• 제목/요약/키워드: Phenyl modification

검색결과 32건 처리시간 0.023초

Enhancement in the Textural Properties and Hydrophobicity of Tetraethoxysilane-based Silica Aerogels by Phenyl Surface Modification

  • Dhavale, Rushikesh P.;Parale, Vinayak G.;Kim, Taehee;Choi, Haryeong;Kim, Younghun;Lee, Kyu-Yeon;Jung, Hae-Noo-Ree;Park, Hyung-Ho
    • 마이크로전자및패키징학회지
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    • 제27권2호
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    • pp.27-32
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    • 2020
  • Robust and hydrophobic tetraethoxysilane (TEOS) based silica aerogel was synthesized by supercritical alcohol drying with surface modification using the phenyl based silica co-precursor (PTMS). The aerogels were synthesized by hydrolysis and polycondensation reaction in which TEOS and PTMS in methanol were reacted together in presence of oxalic acid and ammonium hydroxide as the catalysts. Supercritical alcohol dried PTMS/TEOS composite silica aerogel were examined for the hydrophobicity, chemical interaction, surface morphology, and textural characteristics. The hydrophobic silica-based aerogels were characterized by Fourier transform infrared spectroscopy to investigate the presence of functional groups and chemical bonds. The prepared silica demonstrates hydrophobicity (76°-149°), a high specific surface area (398 ㎡/g to 739 ㎡/g). The present investigation provides a simple approach to synthesize hydrophobic and thermally stable silica aerogels.

A Kinetic Study on Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Z-Substituted-Phenoxides: Effect of Modification of Nonleaving Group from Benzoyl to Phenyloxycarbonyl on Reactivity and Reaction Mechanism

  • Min, Se-Won;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제33권10호
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    • pp.3253-3257
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    • 2012
  • Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

Aminolysis of Y-Substituted Phenyl 2-Thiophenecarboxylates and 2-Furoates: Effect of Modification of Nonleaving Group from 2-Furoyl to 2-Thiophenecarbonyl on Reactivity and Mechanism

  • Um, Ik-Hwan;Min, Se-Won
    • Bulletin of the Korean Chemical Society
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    • 제29권3호
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    • pp.585-589
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    • 2008
  • Second-order rate constants (kN) have been measured for reactions of Y-substituted phenyl 2-thiophenecarboxylates (6a-h) with morpholine and piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the reactions of 6a-h with morpholine is linear with b lg = 1.29, indicating that the reactions proceed through a tetrahedral zwitterionic intermediate (T?). On the other hand, the Brnsted-type plot for the reactions of 6a-h with piperidine exhibits a downward curvature, implying that a change in the rate-determining step occurs on changing the substituent Y in the leaving group. Dissection of kN into microscopic rate constants (i.e., k1 and k2/k1 ratio) has revealed that k1 is smaller for the reactions of 6a-h than for those of Y-substituted phenyl 2-furoates (5a-h), while the k2/k1 ratio is almost the same for the reactions of 5a-h and 6a-h. It is also reported that modification of the nonleaving group from the furoyl (5a-h) to the thiophenecarbonyl (6a-h) does not influence pKao (defined as the pKa at the center of the Brnsted curvature) as well as the k2/k1 ratio.

Alkaline Hydrolysis of Y-Substituted Phenyl Phenyl Thionocarbonates: Effect of Changing Electrophilic Center from C=O to C=S on Reactivity and Mechanism

  • Kim, Song-I;Park, Hey-Ran;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제32권1호
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    • pp.179-182
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    • 2011
  • Second-order rate constants ($k_{OH^-}$) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with $OH^-$ in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The $k_{OH^-}$ values for the reactions of 4a-i have been compared with those reported previously for the corresponding reactions of Y-substituted phenyl phenyl carbonates (3a-i) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and mechanism. Thionocarbonates 4a-i are less reactive than the corresponding carbonates 3a-i although 4a-i are expected to be more reactive than 3a-i. The Bronsted-type plot for reactions of 4a-i is linear with $\beta_{lg}$ = -0.33, a typical $\beta_{lg}$ value for reactions reported to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step (RDS). Furthermore, the Hammett plot correlated with $\sigma^o$ constants results in much better linearity than that correlated with $\sigma^-$ constants, indicating that expulsion of the leaving group is not advanced in the RDS. Thus, alkaline hydrolysis of 4a-i has been concluded to proceed through a stepwise mechanism with formation of an intermediate being RDS, which is in contrast to the forced concerted mechanism reported for the corresponding reactions of 3a-i. Enhanced stability of the intermediate upon modification of the electrophilic center from C=O to C=S has been concluded to be responsible for the contrasting mechanisms.

Quantum Chemical Designing of Novel Organic Non-Linear Optical Compounds

  • Mahmood, Asif;Abdullah, Muhammad Imran;Nazar, Muhammad Faizan
    • Bulletin of the Korean Chemical Society
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    • 제35권5호
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    • pp.1391-1396
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    • 2014
  • In the present study, ten metal free non-linear optical (NLO) compounds have been designed. These compounds have designed by structural modification of (2-cyano-5-(4-(phenyl(4-vinylphenyl)amino)phenyl) penta-2,4-dienoic acid (TC4). Density functional theory was used for structure optimization and determination of photo-physical properties. These compounds contain triphenylamine as electron-donor and cyanoacrylic acid as acceptor. Five ${\pi}$-spacers are used to connect the donor and acceptor. Two auxiliary donors are also used to assist the donor. Results of this study indicate that stronger electron-donating auxiliary groups and longer ${\pi}$-conjugation enhance NLO response. Major absorption peaks of all systems were in the visible region. These absorption peaks are associated with the ${\pi}-{\pi}^*$ transitions of the entire molecule. From calculations it is clear that all system will be good NLO material. The present calculations will provide new ways for experimentalists to synthesize high-performance NLO material.

Anionic Indicators on the Surface of Submicrospheres Consisting of Ionic Palladium(II) Complex

  • Kim, Cho-Rong;Noh, Tae-Hwan;Yoo, Kyung-Ho;Yoo, Bok-Ryul;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • 제30권12호
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    • pp.3057-3060
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    • 2009
  • Ionic palladium(II) complex, [($Me_4en)Pd(L)]_2(ClO_4)_4\;(Me_4$en = N,N,N',N'-tetramethylethylenediamine; L = bis-(4-(4-pyridylcarboxyl)phenyl)methane), allows to form a monodisperse submicrosphere without any template or additive. Surface-perchlorates on the submicrosphere have been exchanged by anionic pH indicators such as thymol blue, bromothymol blue, and bromocresol green. The ionic and amphiphilic properties of the palladium(II) complex appear to be primarily associated with the formation and easy surface-anion exchange of submicrosphere. The surface-anion exchange through the electrostatic interaction is a very good tool for the surface-modification. The color of the pH indicator-exchanged submicrospheres is very sensitive to pH and Hg$^{2+}$ cation, and thus they are promising to submicrospherical indicators.

Surface modification for block copolymer nanolithographyon gold surface

  • 황인찬;방성환;이병주;이한보람;김형준
    • 한국재료학회:학술대회논문집
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    • 한국재료학회 2009년도 추계학술발표대회
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    • pp.33.2-33.2
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    • 2009
  • Block copolymer lithography has attracted great attention for emerging nanolithography since nanoscaleperiodic patterns can be easily obtained through self-assembly process without conventional top-down patterning process. Since the morphologies of self-assembled block copolymer patterns are strongly dependent on surface energy of a substrate, suitable surface modification is required. Until now, the surface modification has been studied by using random copolymer or self-assembled mono layers (SAMs). However, the research on surface modifications has been limited within several substrates such as Si-based materials. In present study, we investigated the formation of block copolymer on Au substrate by $O_2$ plasma treatment with the SAM of 3-(p-methoxy-phenyl)propyltrichloro-silane [MPTS, $CH_3OPh(CH_2)_3SiCl_3$]. After $O_2$ plasma treatment, the chemical bonding states of the surface were analyzed by X-ray photoelectron spectroscopy (XPS). The static contact angle measurement was performed to study the effects of $O_2$ plasma treatment on the formation of MPTS monolayer. The block copolymer nanotemplates formed on Au surface were analyzed by scanning electron microscopy. The results showed that the ordering of self-assembled block copolymer pattern and the formation of cylindrical nano hole arrays were enhanced dramatically by oxygen plasma treatment. Thus, the oxidation of gold surface by $O_2$ plasma treatment enables the MPTS to form the monolayer assembly leading to surface neutralization of gold substrates.

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항진균제 알릴아민류의 합성과 생물학적 평가 (Synthesis and Biological Evaluation of Allylamine Antimycotics)

  • 정병호;조원제;천승훈;박면지;유진철;천문우
    • 약학회지
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    • 제41권2호
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    • pp.187-194
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    • 1997
  • For the development of antifungal agents, modification of naftifine which exhibits significant antimycotic activity was performed by replacing the naphthalene ring of it to hete ro cyclic rings such as morpholine. benzothiazole, piperidine and pyridine derivatives. The synthesized compounds were tested in vitro antifungal activity against five different fungi with naftifine as a comparative antimycotic molecule. From the biological evaluation two compounds, (E)-N-(3-phenyl-2-propenyl)-N-(4-piperidinylmethyl)amine(3d) and (E)-N-(3-phenyl-2-propenyl)-N-(3-pyridylmethyl)amine(3f) showed relatively noticeable activity(MIC=50${\mu}g$/ml). On the other hand, the other compounds had no activity.

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Synthesis of New Uraci1-5-Sulphonamide-p-Phenyl Derivatives and Their Effect on Biomphalaria alexandrina Snail's Nucleoproteins

  • Fathalla, O.A.;Gad, H.S.M.;Maghaby, A.S.
    • Archives of Pharmacal Research
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    • 제23권2호
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    • pp.128-138
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    • 2000
  • In continuation of the previous work (Fathalla, 1992) on the synthesis of some heterocycles containing uracil moiety, we report herein the incorporation of uracil moiety into cyan-opyridine thione, thiosemecarbazone, semicarbazone, cyanopyridine, ami nocyano pyridine, isoxazoline, pyrazoline, pyrimidine, triazolo pyrimidine, pyran, selena and thiazole derivatives which might modify their biological activities. The biological studies revealed that the chemical compound III f showed high molluscicdal activity than other compounds. The profile of the nucleoprotein extracted from chemically (compound IIIc, e, f and g) treated or UV-irradiated B.alexandrina snails did not show appreciable differences when compared to non-treated (native) snails by using SDS-PAGE, where no obvious qualitative or quantitative differences were observed. Immunization of experimental animals with the nucleoprotein extracted from native, chemically (compound III f & g) treated or physically treated B.alexandrina snails induced significant protection against challenge with normal S.mansoni cercariae, as compared to the non-immunized challenged control. As well as , a decrease in the number of granuloma formation and the size range of granuloma was also observed in immunized animals. It is concluded that, compounds III f and g have a potent molluscicidal activity. They also induced chemical modification comparable to that induced by physical treatment in the snail's nucleoprotein, which could possibly be used in immunization against S. mansoni infection.

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