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Effect of Substituted Groups on the Retention of Monosubstituted Phenols in Reversed-Phase Liquid Chromatography (역상 액체 크로마토그래피에서 페놀 일치환체들의 머무름에 미치는 치환기들의 영향)

  • Kim, Hun Ju;Lee, In Ho;Lee, Dae Un
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.562-569
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    • 1994
  • The retention data of twenty one monosubstituted phenols in the eluent systems containing 30∼70% of methanol or acetonitrile as organic modifiers, on $ C_{18}$ and Phenyl columns were collected to investigate the effect of the substituted groups on the retention of phenols. The capacity factors of the solutes except amino phenols are greater on $ C_{18}$ than on Phenyl column. And all the solutes have shown greater capacity factors in methanol-water than that in acetonitrile-water as a mobile phase. Generally the elution order between meta and para isomers of monosubstituted phenols in consistent (p < m) regardless of the polarity of the substituted group. But the elution order between ortho and meta isomers of phenol varies with regard to the polarity of the substituted group. The retention of the monosubstituted phenols has been influenced by the interaction between the solute and unreacted silanol of columns as well as the interaction between the solute and $ C_{18}$ or phenyl group of columns. And then, the effect of unreacted silanol on the retention of the monosubstituted phenols is greater on $ C_{18}$ than on Phenyl column. And the greater hydrogen bonding acceptor basicity(${\beta}$) of the substituted group is, the greater this effect is. The relationship between the retention of the monosubstituted phenols and their parameters such as van der Waals volume(VWV) and hydrogen bonding acceptor basicity(${\beta}$) has been investigated. The good linearity has been observed in the plot log k' vs. (1.01VWV/100-1.84${\beta}$). In consequence, the retention of the monosubstituted phenols on $ C_{18}$ and Phenyl columns can be easily predicted by the parameter (1.01VWV/100-1.84${\beta}$).

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New Fluorescent Blue OLED Host and Dopant Materials Based on the Spirobenzofluorene

  • Lee, In-Ho;Gong, Myoung-Seon
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1475-1482
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    • 2011
  • New spiro[benzo[c]fluorene-7,9'-fluorene] (SBFF)-based blue host materials, 9-phenyl-SBFF (BH-4P) and 5,9-diphenyl-SBFF (BH-6DP), were successfully prepared by spiro-formation of 9-phenyl-7H-benzo[c]fluoren-7-one with 2-bromobiphenyl via lithiation and reaction of 5,9-dibromo-SBFF with phenylboronic acid through the Suzuki reaction, respectively. Diphenyl-[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)-phenyl]-amine (BD-1) and N,N-diphenyl-N',N'-diphenyl-SBFF-5,9-diamine (BD-6DPA) were used as dopant materials. Blue OLEDs with the configuration ITO/N,N'-bis-[4-(di-m-tolylamino)phenyl]-N,N'-diphenylbiphenyl-4,4'-diamine (DNTPD)/bis[N-(1-naphthyl)-N-phenyl]benzidine (NPB)/host:5% dopant/SFC-137/Al-LiF were prepared from the two host materials doped with BD-1 and BD-6DPA dopants and the devices composed of BH-4P and BH-6DP doped with BD-6DPA showed blue EL spectra at 458 and 463 nm at 7 V and luminance efficiencies of 4.58 and 4.88 cd/A, respectively.

Kinetics and Mechanism of Alkaline Hydrolysis of Y-Substituted Phenyl Phenyl Carbonates

  • Kim, Song-I;Hwang, So-Jeong;Jung, Eun-Mi;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.7
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    • pp.2015-2018
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    • 2010
  • Second-order rate constants $(k_{OH^-})$ have been measured spectrophotometrically for alkaline hydrolysis of Y-substituted phenyl phenyl carbonates (2a-j) and compared with the $k_{OH^-}$ values reported previously for the corresponding reactions of Y-substituted phenyl benzoates (1a-j). Carbonates 2a-j are 8~16 times more reactive than benzoates 1a-j. The Hammett plots correlated with $\sigma^-$ and $\sigma^o$ constants exhibit many scattered points, while the Yukawa-Tsuno plot results in excellent linear correlation with $\rho$ = 1.21 and $\gamma$ = 0.33. Thus, the reaction has been concluded to proceed through a concerted mechanism in which expulsion of the leaving group is advanced only a little. However, one cannot exclude a possibility that the current reaction proceeds through a forced concerted mechanism with a highly unstable intermediate.

Pore Size Control of Silica-Coated Alumina Membrane for $CO_2$ Separation ($CO_2$ 선택투과 분리를 위한 Silica 코팅 Alumina 막의 세공 제어)

  • 서봉국;김성수;김태옥
    • Journal of Environmental Science International
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    • v.8 no.2
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    • pp.263-269
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    • 1999
  • For effective $CO_2$ separation using pore size controlled membrane, silica was deposited in the mesopores of a $\gamma$-alumina film by chemical vapor deposition of tetraethoxysilane (TEOS) and phenyl-substituted ethoxysilanes at 773-873K. The membranes prepared with phenyl-substituted ethoxysilanes were calcined to remove the phenyl group and control the pore size. The gas permaselectivity of prepared membranes was evaluated by using $H_2$, $CO_2$ $N_2$, $CH_2$ and $C_3H_8$ single component and a mixture of $CO_2$ and $N_2$. The membranes produced using TEOS contained micropores having permselectivity only to hydrogen, but the phenyl-subsitituted ethoxysilane derived membranes possessed micorpores which are recognizable molecules of $CO_2$, $N_2$ and $CH_4$. In the diphenyl-diethoxysilane-derived membrane, the $CO_2$ permeance and selectivity of $CO_2$/$CH_4$ were $10^{-6} m^3(STP) \cdot m^{-2} \cdot s^{-1} \cdot kPa^{-1}$ and 11, respectively. Therefore, the use of phenyl-substituted ethoxysilane was effective in controlling micropore size for $CO_2$ separation.

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D-A-D type molecules based on dibenzophosphole-chalcogenides and triphenylamine moieties; effects of chalcogenide atoms on their photochemical properties

  • Iijima, Shunsuke;Hori, Keichi;Nakashima, Takuya;Kawai, Tsuyoshi
    • Rapid Communication in Photoscience
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    • v.3 no.4
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    • pp.61-63
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    • 2014
  • 3,7-bis(4-(diphenylamino)phenyl)-5-phenyl-5H-benzo[b]phosphinedole 5-sulfide (DBPPS-TPA) and 3,7-bis(4-(diphenylamino)phenyl)-5-phenyl-5H-benzo[b]phosphinedole 5-selenide (DBPPSe-TPA) are newly synthesized D-A-D type molecules based on dibenzophospholes and their physic-chemical properties are studied in comparison with a P=O type compouond, 3,7-bis(4-(diphenylamino)-5-phenyl-5H-benzo[b]phosphinedole 5-oxide (DBPPO-TPA). Fluorescence emission and electrochemical redox properties of these compounds are investigated regarding results of density functional theory (DFT) calculations, X-ray crystallographic structures and UV-vis absorption spectra. These results exhibit systematic variation in optical properties of these compounds having P=O, P=S, and P=Se units. LUMO energy level is systematically modulated with different chalcogenide atoms.

Kinetic Study on the Alkaline Hydrolysis of the 4-Substituted Phenyl Ethyl Benzylphosphonates (4-치환 Phenyl Ethyl Benzylphosphonate의 알칼리 가수분해 반응에 대한 속도론적 연구)

  • Shon, Kyoung Hwa;Park, Kyung Kone;Lee, Bu Young;Shin, Bu Young
    • Journal of the Korean Chemical Society
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    • v.41 no.6
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    • pp.299-303
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    • 1997
  • The rate constants($k_{OH}$) for the alkaline hydrolysis of the 4-substituted phenyl ethyl benzylphosphonates were determined in various buffer solutions by UV(Vis spectrophotometer. The activation entropies of the title reactions show negative values and this result is not consistent with a dissociative mechanism (EA) for which a positive or slightly negative value of the entropy of activation should be expected. An associative mechanism(AE) is favorable because the negligible negative charge is generated on the leaving group in the rate determining step from a good Hammett relationship(ρ=1.89). By the results of a kinetic study, we conclude that a dissociative mechanism is not proceeded in the title reactions.

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New Bipolar Green Host Materials Containing Benzimidazole-Carbazole Moiety in Phosphorescent OLEDs

  • Park, Jung-Hwan;Kim, Eun-Kyung;El-Deeb, Ibrahim M.;Jung, Su-Jin;Choi, Dae-Hyuk;Kim, Dong-Ha;Yoo, Kyung-Ho;Kwon, Jang-Hyuk;Lee, So-Ha
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.841-846
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    • 2011
  • New green host materials, 9-phenyl-3-(4-(1-phenyl-1H-benzo[d] imidazol-2-yl)phenyl)-9H-carbazole (3a) and 9-(naphthyl-2-yl)-3-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-9H-carbazole (3b), have been designed and synthesized by attaching the electron transporting benzimidazole moiety to the hole transporting carbazole unit. These compounds have similar HOMO, LUMO levels and band-gap characteristics compared with CBP (4,4'-di(N-carbazolyl)biphenyl). The fabricated green phosphorescent OLED with this 3a host shows much better device performances compared to CBP-based one. The current and power efficiency is enhanced at least by 60 percent at a given constant luminance of 1000 cd/$m^2$.

A Novel 3-(8-Chloro-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-yl)phenyl Acetate Skeleton and Pharmacophore Model as Glucagon-like Peptide 1 Receptor Agonists

  • Gong, Young-Dae;Cheon, Hyae-Gyeong;Lee, Tae-Ho;Kang, Nam-Sook
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3760-3764
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    • 2010
  • We screened 10,000 heterocyclic small molecules and identified a novel hit core skeleton of 3-(8-chloro-6-(trifluoromethyl) imidazo[1,2-a]pyridine-2-yl)phenyl acetate derivatives. It has been selected as a potential glucagon-like peptide 1 receptor (GLP-1R) activator and demonstrated its effects in increasing GLP-1 secretion, and thereby increasing the glucose responsiveness in both in vitro and pharmacology analyses. Further studies are currently underway to optimize the potency and selectivity of 3-(8-chloro-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-yl)phenyl acetate derivatives (hit compounds 2 and 8), and address their in vivo efficacy and therapeutic potential. These molecules may serve as useful evidence showing that compounds with a 3-(8-chloro-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-yl)phenyl acetate moiety are selective GLP-1R agonists, and have potential as anti-diabetic treatment agents.

Blue OLEDs Utilizing Spiro[fluorene 7,9'-benzofluorene]-type Compounds as Hosts and Dopants

  • Kim, Joo-Han;Jeon, Young-Min;Jang, Ji-Geun;Ryu, Sang-Ouk;Chang, Ho-Jung;Lee, Chil-Won;Kim, Joon-Woo;Gong, Myoung-Seon
    • Bulletin of the Korean Chemical Society
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    • v.30 no.3
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    • pp.647-652
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    • 2009
  • A novel spiro-type host material, 5-[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9'-benzofluorene] (BH-1PN) and three new dopants, namely, 5-[diphenylamino)phenyl]-spiro[fluorene-7,9'-benzofluorene] (BH-1TPA), 5-[4-(N-phenyl (m-tolyl)amino]-spiro[fluorene-7,9'-benzofluorene] (BH-1MDPA) and 5-[(N-phenyl)-2-naphthyl]amino-spiro[fluorene- 7,9'-benzofluorene] (BH-1NPA) were designed and successfully prepared using the Suzuki or amination reactions. The electroluminescence characteristics of BH-1PN as a blue host material doped with each of the blue dopants were evaluated. The structure of the device is ITO/DNTPD/NPB/BH-1PN:5% dopant/Alq3/Al-LiF. The device obtained from BH-1PN doped with diphenyl-[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)phenyl]-amine (BD-1) showed good color purity, efficiency, luminance, and current-density characteristics.

Transition-State Variation in the Solvolyses of para-Substiuted Phenyl Chloroformates in Alcohol-Water Mixtures

  • 구인선;양기율;강금덕;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.968-973
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    • 1998
  • Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.