• Title/Summary/Keyword: 용액합성

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Kinetics and Hydrolysis Mechanism of Herbicidal N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide Derivatives (제초성, N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-치환(Z)-6-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide 유도체의 가수분해 반응 메카니즘)

  • Lee, Chan-Bog;Ryu, Jae-Wook;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.38 no.5
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    • pp.455-462
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    • 1995
  • The new six herbicidal N-[(pyrimidin-2-yl)aminocarbonyl]-2-substituted-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide derivatives(S) were synthesized and rate constants for the hydrolysis of thier in the range of pH $1.0{\sim}10.0$ have been studied in 15%(v/v) aqueous acetonitrile solution at $45^{\circ}C$. From the basis of the results, pH-effect, solvent effect, ortho-substituent effect, thermodynamic parameters(${\Delta}H^{\neq}$ & ${\Delta}S^{\neq}$), pKa constant(4.80), rate equation, analysis of hydrolysis products(2-(1-hydroxy-2-fluoroethyl)benzenesulfonamide & 4,6-dimethoxyaminopyrimidine), it may be concluded that the general acid catalyzed hydrolysis through $A-S_E2$ mechanism and specific acid catalyzed hydrolysis through A-2 type(or $A_{AC}2$) mechanism proceeds via conjugate acid($SH^+$) and tetrahedral intermediate(I) below pH 8.0, whereas, above pH 9.0, the general base catalyzed hydrolysis by water molecules(B) through $(E_1)_{anion}$ mechanism proceeds via conjugate base(CB). In the range between $pH\;7.0{\sim}pH\;9.0$, these two reactions occur competitively.

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Effect of fluoride concentration in pH 4.3 and pH 7.0 supersaturated solutions on the crystal growth of hydroxyapatite (pH 4.3과 pH 7.0의 과포화용액에서 불소의 농도가 합성 수산화인회석의 결정 성장에 미치는 영향)

  • Shin, Han-Eol;Park, Sung-Ho;Park, Jeong-Won;Lee, Chan-Young
    • Restorative Dentistry and Endodontics
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    • v.37 no.1
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    • pp.16-23
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    • 2012
  • Objectives: Present study was undertaken to investigate the crystal growth onto synthetic hydroxyapatite (HA) seeds in pH 4.3 and pH 7.0 supersaturated solutions with different fluoride concentrations. Materials and Methods: 8 groups of pH 4.3 and 7.0 calcium phosphate supersaturated solutions were prepared with different fluoride concentrations (0, 1, 2 and 4 ppm). Calcium phosphate precipitates yield crystal growth onto the HA seed surface while solutions flow. For evaluation of crystallizing process, the changes of $Ca^{2+}$, $PO{_4}^{3-}$, $F^-$ concentrations of the inlet and outlet solutions were determined. The recovered solid samples were weighed to assess the amount of minerals precipitated, and finally determined their composition to deduce characteristics of crystals. Results: During the seeded crystal growth, there were significantly more consumption of $Ca^{2+}$, $PO{_4}^{3-}$, $F^-$ in pH 4.3 solutions than pH 7.0 (p < 0.05). As fluoride concentration increased in pH 4.3 solution, $Ca^{2+}$, $PO{_4}^{3-}$, $F^-$ consumption in experimental solutions, weight increment of HA seed, and fluoride ratio in crystallized samples were increased. There were significant differences among the groups (p < 0.05). But in pH 7.0 solution, these phenomena were not significant. In pH 7.0 solutions, analyses of crystallized samples showed higher Ca/P ratio in higher fluoride concentration. There were significant differences among the groups (p < 0.05). But in pH 4.3 solution, there were not significant differences in Ca/P ratio. Conclusions: Crystal growth in pH 4.3 solutions was superior to that in pH 7.0 solutions. In pH 4.3 solutions, crystal growth increased with showed in higher fluoride concentration up to 4 ppm.

Spectrofluorimetric Determination of Fe(Ⅲ) with 4,5-Dihydroxy-1,3-Benzenedisulfonic Acid (4,5-Dihydroxy-1,3-Benzenedisulfonic Acid를 이용한 Fe(Ⅲ)의 분광형광법 정량)

  • Kim, Hye Seon;Choi, Hee Seon
    • Journal of the Korean Chemical Society
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    • v.43 no.4
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    • pp.423-429
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    • 1999
  • A spectrofluorimetric method for the determination of Fe(III) in aqueous solution with 4,5-dihydroxy-1,3-benzenedisulfonic acid(Tiron) as a fluorimetric reporter was developed. Tiron, which is very soluble in water,is a good fluorimetric reagent. However, when Tiron was complexed with Fe(III), the fluorescent intensity was decreased proportionally with the concentration of Fe(III) by a quenching effect. The excitation and fluorescene wavelength of Tiron showing the quenching effect by Fe(III) at pH 4.5 were 312 nm and 341 nm, respectively. The highest sensitivities were shown at Tiron concentration of $1.0{\times}10^{-2}M$. To enhance the quenching effect, the Fe(III)-Tiron complex solution was heated to 80$^{\circ}C$ for 90 minutes. As for Fe(III), the most interfering ion was Cu(II). The interference effects could be mostly eliminated by pH adjustment or by adding EDTA. The concentration ranges showing the linear response to Fe(III) was from $5.0{\times}10^{-7}M\;to\;6.0{\times}10^{-5}M$ With this proposed method, the detection limits of Fe(III) was $2.8{\times}10^{-6}M$. Recovery of Fe(lII) in a synthetic sample was almost quantitative. Based on experimental results, it is proposed that the above technique can be applied to the practical determination of Fe(III).

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Hydrogen Production from Splitting of Methanol/Water Solution Using Perovskite Structured NbxSrTi1-xO3 Photocatalyts (Perovskite NbxSrTi1-xO3 광 촉매를 이용한 메탄올/물 분해로부터 수소제조)

  • Kim, Dongjin;Han, Gi Bo;Park, No-Kuk;Lee, Tae Jin;Kang, Misook
    • Korean Chemical Engineering Research
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    • v.51 no.4
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    • pp.513-517
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    • 2013
  • This study focused on the synthesis of $Nb_xSrTi_{1-x}O_3$ photocatalysts which partially inserted Nb ions with excellent ability of fluorescence into the perovskite structured $SrTiO_3$ frameworks and their photocatalytic hydrogen productions from methanol/water splitting corresponding to the molar ratios of Ti and Nb. The characteristics of the synthesized $SrTiO_3$ and $Nb_xSrTi_{1-x}O_3$ powders were analyzed by X-ray diffraction (XRD), energy dispersive X-ray spectrometer (EDS), and UV-Visible spectrometer. The hydrogen evolution from methanol/water photo-splitting was enhanced over $Nb_{0.05}SrTi_{0.95}O_3$ compared to those over $SrTiO_3$ and another $Nb_xSrTi_{1-x}O_3$; 4.9 mL of hydrogen gases was collected after 8 h when 0.5g of $Nb_{0.05}SrTi_{0.95}O_3$ catalyst was used in pH 10.

Synthesis, Potentiometric, Spectral Characterization and Microbial Studies of Transition Metal Complexes with Tridentate Ligand (세자리 리간드의 전이금속 착물에 대한 합성과 전위차 및 분광학적 확인 그리고 미생물학적 연구)

  • Jadhav, S.M.;Munde, A.S.;Shankarwar, S.G.;Patharkar, V.R.;Shelke, V.A.;Chondhekar, T.K.
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.515-522
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    • 2010
  • A relation between antimicrobial activities and the formation constants of solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with tridentate Schiff base ligand, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2Hpyran-2-one (HL) derived from o-phenylene diamines, dehydroacetic acid (DHA) and p-chloro benzaldehyde have been studied. The ligand and metal complexes were characterized by elemental analysis, conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, $^1H$-NMR, UV-vis and mass spectra. From the analytical data, the stiochiometry of the complexes was found to be 1:2 (metal:ligand) with octahedral geometry. The molar conductance values suggest the nonelectrolytic nature of metal complexes. The X-ray diffraction data suggests monoclinic crystal system for Ni(II) and orthorhombic crystal system for Cu(II) and Co(II) complexes. The IR spectral data suggest that the ligand behaves as tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behavior (TG/DTA) and kinetic parameters calculated by Coats-Redfern method suggests more ordered activated state in complex formation. The protonation constants of the complexes were determined potentiometrically in THF:water (60:40) medium at $25^{\circ}C$ and ionic strength ${\mu}=0.1\;M$ ($NaClO_4$). Antibacterial activities in vitro were performed against Staphylococcus aureu and Escherichia coli. Antifungal activities were studied against Aspergillus Niger and Trichoderma. The effect of the metal ions and stabilities of complexes on antimicrobial activities are discussed.

Large-strain Soft Sensors Using Elastomers Blended with Exfoliated/Fragmented Graphite Particles (탄성중합체와 박리 후 파쇄된 흑연입자 복합재를 이용한 대변형률 연성 센서)

  • Park, Sungmin;Nam, Gyungmok;Kim, Jonghun;Yoon, Sang-Hee
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.40 no.9
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    • pp.815-820
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    • 2016
  • An elastic polymer (e.g., PDMS) blended with EFG particles is a promising conductive composite for fabricating soft sensors that can detect an object's deformation up to or more than 50%. Here, we develop large-strain, sprayable soft sensors using a mixture of PDMS and EFG particles, which are used as a host elastomer and electrically conductive particles, respectively. A solution for a conductive composite mixture is prepared by the microwave-assisted graphite exfoliation, followed by ultrasonication-induced fragmentation of the exfoliated graphite and ultrasonic blending of PDMS and EFG. Using the prepared solutions for composite and pure PDMS, 1-, 2-, and 3-axis soft sensors are fabricated by airbrush stencil technique where composite mixture and pure PDMS are materials for sensing and insulating layers, respectively. We characterize the soft strain sensors after investigating the effect of PDMS/EFG wt% on mechanical compliance and electrical conductance of the conductive composite.

Reaction of the Fe(II) Macrocyclic Complexes with Dioxygen : Preparation of New Unsaturated Ring Systems by Oxidative Dehydrogenation Reactions of Fe(II) Macrocyclic Ligands (이가철 거대고리 리간드의 착화합물과 산소 분자간의 반응 : 이가철 거대고리 리간드 착화합물의 산화성 탈수소 반응에 의한 새로운 불포화 고리계의 합성)

  • Myunghyun Paik;Shin-Geol Kang;Kyu Whan Woo
    • Journal of the Korean Chemical Society
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    • v.28 no.6
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    • pp.384-392
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    • 1984
  • Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

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Transparent Polyimide Nanocomposite Films with Various Equi-biaxial Stretching Ratios (다양한 이축연신 비율에 따른 투명 폴리이미드 나노복합체 필름)

  • Kim, Young-Min;Chang, Jin-Hae
    • Polymer(Korea)
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    • v.36 no.4
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    • pp.478-485
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    • 2012
  • A series of transparent polyimide (PI) nanocomposite films was synthesized from bicyclo(2,2,2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTDA) and 1,3-bis(3-aminophenoxy)benzene (BAPB) with various organoclay contents via solution intercalation polymerization to poly(amic acid)s, followed by thermal imidization. Varying organoclay loading in a range of 0 to 1.5 wt% produced variations in the optical transparency, morphology, and oxygen barrier property of the hybrids. An optimum oxygen barrier property was observed for the hybrids containing 1.0 wt% Cloisite 30B; these properties were degraded gradually by further increases in the clay content. The PI hybrid films were found to exhibit excellent optical transparency and almost no color. However, the transparency of the hybrid films decreased slightly with increasing organoclay content. Transparent PI hybrid films containing 1.0 wt% Cloisite 30B were stretched equi-biaxially with various stretching ratios in a range of 100-140% to investigate their optical transparency and oxygen permeability in detail; the variations of clay dispersion and morphology were also determined as a function of equi-biaxial stretching ratio. PI hybrid films with ${\geq}120%$ stretching were found to contain homogeneously dispersed clay in the polymer matrix and exfoliated nanocomposites. The highest barrier to oxygen permeation was found at an equi-biaxial stretching ratio of 130%.

Preparation of Poly(imide-aramid-sulfone)s and their Thermal Properties (폴리(이미드-아라미드-설폰)의 합성과 그들의 열적성질)

  • Park, Hyung-Seok;Gong, Myoung-Seon
    • Polymer(Korea)
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    • v.36 no.4
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    • pp.427-433
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    • 2012
  • A series of poly(imide-aramid-sulfone)s with alternatingly introduced imide/aramid groups were prepared by reacting divinyl sulfone (DVS) and $N^1,N^4$-bis(4-(vinylsulfonyl)phenyl)terephthalamide (2) with pyromellitic diimide. Three model compounds, N-[2-(p-aminophnenylsulfonyl)ethyl]phthalimide (3), 2,2'-(2,2'-sulfonylbis(ethane-2,1-diyl))diisoindoline-1,3-dione (4), and N,N-bis(4-(2-(1,3-dioxoisoindolin-2-yl)ethylsulfonyl)phenyl)terephthalamide (5), resembling polymers were prepared with good yields by reacting p-aminophenyl vinyl sulfone, DVS, and 2 with phthalimide. Condensation polymerization was carried out by Michael-type addition reaction of the difunctional phthalimide group with the DVS group in the presence of tetrabutylammonium hydroxide (TBAH), resulting in poly(imide-aramid-sulfone)s 6-12 with moderate molecular weights and good yields. They were highly soluble in polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone and tetrahydrofuran. The ratios of DVS/2 were 1/0, 3/1, 2/1, 1/1, 1/2, 1/3, and 0/1. Molecular weight and physical properties such as solubility, viscosity, and thermal properties of the polymers were examined.

Colorless Copolyimide Films: Thermo-mechanical Properties, Morphology, and Optical Transparency (무색 투명한 폴리이미드 공중합체 필름 : 열적-기계적 성질, 모폴로지, 및 광학 투명성)

  • Jin, Hyo-Seong;Chang, Jin-Hae
    • Polymer(Korea)
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    • v.32 no.3
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    • pp.256-262
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    • 2008
  • Copolyimides containing pendant trifluoromethyl ($CF_3$) groups were synthesized from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS) with various concentrations of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane(BAPP) to poly(amic acid)(PAA), followed by thermal imidization. These copolyimides were readily soluble in N,N'-dimethylacetamide (DMAc) and could be solution-cast into a flexible and tough film. The thermomechanical properties, morphology and an optical transparency of the copolyimide films were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), scanning electron microscopy (SEM), universal tensile machine (UTM), and a UV-Vis spectrometer. The cast copolyimide films exhibited high optical transparency with a cut-off wavelength (${\lambda}_0$) of $275{\sim}319\;nm$ in UV-vis absorption and a low yellow index(YI) value of $3.65{\sim}10.37$. The thermo-mechanical properties of copolyimide films were enhanced linearly with increasing a BAPP content. In contrast, the optical transparency of the copolyimide films was found to get worse with increasing a BAPP content.