
    • Transactions of the Korean hydrogen and new energy society
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    • v.19 no.6
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    • pp.490-497
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    • 2008
  • For continuous operation of the sulfur-iodine(SI) thermochemical cycle, which is expected practical method for massive hydrogen production, suggesting operation conditions at steady state is very important. Especially, in the Bunsen reaction section, the Bunsen reaction as well as side reactions is occurring simultaneously. Therefore, we studied on the relation between the variation of compositions in product solution and side reactions. The experiments for Bunsen reaction were carried out in the temperature range, from 268 to 353 K, and in the $I_2/H_2O$ molar ratio of $0.094{\sim}0.297$ under a continuous flow of $SO_2$ gas. As the result, sulfur formed predominantly with increasing temperature and decreasing $I_2/H_2O$ molar ratios. The molar ratios of $H_2O/H_2SO_4$ and $HI/H_2SO_4$ in global system were decreased as the more side reaction occurred. A side reactions did not appear at $I_2/H_2O$ molar ratios, saturated with $I_2$, irrespective of the temperature change. We concluded that it caused by the increasing stability of an $I_{2x}H^+$ complex and a steric hindrance with increasing $I_2/HI$ molar ratios.

Effect of External and Intramolecular Nucleophiles on Nature of Products of Carboxypeptidase A-Catalyzed Hydrolysis of Esters. Attempted Trapping of Acyl-Enzyme Intermediate (카르복시펩티다제A의 에스테르 가수분해 반응생성물의 종류에 대한 외부 및 분자내 친핵체의 영향. 아실-효소중간체의 포획시도)

  • Junghun Suh;Emil Thomas Kaiser
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.164-172
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    • 1978
  • Carboxypeptidase A-catalyzed hydrolysis of ester substrates was carried out at room temperature in the presence of a number of external reagents. If the acyl-enzyme intermediate, an anhydride, is attacked by the external reagents, products formed by trapping at the acyl portion or at the enzyme portion of the anhydride group can be obtained. Examination of the uv/vis spectral properties of the reaction products and of changes in enzyme activity indicated that such trapping reactions did not occur. Also performed was evaluation of enzymatic rate parameters for the the hydrolysis of O-(o-hydroxyphenylacetyl)-L-${\beta}$-phenyllactate. Detection of 2-coumaranone possibly formed by attack of the o-hydroxy group as an intramolecular trapping group at the acyl-enzyme intermediate was tried, but no evidences for the intramolecular trapping reaction were obtained. Failure to trap the intermediate was discussed in terms of steric hindrance imposed on the approach of the trapping reagents to the anhydride group of the acyl-enzyme intermediate and of the fast enzymatic breakdown of the intermediate.

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Advanced Low-k Materials for Cu/Low-k Chips

  • Choi, Chi-Kyu
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.71-71
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    • 2012
  • As the critical dimensions of integrated circuits are scaled down, the line width and spacing between the metal interconnects are made smaller. The dielectric film used as insulation between the metal lines contributes to the resistance-capacitance (RC) time constant that governs the device speed. If the RC time delay, cross talk and lowering the power dissipation are to be reduced, the intermetal dielectric (IMD) films should have a low dielectric constant. The introduction of Cu and low-k dielectrics has incrementally improved the situation as compared to the conventional $Al/SiO_2$ technology by reducing both the resistivity and the capacitance between interconnects. Some of the potential candidate materials to be used as an ILD are organic and inorganic precursors such as hydrogensilsequioxane (HSQ), silsesquioxane (SSQ), methylsilsisequioxane (MSQ) and carbon doped silicon oxide (SiOCH), It has been shown that organic functional groups can dramatically decrease dielectric constant by increasing the free volume of films. Recently, various inorganic precursors have been used to prepare the SiOCH films. The k value of the material depends on the number of $CH_3$ groups built into the structure since they lower both polarity and density of the material by steric hindrance, which the replacement of Si-O bonds with Si-$CH_3$ (methyl group) bonds causes bulk porosity due to the formation of nano-sized voids within the silicon oxide matrix. In this talk, we will be introduce some properties of SiOC(-H) thin films deposited with the dimethyldimethoxysilane (DMDMS: $C_4H_{12}O_2Si$) and oxygen as precursors by using plasma-enhanced chemical vapor deposition with and without ultraviolet (UV) irradiation.

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Kinetics and Mechanism of Hydrolysis of Insecticidal $O,O-diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothiate\;(Volaton^{\circledR})$ (살충성 $O,O-Diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothioate\;(Volaton^{\circledR})$의 가수분해 반응메카니즘)

  • Sung, Nack-Do;Kim, Hyune-Yi;Park, Cheon-Kyu
    • Applied Biological Chemistry
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    • v.37 no.2
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    • pp.124-129
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    • 1994
  • The rate of hydrolysis of insecticidal $O,O-diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothioate\;(Volaton^{\circledR})$ has been studied in 25% (v/v) aqueous dioxane. On the basis of solvent effect (pH 6.0; m=0.21, n=1.55, pH 12.0; m=0.42, n=3.14 & $|m|{\ll}|l|$), general base catalysis, hydrolysis product analysis, calculation of molecular orbital (MO) and rate equation, it may be concluded that the hydrolysis of Volaton proceeds through the $A_{AC}2$ mechanism via trigonal bipyramidal $(sp^3d^2)$ intermediate below pH 7.0, while above pH 9.0 the hydrolysis proceeds through the $B_{AC}2$ mechanism. Hydrolysis reactivity of Volaton depends on positive charge strength $(p{\gg}{\alpha}C_2)$ rather than steric hindrance. In the range between pH 7.0 and pH 9.0, these two reactions occur competitively.

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Well aligned carbon nanotubes grown on a large area Si substrate by thermal CVD

  • Lee, Cheol-Jin;Park, Jung-Hoon;Son, Kwon-Hee;Kim, Dae-Woon;Lee, Tae-Jae;Lyu, Seung-Chul;Kang, Seung-Youl;Lee, Jin-Ho;Park, Hyun-Ki;Lee, Chan-Jae;You, Jong-Hun
    • 한국정보디스플레이학회:학술대회논문집
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    • 2000.01a
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    • pp.57-58
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    • 2000
  • we have grown vertically aligned carbon nanotubes on a large area of Co-Ni codeposited Si substrates by thermal chemical vapor deposition using $C_2H_2$ gas. The carbon nanotubes grown by the thermal chemical vapor deposition are multi-wall structure, and the wall suface of nanotubes is covered with defective carbons or carbonaceous particles. The carbon nanotubes range from 50 to 120 nm in diameter and about 130 ${\mu}m$ in length at $950\;^{\circ}C$. Steric hindrance between nanotubes at an initial stage of the growth forces nanotubes to align vertically. The turn-on voltage was about 0.8 $V/{\mu}m$ with a current density of 0.1 ${\mu}A/cm^2$ and emission current reveals the Fowler-Nordheim mode.

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Synthesis of Poly(MMA-co-PEGMA) Electrolytes by Grafting-onto Method and Effect of Composition on Ionic Conductivities (Grafting-onto법에 의한 poly(MMA-co-PEGMA) 전해질의 합성과 이온전도도에 대한 조성의 영향)

  • Lee, Ju-Hyung;Ryu, Sang-Woog
    • Journal of the Korean Electrochemical Society
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    • v.16 no.4
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    • pp.198-203
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    • 2013
  • Copolymer consisted of MMA and tBMA was synthesized by radical polymerization and poly(MMA-co-MA) was prepared by selective hydrolysis of tert-butyl group. The obtained polymer was coupled with epoxy functionalized PEO of various molecular weight to synthesize poly(MMA-co-PEGMA) with different side chain length. The AC-impedance measurement shows $1.88{\times}10^{-6}Scm^{-1}$ of room temperature ionic conductivity from 48mol% of MMA while $5.11{\times}10^{-8}Scm^{-1}$ was observed in 82mol% sample. In addition, there was an effect of PEGMA molecular weight on ionic conductivity possibly due to the steric hindrance in grafting-onto coupling reaction. Finally, the polymer electrolytes shows electrochemical stability up to 6V at room temperature.

Synthesis of High Molecular Weight Poly(vinyl alcohol) by Low Temperature Polymerization of Vinyl Acetate in Tertiary Butyl Alcohol and the Following Saponification (아세트산비닐의 삼차부틸알코올계 저온 중합 및 비누화에 의한 고분자량 폴리비닐알코올의 합성)

  • 류원석;한성수;최진현;유상우;홍성일
    • Polymer(Korea)
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    • v.24 no.5
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    • pp.610-620
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    • 2000
  • Vinyl acetate (VAc) was polymerized at 30, 40, and 5$0^{\circ}C$ using 2,2'-azobis (2,4-dimethylvaleronitrile) (ADMVN) and tertiary butyl alcohol (TBA) as the initiator and the solvent, respectively. High molecular weight (HMW) atactic poly(vinyl alcohol) (PVA) was prepared by saponifying the poly(vinyl acetate) (PVAc) synthesized. The effect of polymerization conditions were investigated in terms of conversion, degree of branching for acetyl group of PVAc, and molecular weight of both PVAc and PVA. The polymerization rate of VAc in TBA was proportional to the 0.49th power of ADMVN concentration in good accordance with the theoretical value of 0.5. HMW-PVA with high yield could be obtained successfully, probably due to lower polymerization temperature and decreased chain transfer reaction rate which was achieved by adopting ADMVN and TBA. PYAc having average degree of polymerization (P$_{n}$) of 10000~13000 was obtained at the conversion of 35~70%. Saponification of so prepared PVAc yielded PVA having P$_{n}$ of 2400~6100. The syndiotactic diad content increased with decreasing polymerization temperature and increasing VAc concentration due to a steric hindrance effect of TBA during polymerization.

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Effect of Phenolic Antioxidants System on Yellowing of Amorphous Poly-α-olefin (페놀계 산화방지제에 의한 비결정성 올레핀 수지의 황변 거동)

  • Kim, Si-Yong;Kim, Ho-Gyum;Park, Sang-Cheol;Min, Kyung-Eun
    • Polymer(Korea)
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    • v.37 no.2
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    • pp.156-161
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    • 2013
  • Phenolic antioxidants are effective stabilizers that provide excellent long-term heat stability by preventing thermo-oxidative degradation during processing and service life. However, under a selected set of circumstances, certain types of phenolics have been susceptible to discoloration due to prolonged storage in an environment containing oxides of nitrogen. It is investigated that the effect of addition of secondary antioxidant and chemical structure of primary antioxidant on discoloration of amorphous poly-${\alpha}$-olefin (APAO), which is especially prone to be decomposed in high processing temperature. From the result, it is concluded that a higher level of steric hindrance of phenolic antioxidant provided by long alkyl chain allows a more enhanced synergic effect with secondary antioxidant.