• 제목/요약/키워드: ${\Delta}C_p$

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에탄올-물 혼합용매내에서의 p-니트로벤질클로라이드의 가용매 분해반응에 대한 압력의 영향 (The Effect of Pressure on the Solvolysis Reaction of p-Nitrobenzyl Chloride in Binary Mixture of Ethanol-Water)

  • 권오천;김정림;유지철
    • 대한화학회지
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    • 제25권3호
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    • pp.152-159
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    • 1981
  • p-니트로벤질클로라이드의 가용매분해 반응속도를 50 와 $60{\circ}C$에서 압력을 1∼1200bar로 변화시키고 에탄올-물 혼합용매의 조성이 0.0∼0.5인 에탄올 몰분율의 범위내에서 전기전도도법으로 측정하였다. 반응의 속도상수로부터 활성화 파라미터, ${\Delta}V_\0^{\neq},\ {\Delta}H^{\neq}$${\Delta}S^{\neq}$를 구한결과 ${\Delta}V_\0^{\neq}$는 혼합용매의 몰분율이 0.3부근에서 extremum을 나타내었고 ${\Delta}H^{\neq}$${\Delta}S^{\neq}$는 0.1 부근에서 extremum을 나타내었다. 이러한 현상은 용매구조의 변화에 의하여 검토되었고 ${\Delta}V^{\neq}$의 압력의존성도 고찰하였다. ${\Delta}H^{\neq}$${\Delta}S^{\neq}$이 압력의존성은 그 부호에 있어서 고전열역학계에 대한 Maxwell관계의 식과 일치함을 보여주었다.

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$^{13}C-^{1}H$ Coupling Constant as a Criterion for the Presence of $\pi$ Bridging in Substituted 9-Benzonorbornenyl Cation

  • Gweon-Young Ryu;Jung-Hyu Shin
    • Bulletin of the Korean Chemical Society
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    • 제14권5호
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    • pp.546-548
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    • 1993
  • The discrete structure of substituted 9-benzonorbornenyl cation 3a and 3c was studied using the empirical ${\Delta}$J equation which was developed by Kelly and coworker$^5$. The ${\Delta}$J values of substituted 9-benzonorbornenyl cations were obtained from p-methyl-6,7-dimethyl benzonorbornen-9-yl (3a) and 9-methyl-6,7-dimethyl benzonorbonen-9-yl (3c) cations under stable ion conditions, and were compared with those of the corresponding ketone analog; these cations were generated by dissolving the corresponding carbinols in superacid at -120$^{\circ}$C and the nmr spectra taken at -60$^{\circ}$C~-90$^{\circ}$C. The ${\Delta}$J values are 8.7 Hz for the bridgehead carbons in cation 3c and 3.1 Hz for cation 3b. The ${\Delta}$J values at C5,8 in fused benzene ring are 14.3 Hz for cation 3c and 8.7 Hz for cation 3a. The excellent correlation of the ${\Delta}$J values with 1$^9F$ chemical shifts of p-fluorophenyl-6,7-dimethylbenzonorbornenyl cation (3d) indicate that ${\Delta}$J value is a reliable probe to charge density at adjacent cationic carbon. These NMR parameters strongly support that the symmetrically ${\pi}$-bridged nonclassical structure (type 2) of substituted 9-benzonorbornenyl cations in stable ion conditions.

염화벤질류의 가용매분해반응에 대한 압력의 영향 (제 2 보). 에탄올-물 혼합용매내에서 p-클로로 염화벤질의 분해반응 (The Effect of Pressure on the Solvolysis of Benzylchlorides (II). p-Chlorobenzyl Chloride in Ethanol-Water Mixtures)

  • 권오천;경진범
    • 대한화학회지
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    • 제30권2호
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    • pp.188-194
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    • 1986
  • 에탄올-물 혼합용매내에서 p-클로로 염화벤질의 가용매분해반응에 대한 속도상수를 압력 1~1,600bar, 온도를 30${\circ}$, 40${\circ}$C 에서 측정하였다. 반응속도들은 온도와 압력이 증가함에 따라 증가하고, 에탄올 몰 분율이 증가함에 따라 감소하였다. ln k대 압력의 플로트는 압력에 따라 이차함수꼴로 변함을 알았고, 이 플로트로부터 ${\Delta}V^{\neq}$${\Delta}{\beta}^{\neq}$의 값을 얻었다. 그 결과 ${\Delta}V^{\neq}$${\Delta}{\beta}^{\neq}$의 값은 약 0.20몰 분율에서 Extremum behavior가 나타남을 알았다. 이 현상을 용매구조 변화로 논의하였다. ln k대 용매파라미터, q 및 ln $C_w$의 플로트사이의 관계로부터 본 연구의 반응은 $S_N1(2)$메카니즘으로 진행됨을 추정할 수 있었다.

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TTAB 용액에서 Benzenesulfonate 음이온과 유도체들의 가용화에 대한 연구 (Solubilization of Benzenesulfonate anion and Its Derivatives by the Micellar System of TTAB)

  • 이병환
    • 대한화학회지
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    • 제45권1호
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    • pp.7-13
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    • 2001
  • 양이온 계면활성제인 TTAB(tetradecyltrimethylammonium bromide)의 수용액에서 benzenesulfonate 음이온과 유도체($C_6H_5SO_3^-, p-$CH_3C_6H_4SO_3^-$p-C_2H_5C_6H_4SO_3^-$)들의 가용화 현상을 UV/Vis 분광광도법을 이용하여 연구하였다. 온도의 변화에 따른 가용화상수($K_s$)의 변화를 측정하고 분석하였으며, 또한 가용화에 영향을 미치는 n-펜탄올과 NaBr의 효과에 대하여 조사하였다. 이러한 첨가제는 $K_s$와 CMC 값을 동시에 큰 폭으로 감소시키는 경향을 나타내었으며, 측정한 In$K_s$ 값은 InCMC 값에 대하여 일차함수의 관계를 나타내었다. 그리고 열역학적 고찰을 위하여 온도에 따른 $K_s$ 값의 변화로부터 여러 가지 열역학 함수값(${\Delta}G^0_s$, ${\Delta}H^0_s$${\Delta}S^0_s$)을 계산하고 분석하였다.

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AN EXTENSION ON GENERALIZED HYPERGEOMETRIC POLYNOMIALS

  • Shah, Manilal
    • Kyungpook Mathematical Journal
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    • 제11권1호
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    • pp.93-99
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    • 1971
  • In this paper, the author has established the formulae for product of two generalized hypergeometric polynomials by defining the polynomial in the form $$F_n(x)=x^{({\delta}-1)n}{_{p+{\delta}}F_q}\[\array{{\Delta}({\delta},-n),&a_1,&{\cdots}{\cdots},&a_p\\&b_1,&{\cdots}{\cdots},&b_q};\;{\lambda}x^c\]$$, where the symbol ${\Delta}({\delta},-n)$ represents the set of ${\delta}$-parameters: $${\frac{-n}{\delta}},\;{\frac{-n+1}{\delta}},\;{\cdots}{\cdots},\;{\frac{-n+{\delta}-1}{\delta}}$$ and ${\delta}$, n are positive integers. A number of known as well as new results have been also obtained with proper choice of parameters.

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Band gap control by tri-block nanoribbon structure of graphene and h-BN

  • 이지우;정가운
    • EDISON SW 활용 경진대회 논문집
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    • 제4회(2015년)
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    • pp.324-329
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    • 2015
  • First-principles investigations on the hybrid one dementional hexagonal hybrboron-nitride nano ribbons (BNNRs) with a armchair graphene nano-ribbons(AGRNRs), are presented. Electronics properties of the mixed armchair BNC nano-ribbon (BNCNRs) structure show control of a band gap on all cases at the special K-point. And we have studied, the band gap is direct in all cases. The band gap of mixed ABNCNRs could be divided into three groups (${\Delta}3p$, ${\Delta}3p+1$ and ${\Delta}3p+2$) and decrease with the increase of the width. Also these results show similar to the AGNRs case. Different from the band gap value ordering of AGNRs (${\Delta}3p+1$ > ${\Delta}3p$ > ${\Delta}3p+2$), the ordering of ABNCNRs is ${\Delta}3p$ > ${\Delta}3p+1$ > ${\Delta}3p+2$. The discrepancy may come from the differences between the edges of AGRNRs and the boundaries of hybrid BNCNRs. In addition, the bandgap of ABNCNRs are much smaller than those of the corresponding AGNRs. Our results show that the origin of band gap for BNCNRs with armchair shaped edges arises from both quantum confinement effect of the edges. These results similar to thecase of AGNRs. These properties of hybrid BN/C nano-ribbon structure may offer suitable bandgap to develop nnanoscale electronics and solar cell beyond individual GNRs and BNNRs.

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Characterization of the Wild-Type and Truncated Forms of a Neutral GH10 Xylanase from Coprinus cinereus: Roles of C-Terminal Basic Amino Acid-Rich Extension in Its SDS Resistance, Thermostability, and Activity

  • Hu, Hang;Chen, Kaixiang;Li, Lulu;Long, Liangkun;Ding, Shaojun
    • Journal of Microbiology and Biotechnology
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    • 제27권4호
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    • pp.775-784
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    • 2017
  • A neutral xylanase (CcXyn) was identified from Coprinus cinereus. It has a single GH10 catalytic domain with a basic amino acid-rich extension (PVRRK) at the C-terminus. In this study, the wild-type (CcXyn) and C-terminus-truncated xylanase ($CcXyn-{\Delta}5C$) were heterologously expressed in Pichia pastoris and their characteristics were comparatively analyzed with aims to examine the effect of this extension on the enzyme function. The circular dichorism analysis indicated that both enzymes in general had a similar structure, but $CcXyn-{\Delta}5C$ contained less ${\alpha}-helices$ (42.9%) and more random coil contents (35.5%) than CcXyn (47.0% and 32.8%, respectively). Both enzymes had the same pH (7.0) and temperature ($45^{\circ}C$) optima, and similar substrate specificity on different xylans. They all hydrolyzed beechwood xylan primarily to xylobiose and xylotriose. The amounts of xylobiose and xylotriose accounted for 91.5% and 92.2% (w/w) of total xylooligosaccharides (XOS) generated from beechwood by CcXyn and $CcXyn-{\Delta}5C$, respectively. However, truncation of the C-terminal 5-amino-acids extension significantly improved the thermostability, SDS resistance, and pH stability at pH 6.0-9.0. Furthermore, $CcXyn-{\Delta}5C$ exhibited a much lower $K_m$ value than CcXyn (0.27 mg/ml vs 0.83 mg/ml), and therefore, the catalytic efficiency of $CcXyn-{\Delta}5C$ was 2.4-times higher than that of CcXyn. These properties make $CcXyn-{\Delta}5C$ a good model for the structure-function study of $({\alpha}/{\beta})_8$-barrel-folded enzymes and a promising candidate for various applications, especially in the detergent industry and XOS production.

Optimum Combination of Thermoplastic Formability and Electrical Conductivity in Al-Ni-Y Metallic Glass

  • Na, Min Young;Park, Sung Hyun;Kim, Kang Cheol;Kim, Won Tae;Kim, Do Hyang
    • Metals and materials international
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    • 제24권6호
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    • pp.1256-1261
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    • 2018
  • Both thermoplastic formability and electrical conductivity of Al-Ni-Y metallic glass with 12 different compositions have been investigated in the present study with an aim to apply as a functional material, i.e. as a binder of Ag powders in Ag paste for silicon solar cell. The thermoplastic formability is basically influenced by thermal stability and fragility of supercooled liquid which can be reflected by the temperature range for the supercooled liquid region (${\Delta}T_x$) and the difference in specific heat between the frozen glass state and the supercooled liquid state (${\Delta}C_p$). The measured ${\Delta}T_x$ and ${\Delta}C_p$ values show a strong composition dependence. However, the composition showing the highest ${\Delta}T_x$ and ${\Delta}C_p$ does not correspond to the composition with the highest amount of Ni and Y. It is considered that higher ${\Delta}T_x$ and ${\Delta}C_p$ may be related to enhancement of icosahedral SRO near $T_g$ during cooling. On the other hand, electrical resistivity varies with the change of Al contents as well as with the change of the volume fraction of each phase after crystallization. The composition range with the optimum combination of thermoplastic formability and electrical conductivity in Al-Ni-Y system located inside the composition triangle whose vertices compositions are $Al_{87}Ni_3Y_{10}$, $Al_{85}Ni_5Y_{10}$, and $Al_{86}Ni_5Y_9$.

TAp73 and ΔNp73 Have Opposing Roles in 5-aza-2'-Deoxycytidine-Induced Apoptosis in Breast Cancer Cells

  • Lai, Jing;Yang, Fang;Zhang, Wenwen;Wang, Yanru;Xu, Jing;Song, Wei;Huang, Guichun;Gu, Jun;Guan, Xiaoxiang
    • Molecules and Cells
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    • 제37권8호
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    • pp.605-612
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    • 2014
  • The p73 gene contains an extrinsic P1 promoter and an intrinsic P2 promoter, controlling the transcription of the pro-apoptotic TAp73 isoform and the anti-apoptotic ${\Delta}Np73$ isoform, respectively. The DNA methylation status of both promoters act equally in the epigenetic transcriptional regulation of their relevant isoforms. The aim of this study was to analyze the different effects of these p73 isoforms in 5-aza-2'-deoxycytidine (5-aza-dC)-induced apoptosis in breast cancer cells. We investigated the effects of the DNA demethylation agent, 5-aza-dC, on the T-47D breast cancer cell line, and evaluated the methylation status of the p73 promoters and expression of TAp73 and ${\Delta}Np73$. Furthermore, we assessed the expression of p53 and p73 isoforms in 5-aza-dC-treated T-47D cells and p53 knockout cells. 5-aza-dC induced significant anti-tumor effects in T-47D cells, including inhibition of cell viability, G1 phase arrest and apoptosis. This was associated with p73 promoter demethylation and a concomitant increase in TAp73 mRNA and protein expression. In contrast, the methylation status of promoter P2 was not associated with ${\Delta}Np73$ mRNA or protein levels. Furthermore, demethylation of P2 failed to inhibit the expression of ${\Delta}Np73$ with 5-aza-dC in the p53 knockdown cell model. Our study suggests that demethylation of the P1 and P2 promoters has opposite effects on the expression of p73 isoforms, namely up-regulation of TAp73 and down-regulation of ${\Delta}Np73$. We also demonstrate that p53 likely contributes to 5-aza-dC-induced ${\Delta}Np73$ transcriptional inactivation in breast cancer cells.

Identification of Petroselinic Acid (Cis-6-octadecenoic Acid) in the Seed Oils of Some of the Family Umbelliferae (Panax schinseng, Aralia continentalis and Acanthopanax sessiliflorus) by GC-MS, IR, $^1H-and$ $^13C-NMR$ Spectroscopic Techniques

  • Kim, Seong-Jin
    • 한국응용과학기술학회지
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    • 제22권4호
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    • pp.323-331
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    • 2005
  • Fatty acid compositions of the seed oils of P. schinseng, A. continentalis and A. sessiliflorus, were analyzed by gas chromatography (GC) equipped with a capillary column. A large unusual peak was observed just before the peak corresponding to oleic acid $(cis-9-C_{18:1})$. This unknown fatty acid was isolated by silver ion chromatography and then derivatized into the picolinyl ester. The mass spectrum of the picolinyl ester showed molecular ion at m/z=373 with other diagnostic ions such as m/z=178, 218, 232, 246, 274, 288, 302 and 344. Characteristic absorption peaks at $720\;cm^{-1}$, $1640\;cm^{-1}$ and $3010\;cm^{-1}$ in IR spectrum indicated the presence of cis-configurational double bond in the molecule. The $^1H-NMR$ spectrum of this acid gave two quintets centered at ${\delta}1.638$ (2H, C-3) and ${\delta}1.377$ (2H, C-4), and two multiplets centered at ${\delta}2.022{\sim}2.047$ (2H, C-5) and ${\delta}2.000{\sim}2.022$ (2H, C-8), and multiplet signals of olefinic protons centered at ${\delta}5.3015{\sim}5.3426$ (C-6, J=9.5 Hz) and ${\delta}\;5.3465{\sim}5.3877$ (C-7, J=9.5 Hz). The $^13C-NMR$ spectrum showed 18 carbon resonance signals including an overlapped signal at ${\delta}29.7002$ for C-12 and ${\delta}29.6520$ for C-13 (or they can be reversed), and other highly resolved signals at ${\delta}33.950$, ${\delta}24.558$, ${\delta}26.773$ and ${\delta}27.205$ due to C-2, C-3, C-5 and C-8 of a ${\Delta}^6-octadecenoic$ acid, respectively. From analysis results this unknown fatty acid could be identified as cis-6-octadecenoic acid. The seed oils of P. schinseng and A. sessiliflorus contained petroselinic acid (59.7%, 56.0%), oleic acid (18.3%, 6.1%) and linoleic acid (16.2%, 30.4%) with small amount of palmitic acid (3.0%, 3.1%) while the seed oil of A. continentalis comprised mainly oleic acid (30.2%), petroselinic acid (29.0%), linoleic acid (24.1%) and palmitic acid (13.1%).