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Theoretical Studies on the Structure and Acidity of Meldrum's Acid and Related Compounds

  • Lee, Ik-Choon;Han, In-Suk;Kim, Chang-Kon;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.24 no.8
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    • pp.1141-1149
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    • 2003
  • The structures and gas-phase ionization energies (ΔG°) of Meldrum's acid (I) and related cyclic (II-VI) and acyclic compounds (VII-IX) are investigated theoretically at the MP2/6-31+$G^*$, B3LYP/6-31+$G^*$, B3LYP/6- 311+$G^{**}$, B3LYP/6-311++G(3df,2p) and G3(+)(MP2) levels. Conformations of three neutral cyclic series vary gradually from boat (Meldrum's acid, I), to twisted chair (II) and to chair (III) as the methylene group is substituted for the ether oxygen successively. The preferred boat form of I can be ascribed to the two strong $n_O$ → σ* c-c antiperiplanar vicinal charge transfer interactions and electrostatic attraction between negatively charged C¹ and positively charged C⁴at the opposite end of the boat. All the deprotonated anionic forms have half-chair forms due to the two strong $n_C$ → π* c=0 vicinal charge transfer interactions. The dipole-dipole interaction theory cannot account for the higher acidity of Meldrum's acid (I) than dimedone (III). The origin of the anomalously high acidity of I is the strong increase in the vicinal charge transfer ($n_C$ → π* c=0) and 1,4-attrative electrostatic interactions (C¹↔C⁴) in the ionization (I → $I^-$ + $H^+$). In the acyclic series (VII-IX) the positively charged end atom, C⁴, is absent and the attractive electrostatic stabilization (C¹↔C⁴) is missing in the anionic form so that the acidities are much less than the corresponding cyclic series.

Kinetic Properties of Lactate Dehydrogenase in Tissues from Rana catesbeiana (황소개구리(Rana catesbeiana) 조직의 젖산탈수소효소의 역학적 특성)

  • Yum, Jung Joo;Ha, Eun Sung
    • Journal of Life Science
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    • v.24 no.2
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    • pp.118-127
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    • 2014
  • The kinetic properties and isozyme expression of lactate dehydrogenase (EC 1.1.1.27; LDH) in tissues from Rana catesbeiana I and II collected from February (I) and August (II) were studied. LDH activities, A4 isozyme, and LDH/citrate synthase (EC 4.1.3.7; CS) were high in skeletal muscle from R. catesbeiana I, and LDH $B_4$ isozyme increased in several tissues of R. catesbeiana II. In particular, LDH activities were high in heart and brain tissues from R. catesbeiana II. LDH eye-specific C isozyme, detected by native polyacrylamide gel electrophoresis after immunoprecipitation, was expressed in eye tissue and was more similar to the $B_4$ than $A_4$ isozyme. LDH $A_4$ isozyme was purified by oxamate-linked affinity chromatography, and the molecular weight of subunit A was 32.0 kDa. In R. catesbeiana II, levels of $Km^{PYU}$, $Vmax^{LAC}$, and tolerance to lactate of LDH were high in all tissues, and $Vmax^{PYU}$ of LDH in heart and brain tissue was highly detected. Purified $A_4$ isozyme and LDH in eye tissue were highly tolerate compared to others. The $Km^{LAC}$ value was highly measured compared to $Km^{PYU}$. The degree of inhibition by 10 mM of pyruvate on LDH activities in tissues from R. catesbeiana I and II was more pronounced as the ratio of subunit B increased. As a result, characteristic expression of LDH eye-specific C was found in R. catesbeiana. Anaerobic metabolism seemed to predominate as the LDH of skeletal muscle from I showed higher activity. It also appeared that R. catesbeiana II adapted well to incremental increases in LDH B, becoming tolerant to the lactate of LDH in tissues.

Estimation of Electrical Parameters of OD Organic Semiconductor Diode from Measured I-V Characteristics

  • Moiz, Syed Abdul;Ahmed, Mansoor M.;Karimov, Kh. S.
    • ETRI Journal
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    • v.27 no.3
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    • pp.319-325
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    • 2005
  • In this paper the effect of temperature on the electrical properties of organic semiconductor disperse orange dye 25 (OD) have been examined. Thin films of OD have been deposited on $In_{2}O_{3}$ substrates using a centrifugal machine. DC current-voltage (I-V) characteristics of the fabricated devices $(Al/OD/In_{2}O_{3)$ have been evaluated at varying temperatures ranging from 40 to $60^{\circ}C$. A rectification behavior in these devices has been observed such that the rectifying ratio increases as a function of temperature. I-V characteristics observed in $Al/OD/In_{2}O_{3)$ devices have been classified as low temperature $({\leq} 50^{\circ}C)$ and high temperature characteristics (approximately $60^{\circ}C$). Low temperature characteristics have been explained on the basis of the charge transport mechanism associated with free carriers available in OD, whereas high temperature characteristics have been explained on the basis of the trapped space-charge-limited current. Different electrical parameters such as traps factor, free carrier density, trapped carrier density, trap density of states, and effective mobility have been determined from the observed temperature dependent I-V characteristics. It has been shown that the traps factor, effective mobility, and free carrier density increase with increasing values of temperature, whilst no significant change has been observed in the trap density of states.

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Biochemical Properties, Volatile Compounds and Total Phenol Contents of Yuza Variety (유자의 종류별 생리화학적인 특성과 향기성분, 총 페놀 함량 분석)

  • Hwang, Seong-Hee;Kim, Min-Jeong;Kim, Kang-Sung
    • The Korean Journal of Food And Nutrition
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    • v.26 no.4
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    • pp.685-692
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    • 2013
  • Yuza (Citrus junos) has 3 varieties with variable physiochemical properties. This study analyzed these volatile compounds and physiochemical properties according to variety. Three Yuza varieties, native (Citrus junos I), improved I (Citrus junos I+Poncirus trifoliata), improved II (Citrus junos I+C. junos II) were used. The native Yuza weighted more than the improved varieties, but the peel ratio (weight of peel versus pulp) was high in improved one. Protein and ash contents were high in Improved I than native one. Native had 29.6mg% vit. C in pulp and improved I had 57.7mg% vit. C in peel. Free sugar was mainly fructose, and the main organic acid was citric acid in Yuza. Improved I Yuza had high free sugar contents, and the organic acid levels were high in improved II Yuza. Linoleic acid was the most prevalent fatty acid in Yuza; it was distributed in peel or pulp. The most common volatile flavor component was dl-limonene (64~70%); improved II Yuza showed significantly higher contents of dl-limonen and ${\gamma}$-terpinen. Total phenol level of Yuza was identical in all types, but peels had 2.5 times more than pulps.

Performance Analysis of Simultaneous Heating & Cooling Water Making System(I)-Simulation (냉.온열 동시 제조시스템의 성능분석(I)-Simulation)

  • Park, Seong-Ryong;Park, Jun-Tack;An, Young-Hun
    • Proceedings of the KSME Conference
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    • 2001.06d
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    • pp.266-271
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    • 2001
  • In this study, the performance of the simultaneous heating & cooling water making system using R134a was investigated by simulation. The most important effect upon heating COP was intermediate pressure depending on input water temperature. With the input water temperature of $10^{\circ}C\;and\;20^{\circ}C$, optimum intermediate pressure were 923 and 1040kPa, respectively. At that optimum intermediate pressure, the maximum heating COP of the system operated between $0^{\circ}C$ evaporating temperature and $70^{\circ}C$ condensing temperature were 4.15 and 3.83. With installation of the subcoolers in high or low pressure section, the system COP was increased by reducing the refrigerant mass flow rate. Under the optimum pressure and $10^{\circ}C$ input water temperature, it was found that heating COP was maximized when the low-subcooler and high-subcooler capacity rate were taken by 14% and 13%, respectively.

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A Study on Low-Cycle Fatigue Behavior at Elevated Temperature of High Carbon Steel Used For Structural Purpose (構造용高炭素鋼材 의 高溫 低 사이클 피勞擧動 에 關한 硏究)

  • 옹장우;김재훈
    • Transactions of the Korean Society of Mechanical Engineers
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    • v.6 no.2
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    • pp.101-106
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    • 1982
  • This study was undertaken to determine tensile properties and low-cycle fatigue behavior of 0.6%C high carbon steel used of structural purposes at temperatures up to 500.deg.C. In the low-cycle fatigue test the upper limit was decided by elongation(i.e. the total strain range), while the lower limit was defined by the load (i.e. zero load). The following results were obtained. Both, the ultimate tensile strength and low-cycle fatigue resistance attain the maximum values near 250.deg.C. Above this temperature the values decrease rapidly as the temperature increases. The low-cycle fatigue resistance decreases whenever there is an increase of the total strain range. Because the hardness of cycle fatigued specimen correlates cyclic hardening and cyclic softening, therefore the hardness of cycle fatigued specimen is smaller than that of the nonfatigued specimen at room temperature and 500.deg.C but much larger than the hardness of the nonfatigued specimen near 250.deg.C.

A Study on the Fatigue Crack Growth Behavior in Ti-6Al-4V Alloy(I) (Ti-6Al-4V의 피로균열성장거동에 관한 연구(I))

  • 우흥식;한지원
    • Journal of the Korean Society of Safety
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    • v.16 no.4
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    • pp.52-57
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    • 2001
  • Fatigue crack growth behaviour of Ti-6A-4V alloy is investigated in air and salt solution environment at room temperature and $200^{\circ}C$. Fatigue crack growth rate is blown to be fast for the formation of corrosive product in hot salt environment. For the effect on corrosion fatigue crack growth behaviour of region II. fatigue crack growth rate in atmosphere had a little gap to both case, $200^{\circ}C$ and room temperature. However, it showed very fast tendency in salt corrosive atmosphere, and it was remarkably accelerated in $200^{\circ}C$ temperature salt environment. When $\Delta$K was approximately 30MPa(equation omitted), fatigue crack growth rate had a little difference between at room temperature and at $200^{\circ}C$ high temperature, however in case of salt corrosive environment the room temperature was 3.5 times Inter and $200^{\circ}C$ high temperature for 16 times than air environment respectively.

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Electrical conduction phenomena of $C_{22}$--quinolium(TCNQ) langmuir-blodgett films under the high-electric field ($C_{22}$-quinolium(TCNQ) LB막의 고전게 전기전도 현상)

  • 신동명;김태완;홍언식;송일식;유덕선;강도열
    • Electrical & Electronic Materials
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    • v.7 no.2
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    • pp.138-144
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    • 1994
  • Electrical conduction phenomena of $C_{22}$-quinolium(TCNQ) Langmuir- Blodgett(LB) films are reported through a study of current-voltage(I-V) characteristics along a perpendicular direction. The I-V characteristics were investigated by applying a step or a pulse voltage to the specimen as well as changing temperatures in the range of 20-250[.deg. C] It show an ohmic behavior in low-electric field, and a nonohmic behavior in high-electric field. This nonohmic behavior has been interpreted in terms of a conduction mechanism of space-charge limited current and Schottky effect. When the electric field is near the strength of 10$_{6}$ V/cm, there occur anomalous phenomena similar to breakdown. When step or pulse voltage is applied, the breakdown voltage shifts to the higher one as the step or pulse time width becomes shorter. To see the influence of temperature, current was measured as a function of temperature under the several bias voltages, which are lower than that of breakdown. It shows that the current increases to about 103 times near 60-70[.deg. C], and remains constant for a while up to around 150[.deg. C] and then suddenly drops. We have also performed a DSC(differential scanning calorimetry) measurement with $C_{22}$-quinolium(TCNQ) powder in the range of 30-300[.deg. C]. These results imply that the anomalous phenomena occuring in the high electric field are caused by the electrical and internal thermal effect such as a joule heating.ating.

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Residual bond behavior of high strength concrete-filled square steel tube after elevated temperatures

  • Chen, Zongping;Liu, Xiang;Zhou, Wenxiang
    • Steel and Composite Structures
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    • v.27 no.4
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    • pp.509-523
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    • 2018
  • This paper presents experimental results on the residual bond-slip behavior of high strength concrete-filled square steel tube (HSCFST) after elevated temperatures. Three parameters were considered in this test: (a) temperature (i.e., $20^{\circ}C$, $200^{\circ}C$, $400^{\circ}C$, $600^{\circ}C$, $800^{\circ}C$); (b) concrete strength (i.e., C60, C70, C80); (c) anchorage length (i.e., 250 mm, 400 mm). A total of 17 HSCFST specimens were designed for push-out test after elevated temperatures. The load-slip curves at the loading end and free end were obtained, in addition, the distribution of steel tube strain and the bond stress along the anchorage length were analyzed. Test results show that the shape of load-slip curves at loading ends and free ends are similar. With the temperature constantly increasing, the bond strength of HSCFST increases first and then decreases; furthermore, the bond strength of HSCFCT proportionally increases with the anchoring length growing. Additionally, the higher the temperature is, the smaller and lower the bond damage develops. The energy dissipation capacity enhances with the concrete strength rasing, while, decreases with the temperature growing. What is more, the strain and stress of steel tubes are exponentially distributed, and decrease from the free end to loading end. According to experimental findings, constitutive formula of the bond slip of HSCFST experienced elevated temperatures is proposed, which fills well with test data.

Film Boiling Chemical Vapor Infiltration of C/C Composites: Influence of Mass and Thermal Transfers

  • Delhaes, P.;Trinquecoste, M.;Derre, A.;Rovillain, D.;David, P.
    • Carbon letters
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    • v.4 no.4
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    • pp.163-167
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    • 2003
  • The "Film boiling" Chemical Vapor Infiltration (CVI) process is a rapid densification one developed in particular for the elaboration of carbon/carbon composite materials. In order to optimize this new thermal gradient process, we have carried out several studies, on one hand, about the nature of the complex chemical reactions in a confined medium, and on the other hand, relative to the role of heat and mass transfers inside the preform. We show in this study that the introduction of a permeable sheath around the preform leads to hybrid liquid/gas CVI process which presents the advantages of very high densification rates associated with a moderate input energy.

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