• Title/Summary/Keyword: Dioxane

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Enzymatic Synthesis of Flame Retardant Phenolic Polymers Catalyzed by Horseradish Peroxidase (Horseradish Peroxidase 효소촉매에 의한 난연성 페놀고분자의 합성)

  • Park, Han Sol;Park, Jung Hee;Lee, Hak Sung;Ryu, Keungarp
    • Korean Chemical Engineering Research
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    • v.51 no.1
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    • pp.111-115
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    • 2013
  • The optimum synthetic conditions of poly(p-phenylphenol) by horseradish peroxidase in dioxane:water (80:20 v/v) mixtures were studied. The stability against thermal degradation and structural properties of the synthesized phenolic resins were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. The synthetic yield of poly(p-phenylphenol) increased upon the increase of the amount of enzyme up to 0.25 mg HRP/mL, then leveled off for further increase of the enzyme usage. When sodium acetate (100 mM, pH 4~6) and sodium phosphate (100 mM, pH 7~9) were used as the buffering salts for the aqueous component (20% v/v), the synthetic yield of the resin increased at higher pH of the aqueous buffer. But when the pHs of the aqueous buffer were 6 and 9, the synthetic yield strongly depended on the types of the buffering salts; if sodium phosphate was used instead of sodium acetate at pH 6, the yield decreased by about 15% and if sodium bicarbonate was used instead of sodium phosphate, the yield decreased by almost 20%. When the pH range of the aqueous buffer was from 4 to 7, the addition of a radical mediator, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) (ABTS), up to 2 mM improved the synthetic yield of the resin by about 10%. TGA experiments revealed that the thermal stability of the resin synthesized in dioxane:water (100 mM sodium phosphate, pH 9) (80:20 v/v) was high having the char yield of 47% upon the heating at $800^{\circ}C$. DCS results showed that the structures of the polymers synthesized in acidic aqueous buffers were different from those of the polymers synthesized in the basic aqueous buffers. However, all the synthesized resins were found to have the property of the thermosetting resins.

Hydrophilizing Effect of Support on PRO Membrane Performance through Cellulose Solution Treatment (셀룰로오스에 의한 지지체 친수화가 압력지연삼투막 성능에 미치는 영향)

  • Choi, Myungho;Koo, Kee-Kahb;Lim, Jung Ae;Kim, BeomSik
    • Membrane Journal
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    • v.23 no.6
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    • pp.425-431
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    • 2013
  • This paper has studied the hydrophilizing effect of support on the performance of pressure retarded osmosis (PRO). The hydrophilicity of polyester support has been controlled with cellulose solutions. In order to investigate the effect of hydrophilizing of support, the performance test has been conducted with membrane which compose of active layer and support in absence of support layer. The active layer has been made by casting of cellulose tri-acetate (CTA) 1,4-dioxane solution (13 wt%) and combined with the hydrophilized support. The results show that water fluxes of PRO membranes with hydrophobic or hydrophilized support were measured $0.8L/m^2hr$ and $1.2L/m^2hr$ under $5kgf/cm^2$ pressure, respectively. However, water flux increase did not accord with hydrophilicity of supports treated by cellulose solutions. It is because the porosity and pore size of supports decrease as the cellulose concentration increases. This result confirms that both the hydrophilization of support and the maintenance of membrane porosity are important to enhance the performance of PRO membrane.

Kinetics and Mechanism of Hydrolysis of Insecticidal Imidacloprid (살충성 Imidacloprid의 가수분해 반응 메카니즘)

  • Yu, Sung-Jae;Kang, Moon-Sung;Sung, Nack-Doo
    • Applied Biological Chemistry
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    • v.40 no.1
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    • pp.53-57
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    • 1997
  • The rate of hydrolysis of insecticidal 1-(6-chloro-3-pyridylmethyl) -2-nitro-iminoimidazolidine (common name; imidacloprid) have been investigated in 15%(v/v) aqueous dioxane at $45^{\circ}C$. From the kinetics and non-kinetics data such as pH-effect, solvent effect(m=0.04, n=0.30 IT m<${\Delta}H^{\neq}=16.14kcal{\cdot}mol^{-1}\;&\;{\Delta}S^{\neq}=-0.03e.u.$), rate equation ($k_{obs.}=4.56{\times}10^{-3}[OH^-]$) and analysis of hydrolysis product, 1-(6-chloro-3-pyridylmethyl-2)-imidazolidinon, the hydrolysis mechanism of imidacloprid is proposed that the specific base catalyzed hydrolysis($K_{OH^-}$) through nucleophilic addition-elimination ($Ad_N-E$) mechanism proceed via intermediate, 1-(6-chloro-3- pyridylmethyl)-2-hydroxy-2-imidazolidinylisonitraminate (I) and ${\beta}$-3-(6-chloro-3-pyridylmethyl)aminoethyl-1-nitrourea(III). And the half-life(t1/2) of hydrolytic degradation at pH 8.0 and $45^{\circ}C$ was about 4.5 months.

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Determination of hazardous semi-volatile organic compounds in industrial wastewater using disk-type solid-phase extraction and GC-MS (디스크형 고상 추출법과 GC/MS를 이용한 공장폐수 중 반휘발성유기화합물질 분석)

  • Lee, In-Jung;Lim, Tae-Hyo;Heo, Seong-Nam;Nam, Su-Gyeong;Lee, Jae-Gwan;Cheon, Se-Uk
    • Analytical Science and Technology
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    • v.25 no.4
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    • pp.236-241
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    • 2012
  • There are many industrial factories in the central Nakdong river basin and have been occurred water pollution accidents by hazardous chemicals such as phenol, 1,4-dioxane and perchlorate. In this study, ten compounds of semi-volatile organic compounds (SVOCs) (dichlorvos, toluene-2,4-diisocyanate, 4,4'-methylenedianiline, 4,4'-methylenebis (2-chloroaniline), diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthaltate, bis (2-ethylhexyl) adipate, benzophenone, 4,4'-bisphenol A) of hazardous chemicals which may be potentially discharged into the Nakdong river, were determined by gas chromatography-mass spectrometry (GC-MS) with disk-type solid-phase extraction. Accuracy and precision were in the range of 75.6~110.5%, and 4.6~12.7%, respectively and recovery was in the range of 72.4~127.9%. Three compounds (bis (2-ethylhexyl)adipate, benzophenone, 4,4'-bisphenol A) were detected in industrial wastewater such as wastewater treatment plants (WWTPs) and wastewater discharge facilities in the Nakdong River basin.

The Effects of Solvent and Nonsolvent on Asymmetric Membrane Structure of 6FDA-p-TeMPD Polyimide (6FDA-p-TeMPD 폴리이미드 비대칭막 제조에서 용매와 비용매가 막구조에 미치는 영향)

  • 박노춘;김건중;남세종
    • Membrane Journal
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    • v.8 no.3
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    • pp.157-169
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    • 1998
  • The effects of solvents (DMAc, NMP, 1,4-dioxane) and nonsolvents ($H_2O$, Methanol, n-hexane) on the morphology of 6FDA-p-TeMPD polyimide membrane, prepared by the wet phase inversion method, were studied. In the polymer/solvent/nonsolvent ternary system, the binodal curve, the coagulation value and the relative light transmission were measured, and the solubility parameter difference was calculated. The onset state and rate of liquid-liquid alemixing were predicted and the morphology of membrane was analyzed. It is found that the finger-like pores are formed within discontinuous polymer nodules when the binoclal curve is close to the polymer-solvent (P-S) axis, the coagulation value is small, the reduction of light transmission is easy to occur and the order of solubility parameter difference ($\Delta \delta_{i-j}$) is $\Delta \delta_{S-NS} > \Delta \delta_{P-NS} > \Delta \delta_{P-S}$. The dense skin with small nodules and the sponge type sublayer with macrovoid are formed in the case that the binodal curve is distant from the P-S axis, the onset time of liquid-liquid demixing is long and the order of $\Delta \delta_{i-j}$ is $\Delta \delta_{P-NS} >(\Delta \delta_{S-NS} < > \Delta \delta_{P-S})$. The thick layer of fine nodule coagulation and loosely grown sublayer of nodules appear when the binodal curve is distant from the P-S axis, the onset time of liquid-liquid demixing is very long and the order of $\Delta \delta_{i-j}$$\Delta \delta_{S-NS} > (\Delta \delta_{P-NS}$\lessgtr$ > (\Delta \delta_{P-NS} < >)\Delta \delta_{P-S}$ ).

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Application of a New Scaling Parameter to Chain Expansion in the Systems of Polystyrene/Mixed Solvents (폴리스티렌/혼합용매 계에서 사슬의 팽창에 대한 새로운 스케일링 파라미터의 적용)

  • Park, Il-Hyun;Lee, Dong-Il;Hwang, Mi-Ok;Yu, Young-Chol;Park, Ki-Sang
    • Polymer(Korea)
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    • v.31 no.2
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    • pp.98-104
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    • 2007
  • The expansion behavior of polystyrene (PS) chains with various molecular weights has been investigated above Flory $\Theta$temperature by viscometry after dissolving in the three different mixed solvents systems such as benzene/n-heptane, 1,4-dioxane/isopropanol, and 1,4-dioxane/n-heptane. Two different regimes are observed as increasing temperature: one regime is for the expansion of chain and the other is for the contraction. For the higher molecular weight sample of PS, the higher peak temperature showing its maximum expansion is obtained. Within a certain system of Ps/mixed solvents, the $\tau/\tau_c$ parameter shows universality for the variation of molecular weight. But while each system of Ps/mixed solvents has shown its own different slope, the universality breaks down in the overall system of mixed solvents. However after introducing a new empirical $b^{2/3}\tau/\tau_c$ parameter, all data points of three different systems have dropt on one master curve and the universality of chain expansion has recovered again. Here $\tau$ and $\tau_c$ are defined as $(T-\Theta)/\Theta$ and $(\Theta-T_c)/T_c$, respectively and $T_c$ is the critical solution temperature, and b of Schultz-Flory equation is corresponding to the effective slope in the plot of $1/T_c$ against $1/M_w^{1/2}$.

Stabilization of Nanoemulsion Using PEG-free Surfactant (PEG-free 계면활성제를 사용한 Nanoemulsion의 안정화)

  • Kim, Huiju;Jung, Taek Kyu;Kim, Ja Young;Yoon, Kyung-Sup
    • Journal of the Korean Applied Science and Technology
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    • v.36 no.2
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    • pp.434-447
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    • 2019
  • Polyethylene glycol (PEG) is widely used in cosmetics as a surfactant, detergent and emulsifier. During the manufacturing process, 1,4-dioxane, which is toxic to humans, can be produced as a by-product by dimerization of ethylene oxide. As consumers' interest in cosmetic ingredients has increased, the need for safe emulsion research without PEG ingredients in the personal care market has increased. With increasing consumer interest in cosmetic ingredients, the need for safer emulsion research without the PEG ingredient in the personal care market has increased. In this study, we aimed to develop and stabilize nanoemulsion formulation without PEG. Response Surface Methodology (RSM) was used to develop optimized nanoemulsion formulations. Surfactant content (2~4%), oil content (4~8%) and polyol content (12~24%) were set as independent variables as a result of preliminary experiments for determining independent variables and ranges. The particle size, zeta potential, turbidity, and polydispersity index of the formulation were measured as response variables. As a result of measurement of the prepared nanoemulsion by FIB (Focused ion beam), spherical particles were found to have a size distribution of 100 to 200 nm. The stability of each formulation was evaluated for 30 days at each temperature ($4^{\circ}C$, $25^{\circ}C$, and $45^{\circ}C$). The optimal formulation considering the optimum particle size, turbidity, polydispersity index and zeta potential was found to be surfactant (2%), oil (8%) and polyol (24%).

Fluorescence Quenching of Bis-msb by Carbon Tetrachloride in Different Solvents

  • Thipperudrappa, J.;Biradar, D.S.;Lagare, M.T.;Hanagodimath, S.M.;Inamdar, S.R.;Kadadevaramath, J.S.
    • Journal of Photoscience
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    • v.11 no.1
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    • pp.11-17
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    • 2004
  • Fluorescence quenching of l,4-bis [2-(2-methylphenyl) ethenyl]-benzene (Bis-MSB) by carbon tetrachloride in five different solvents namely hexane, cyclohexane, toluene, benzene and dioxane has been carried out at room temperature with a view to understand the quenching mechanisms. The Stern-Volmer plot has been found to be non-linear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the Ground state complex and Sphere of action static quenching models. Using these models various rate parameters have been determined. The magnitudes of these parameters imply that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation in the Stem-Volmer plots is attributed to the static and dynamic quenching. Further, with the use of Finite Sink approximation model, it was possible to check whether these bimolecular reactions as diffusion limited and to estimate independently distance parameter R' and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R'and D with the values of the encounter distance R and the mutual diffusion coefficient D determined using the Edwardis empirical relation and Stokes-Einstein relation.

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Microscopic Analysis on New Water-soluble Hydrate Systems (새로운 수용성 하이드레이트 시스템에 대한 미세 분광학적 분석연구)

  • Lee, Jong-Won;Lu, Hailong;Moudrakovski, Igor L.;Ratcliffe, Christopher I.;Ripmeester, John A.
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.215.1-215.1
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    • 2010
  • 가스 하이드레이트는 작은 고체 부피 내에 막대한 양의 가스를 저장할 수 있다는 특성으로 인하여, 최근 천연가스 혹은 메탄의 저장 매체로 활용하기 위한 연구가 활발히 진행중에 있다. 하지만 실제 응용을 위해서는 미세구조 분석이 수행되어 하이드레이트 형태로 저장할 수 있는 정확한 저장 용량을 파악할 필요가 있다. 본 연구에서는 여러가지의 고리형 에테르, 고리형 에스테르 및 고리형 케톤 화합물들을 테스트하여 메탄 가스와 반응하는 6가지의 새로운 sII 혹은 sH 하이드레이트 형성제를 파악하였다. 또한 새로이 발견된 형성제 모두에 대하여 하이드레이트 상평형도 측정하였다. 얻어진 상평형 데이터는 하이드레이트 안정영역과 게스트 분자 크기 간에 뚜렷한 상관관계가 있음을 입증하였다. 아울러 형성된 하이드레이트 샘플은 고체 분말 X-선 회절과 고체상 13C NMR 분석을 수행하여 하이드레이트 구조와 게스트 포집률을 조사하였다. 마지막으로, 비슷한 화학 구조식을 갖고 있음에도 2-methyltetrahydrofuran과 3-methyltetrahydrofuran, 혹은 4-methyl-1,3-dioxane과 4-methyl-1,3-dioxolane은 서로 다른 하이드레이트 결정 구조를 보여 주었는데, 이러한 차이는 하이드레이트 결정 구조를 결정짓는 게스트 분자 크기, 즉 임계 게스트 분자 크기를 파악하는 데에도 매우 유용한 정보를 제공할 수 있을 것이라 판단된다.

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Cinnamic Acid Derivatives IV, The Kinetics and Mechanism of the Hydrolysis of Cinnamylidene aniline Derivatives (신남산 유도체 Ⅳ, Cinnamylidene anilin 유도체의 가수분해 반응에 대한 메카니즘과 그 반응속도론적 연구)

  • Lee, Gi-Chang;Park, Su-In;Hwang, Yong-Hyeon;Lee, Gwang-Il;Choe, Bong-Jong;Jeong, Deok-Chae
    • Journal of the Korean Applied Science and Technology
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    • v.8 no.1
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    • pp.1-7
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    • 1991
  • The kinetic of hydrolysis for cinnamylidene aniline derivatives has been investigated by ultraviolet spectrophotometry in 20% (v/v) dioxane - $H_2O$ at $25^{\circ}C$. A rate equation which can be applied over wide pH range was obtained. The substituent effects on cinnamylidene aniline derivatives were studied and the hydrolysis was facilitated by electron attracting group. Final products of the hydrolysis were cinnamaldehyde and aniline. From the rate equation, substituent effect and final products, the hydrolysis of cinnamylidene aniline derivatives was initiated by the neutral molecule of $H_2O$ which does not dissociate at below pH 9.0${\sim}$12.0, but proceeded by the hydrogen ion at above pH 5.0${\sim}$9.0.