• 제목/요약/키워드: $E_c/I_o$

검색결과 882건 처리시간 0.047초

Leaving-Group Substituent Controls Reactivity and Reaction Mechanism in Aminolysis of Phenyl Y-Substituted-Phenyl Carbonates

  • Kang, Ji-Sun;Song, Yoon-Ju;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권7호
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    • pp.2023-2028
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    • 2013
  • A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

Treatments Effect on Biological Values of Defatted Rice Polishings

  • Khalique, Anjum;Lone, K.P.;Khan, A.D.;Pasha, T.N.
    • Asian-Australasian Journal of Animal Sciences
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    • 제19권2호
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    • pp.209-216
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    • 2006
  • Defatted rice polishings (DRP) was subjected to chemical treatments i.e., 0.4 N HCl, and 6% $H_2O_2$, with or without physical treatment i.e. extrusion cooking. The treated DRP was evaluated chemically and biologically using male broiler chicks (108) of approximately uniform weight, selected out of 220 chicks, previously fed on commercial diets for 7 days as a settlement period. The chicks were then divided into 36 experimental units of 3 chicks each. Each experimental diet was randomly allotted to three experimental units and fed for 10 days to broiler chicks. The experimental diets were designated as A (Commercial), B (10% HCl treated DRP), C (20% HCl treated DRP), D (10% HCl plus extruded DRP), E (20% HCl plus extruded DRP), F (10% $H_2O_2$ DRP) and G (20% $H_2O_2$ DRP), H (10% $H_2O_2$ plus extrusion DRP) and I (20% $H_2O_2$ plus extrusion DRP), J (10% untreated DRP), K (20% untreated DRP) and L (Protein free). The birds fed on diet L were used to measure the endogenous nitrogen loss. The biological evaluations of diets containing differently treated DRP were compared with a commercial feed and feeds containing untreated defatted rice polishings. It was observed that these treatments liberated bound nutrients, making them more accessible to the normal digestive enzymes and increased their apparent nutrient availability. This process probably also detoxified the anti-nutritive factors i.e. phytates, lectin, trypsin inhibitor present in DRP. The results of the feeding trials revealed that diets containing 6% $H_2O_2$ treated DRP showed better weight gain, feed consumption and utilization, protein efficiency and digestibility, biological value and net protein utilization than all other treatments.

Microwave Dielectric Properties of Low Temperature Fired (${Pb_{0.45}}{Ca_{0.55}}$) [(${Fe _{0.5}}{Nb_{0.5}}$)$_{0.9}{Sn_{0.1}}$]$O_3$Ceramics with Various Additives

  • Ha, Jong-Yoon;Park, Ji-Won;Yoon, Seok-Jin;Kim, Hyun-Jai;Yoon, Ki-Hyun
    • 한국세라믹학회지
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    • 제38권7호
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    • pp.597-601
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    • 2001
  • The effect of CuO, $B_2$ $O_3$, $V_2$ $O_{5}$ and CuO-B $i_2$ $O_3$additives on microwave dielectric properties of (P $b_{0.45}$C $a_{0.55}$) [(F $e_{0.5}$N $b_{0.5}$)$_{0.9}$S $n_{0.1}$] $O_3$(PCFNS) were investigated. The PCFNS ceramics were sintered at 11$65^{\circ}C$. To decrease the sintering temperature for using as a low-temperature co-firing ceramics (LTCC), CuO, $B_2$ $O_3$, $V_2$ $O_{5}$ and CuO-B $i_2$ $O_3$were added to the PCFNS. As the content of CuO increased, the sintered density and dielectric constant increased and the temperature coefficient of resonance frequency ($\tau$$_{f}$) shifted to the positive value. When the CuO-B $i_2$ $O_3$were added, dielectric properties were $\varepsilon$$_{r}$ of 83, Q. $f_{0}$ of 6085 GHz, and $\tau$$_{f}$ of 8ppm/$^{\circ}C$ at a sintering temperature of 100$0^{\circ}C$. The relationship between the microstructure and properties of ceramics was studied by X-ray diffraction and scanning electron microscopy.icroscopy.y.icroscopy.y.

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Aminolysis of Benzyl 2-Pyridyl Thionocarbonate and t-Butyl 2-Pyridyl Thionocarbonate: Effects of Nonleaving Groups on Reactivity and Reaction Mechanism

  • Kim, Min-Young;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권4호
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    • pp.1115-1119
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    • 2013
  • A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

ZnO 압전박막의 제조와 유량조절밸브로서의 응용 (ZnO Piezoelectric Thin Film Fabrication and Its Application as a Flow-rate Control Microvalve)

  • 박세광
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 1989년도 춘계학술대회 논문집
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    • pp.66-69
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    • 1989
  • After reviewing previous work done on two piezoelectric thin films(PZT, ZnO), ZnO thin piezofim of 1-3UM is fabricated by sputtering on the different substrates(i. e., P+Si/N-Si, SiO2/P+Si/ N-Si, Al/SiO2/ P+Si/ N+Si). The result shows that ZnO piezofilm on the Al has the best c-axis orientation. One of applications for the ZnO piezofilm as an microvalve to control liquid flow is introduced, and which can be controlled electrically and remotely.

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Mn3O4 함량에 따른 ZnO의 결함과 입계 특성 (Defects and Grain Boundary Properties of ZnO with Mn3O4 Contents)

  • 홍연우;신효순;여동훈;김진호
    • 한국전기전자재료학회논문지
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    • 제24권12호
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    • pp.962-968
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    • 2011
  • In this study, we investigated the effects of Mn dopant (0.1~3.0 at% $Mn_3O_4$ sintered at 1000$^{\circ}C$ for 1 h in air) on the bulk trap (i.e. defect) and grain boundary properties of ZnO, ZM(0.1~3.0) using admittance spectroscopy (AS), and impedance-modulus spectroscopy (IS & MS). As a result, three kinds of defect were found below the conduction band edge of ZnO as 0.09~0.14 eV (attractive coulombic center), 0.22~25 eV ($Zn^{{\cdot}{\cdot}}_i$), and 0.32~0.33 eV ($V^{\cdot}_o$). The oxygen vacancy increased with Mn doping. In ZM, an electrically single grain boundary as double Schottky barrier was formed with 0.82~1.0 eV of activation energies by IS & MS. We also find out that the barriers of grain boundary of Mn-doped ZnO (${\alpha}$-factor=0.13) were more stabilized and homogenized with temperature compared to pure ZnO.

Comparative Investigation of Interfacial Characteristics between HfO2/Al2O3 and Al2O3/HfO2 Dielectrics on AlN/p-Ge Structure

  • Kim, Hogyoung;Yun, Hee Ju;Choi, Seok;Choi, Byung Joon
    • 한국재료학회지
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    • 제29권8호
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    • pp.463-468
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    • 2019
  • The electrical and interfacial properties of $HfO_2/Al_2O_3$ and $Al_2O_3/HfO_2$ dielectrics on AlN/p-Ge interface prepared by thermal atomic layer deposition are investigated by capacitance-voltage(C-V) and current-voltage(I-V) measurements. In the C-V measurements, humps related to mid-gap states are observed when the ac frequency is below 100 kHz, revealing lower mid-gap states for the $HfO_2/Al_2O_3$ sample. Higher frequency dispersion in the inversion region is observed for the $Al_2O_3/HfO_2$ sample, indicating the presence of slow interface states A higher interface trap density calculated from the high-low frequency method is observed for the $Al_2O_3/HfO_2$ sample. The parallel conductance method, applied to the accumulation region, shows border traps at 0.3~0.32 eV for the $Al_2O_3/HfO_2$ sample, which are not observed for the $Al_2O_3/HfO_2$ sample. I-V measurements show a reduction of leakage current of about three orders of magnitude for the $HfO_2/Al_2O_3$ sample. Using the Fowler-Nordheim emission, the barrier height is calculated and found to be about 1.08 eV for the $HfO_2/Al_2O_3$ sample. Based on these results, it is suggested that $HfO_2/Al_2O_3$ is a better dielectric stack than $Al_2O_3/HfO_2$ on AlN/p-Ge interface.

Affinity Labeling of E. coli GTP Cyclohydrolase I by a Dialdehyde Derivative of Guanosine Triphosphate

  • Ahn, Chi-Young;Park, Sang-Ick;Kim, Ju-Myeong;Yim, Jeong-Bin
    • BMB Reports
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    • 제28권1호
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    • pp.72-78
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    • 1995
  • Time-dependent inactivation of E. coli GTP cyclohydrolase I with a 2',3'-dialdehyde derivative of GTP (oGTP) was directed to the active site of the enzyme, and was dependent on the concentration of oGTP. The kinetics of inactivation were biphasic with a rapid reaction occurring immediately upon exposure of the enzyme to oGTP followed by a slow rate of inactivation. The $K_i$ value of oGTP for the enzyme was 0.25 mM. Inactivation was prevented by preincubation of the enzyme with GTP, the substrate of the enzyme. At 100% inactivation, 2.3 mol of [8.5'-$^3H$]oGTP were bound per each enzyme subunit, which consists of two identical polypeptides. The active site residue which reacted with the affinity label was lysine. oGTP interacted selectively with the ${\varepsilon}$-amino group of lysine in the GTP-binding site to form a morpholine-like structure which was stable without sodium borohydride treatment. However, triphosphate group was eliminated during the hydrolysis step. To identify the active site of the enzyme, [8.5'-$^3H$]oGTP-labeled enzyme was cleaved by endoproteinase Lys-C, and the $^3H$-labeled peptide was purified by HPLC. The amino acid sequence of the active site peptide was Pro-Ser-Leu-Ser-Lys, which corresponds to the aminoterminal sequence of the enzyme.

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원자층증착법을 이용한 Y2O3 박막 형성 및 저항 스위칭 특성

  • 정용찬;성세종;이명완;박인성;안진호
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.229.2-229.2
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    • 2013
  • Yttrium oxide (Y2O3)는 band gap이 5.5 eV 정도로 상대적으로 넓고, 굴절상수가 1.8, 유전율이 10~15, Silicon 과의 격자 불일치가 작은 특성을 가지고 있다. 또한 녹는점이 높아 열적으로 안정하기 때문에 전자소자 및 광학소자에 다양하게 응용되는 물질이다. Y2O3 박막은 다양한 방법으로 증착할 수 있는데, 그 방법에는 e-beam evaporation, laser ablation, sputtering, thermal oxidation, metal-organic chemical vapor deposition, and atomic layer deposition (ALD) 등이 있다. ALD는 기판 표면에 흡착된 원자들의 자기 제한적 반응에 의하여 박막이 증착되기 때문에 박막 두께조절이 용이하고 step coverage와 uniformity 측면에서 큰 장점이 있다. 이전에는 Y(thd)3 and Y(CH3Cp)3 와 같은 금속 전구체를 이용하여 ALD를 진행하여, 증착 속도가 낮고 defect이 많아 non-stoichiometric한 조성의 박막이 증착되는 문제점이 있었다. 이번 연구에서는, (iPrCp)2Y(iPr-amd)와 탈이온수를 사용하여 Y2O3 박막을 증착하였다. Y2O3 박막 증착에 사용한 Y 전구체는 상온에서 액체이고 $192^{\circ}C$ 에서 1 Torr의 높은 증기압을 갖는다. Y2O3 박막 증착을 위하여 Y 전구체는 $150^{\circ}C$ 로 가열하여 N2 gas를 이용하여 bubbling 방식으로 공정 챔버 내로 공급하였다. Y2O3 박막의 ALD window는 $250{\sim}350^{\circ}C$ 였으며, Y 전구체의 공급시간이 5초에 다다르자 더 이상 증착 두께가 증가하지 않는 자기 제한적 반응을 확인할 수 있었다. 그리고 증착된 Y2O3 박막의 특성 분석을 위해 Atomic force microscopy (AFM)과 X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) 를 진행하였다. 박막의 Surface morphology 는 매끄럽고 uniform 하였으며, 특히 고체 금속 전구체를 사용했을 때와 비교하여 수산화물이 거의 없는 박막을 얻을 수 있었다. 그리고 조성 분석을 통해 증착된 Y2O3 박막이 stoichiometric하다는 것을 알수 있었다. 또한 metal-insulator-metal (MIM) 구조 (Ru/Y2O3/Ru) 의 resistor 소자를 형성하여 저항 스위칭 특성을 확인하였다.

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새로운 파이로클로어의 합성 및 결정화학적 특징 (Synthesis and Crystal Chemistry of New Actinide Pyrochlores)

  • 장영남;채수천;배인국
    • 한국광물학회지
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    • 제15권1호
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    • pp.78-84
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    • 2002
  • New pyrochlore-type phases($A_2$$B_2$$O_{7}$) were synthesized in the systems: CaO-C$eO_2$-T$iO_2$, CaO-$UO_2$(T$hO_2$)-Z$rO_2$, CaO-$UO_2$(T$hO_2$)-$Gd_2$$O_3$-T$iO_2$-Z$rO_2$, 및 CaO-T$hO_2$-S$nO_2$. The starting materials were pressed with the pressure of 200~400 MPa and sintered at 1500~ 155$0^{\circ}C$ for 4~8 hours in air and at 1300~ 135$0^{\circ}C$ for 5 ~50 hours under oxygen atmosphere. The products were characterized using XRD, SEM/EDS and TEM. In the bulk compositions of CaCe$Ti_2$$O_{7}$, CaTh$Zr_2$$O_{7}$,($Ca_{0.5}$ Gd$Th_{0.5}$)(ZrTi)$O_{7}$) ($Ca_{0.5}$Gd$Th_{0.5}$)(ZrTi)$O_{7}$, ($Ca_{0.5}$G$dU_{0.5}$)(ZrTi)$O_{7}$ and CaTh$Sn_2$$O_{7}$ , pyrochlore was the major phase, together with other oxide phase $of_2$$O_{7}$ fluorite structure. In the samples with target compositions CaU$Zr_2$$O_2$$Ca_{0.5}$ G$dU_{0.5}$)$Zr_2$T$iO_{7}$ pyrochlore was not identified, but a fluorite-structured phase was detected. The formation factor as the stable phase depended on crystal chemical characteristics of the actinide and lanthanide elements of the system concerned.