• Title/Summary/Keyword: solvent polarity

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Solvent Effects on the Nucleophilc Addition (I) Effect of Solvent Polarity on the Nucleophilic Addition of Amine to Phenylvinylketone (친핵성 첨가반응에 대한 용매효과 (I) Phenylvinylketone에 대한 아민의 첨가반응속도에 미치는 용매의 극성효과)

  • Gap-Cheol Shin;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.287-292
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    • 1992
  • The rate constants of the nucleophilic addition reaction of amines (piperidine and diethylamine) to phenylvinylketone in various solvents have been determined by UV spectrophotometry at $25^{\circ}C$. On the basis of the high sensitivity of the rate to the polarity of the medium, it may be concluded that the reaction intermediate has zwitterionic character. The effect of the solvents on the rate of the bimolecular nucleophilic addition reaction is described well by the Kirkwood equation: The transition state of the reaction has a cyclic structure formed through an intramolecular hydrogen bond. The addition reaction of primary and secondary amines to phenylvinylketone in all solvents take place considerably faster than that of tertiary amine and this results also can be explained by the intermediate products in the reaction have a cyclic structure formed through an intramolecular hydrogen bond for the primary and secondary amines but not for the tertiary amine.

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Extraction Characteristics of Flavonoids from Lonicera flos by Supercritical Fluid Carbon Dioxide ($SF-CO_2$) with Co-solvent (초임계유체 $CO_2$ 및 Co-solvent 첨가에 따른 금은화(Lonicera fles)의 Flavonoid류 추출특성)

  • Suh, Sang-Chul;Cho, Sung-Gill;Hong, Joo-Heon;Choi, Yong-Hee
    • Korean Journal of Food Science and Technology
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    • v.37 no.2
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    • pp.183-188
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    • 2005
  • Effects of co-solvent polarity, citric acid, pressure, temperature, run time, and co-solvent ratio on extraction of major flavonoids from Lonicera Flos were investigated using supercritical fluid $CO_{2}(SF-CO_{2})$. HPLC analysis revealed addition of pure methanol resulted in low extraction yield of major flavonoids, luteoloin (Lu), Quercetin (Qu), Apigenin (Ap). Under same condition, as co-solvent polarity increased, yields of major flavonoids increased gradually, At optimum co-solvent extraction condirion of 60% aqueous methanol (10%, v/v), yields of Lu, Qu, and Ap were 42.09, 28.18, and 3.49 mg/100 g, respectively. Addition of citric acid to 60% aqueous methanol gave higher, with addition of 1% citrie acid resulting in highest yields of 63.2 (Lu), 39.35 (Qu), and 5.79 (Ap) mg/100 g. Optimum extraction conditions of major flavonoids were 200 bar, $50^{\circ}C$, 60 min, and $CO_{2}$-methanol-water(20: 1.8: 1.2).

Resistive Switching Memory Devices Based on Layer-by-Layer Assembled-Superparamagnetic Nanocomposite Multilayers via Nucleophilic Substitution Reaction in Nonpolar Solvent

  • Kim, Yeong-Hun;Go, Yong-Min;Gu, Bon-Gi;Jo, Jin-Han
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.05a
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    • pp.243.1-243.1
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    • 2011
  • We demonstrate a facile and robust layer-by-layer (LbL) assembly method for the fabrication of nonvolatile resistive switching memory (NRSM) devices based on superparamagnetic nanocomposite multilayers, which allows the highly enhanced magnetic and resistive switching memory properties as well as the dense and homogeneous adsorption of nanoparticles, via nucleophilic substitution reaction (NSR) in nonpolar solvent. Superparamagnetic iron oxide nanoparticles (MP) of about size 12 nm (or 7 nm) synthesized with oleic acid (OA) in nonpolar solvent could be converted into 2-bromo-2-methylpropionic acid (BMPA)-stabilized iron oxide nanoparticles (BMPA-MP) by stabilizer exchange without change of solvent polarity. In addition, bromo groups of BMPA-MP could be connected with highly branched amine groups of poly (amidoamine) dendrimer (PAMA) in ethanol by NSR of between bromo and amine groups. Based on these results, nanocomposite multilayers using LbL assembly could be fabricated in nonpolar solvent by NSR of between BMPA-MP and PAMA without any additional phase transfer of MP for conventional LbL assembly. These resulting superparamagnetic multilayers displayed highly improved magnetic and resistive switching memory properties in comparison with those of multilayers based on water-dispersible MP. Furthermore, NRSM devices, which were fabricated by LbL assembly method under atmospheric conditions, exhibited the outstanding performances such as long-term stability, fast switching speed and high ON/OFF ratio comparable to that of conventional inorganic NRSM devices produced by vacuum deposition.

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Effects of the Variables in the Fabrication of Anode on the Performance of DMFC (직접 메탄올 연료전지용 산화극 제조 변수가 성능에 미치는 영향)

  • Kim, Joon-Hee;Ha, Heung-Yong;Oh, In-Hwan;Hong, Seong-Ahn;Lee, Ho-In
    • Journal of the Korean Electrochemical Society
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    • v.6 no.1
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    • pp.18-22
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    • 2003
  • Single cell performance has been investigated and characterized with variables in the fabrication of DMFC anode. The performance was checked as a function of ionomer content which affects ion conductivity in the catalyst layer, and catalyst slurry solvent which determines structure of agglomerates consisting of an ionomer and a catalyst. Anode with total ionomer to catalyst ratio of 0.6 showed the best performance and the lowest polarization resistance. Also, electrochemically effective surface area increased with ionomer content. As solubility of the ionomer decreases with decreasing solvent polarity, the size of agglomerates consisting of a catalyst and an ionomer became larger in the less polar solvent. The anode using DPK $(\varepsilon=12.60)$ as a solvent, which is less polar than generally-used water or alcohol species, showed the maximum performance and the lowest polarization resistance.

Inhibition of MMP-2 and -9 by Crude Extracts and Their Solvent-partitioned Fractions from the Halophyte Atriplex gmelinii (가는갯능쟁이(Atriplex gmelinii) 추출물과 용매분획물의 MMP-2와 MMP-9 활성 저해효과)

  • Park, Min Jeong;Kim, Junse;Kong, Chang-Suk;Seo, Youngwan
    • Ocean and Polar Research
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    • v.41 no.2
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    • pp.79-88
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    • 2019
  • In this study, the inhibitory effect of Atriplex gmelinii C. A. Mey. against the activity of MMP-2 and MMP-9 secreted from phorbol-12-myristate-13-acetate (PMA)-stimulated HT-1080 cells was evaluated by gelatin zymography and enzyme-linked immunosorbent assay (ELISA), reverse transcription polymerase-chain reaction (RT-PCR), and Western blot assay. Specimens of the halophyte A. gmelinii were extracted twice for 24 hr with methylene chloride ($CH_2Cl_2$), and then twice with methanol (MeOH), in turn. Each extract significantly inhibited the enzymatic activities in gelatin zymography and MMP ELISA kit, and expression of MMP-2 and 9 in mRNA and protein levels. Two crude extracts were combined and then the combined crude extracts were fractionated into n-hexane, 85% aqueous methanol (85% aq.MeOH), n-butanol (n-BuOH), and water ($H_2O$) fractions, according to solvent polarity. Among solvent-partitioned fractions, the 85% aq.MeOH fraction showed the strongest inhibitory effect against MMP-2 and -9 in gelatin zymography and MMP ELISA kit. In RT-PCR, all solvent-partitioned fractions significantly suppressed mRNA expression of MMP-2 and -9. On the other hand, in Western blot assay, all solvent-partitioned fractions except $H_2O$ significantly reduced expression levels of protein. HT 1080 cell migration was most significantly inhibited by the n-BuOH fraction followed by the 85% aq.MeOH and $H_2O$ fractions. These results suggest that A. gmelinii could be used as a potential source to inhibit tumor cell metastasis.

Crude Extract and Solvent-Partitioned Fractions of the Halophyte Atriplex gmelinii Inhibit Adipogenesis in 3T3-L1 Preadipocytes (3T3-L1 지방전구세포에서 염생식물 Atriplex gmelinii의 조추출물과 용매 분획물의 지방세포분화 억제)

  • Jung Im Lee;Jung Hwan Oh;Chang-Suk Kong;Youngwan Seo
    • Journal of Korean Medicine for Obesity Research
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    • v.23 no.2
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    • pp.69-77
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    • 2023
  • Objectives: Atriplex gmelinii C. A. Meyer is a halophyte belonging to the Chenopodiaceae family, and its young leaves and stems are used as fodder for livestock. The aim of the present study was to investigate the effects of A. gmelinii extract and its solvent fractions on lipid accumulation during adipogenesis of 3T3-L1 preadipocytes. Methods: The samples of A. gmelinii were separately extracted using methylene chloride and methanol. Subsequently, they were combined to formulate the initial extract, which was then partitioned based on polarity to prepare solvent fractions. Oil Red O staining was employed to measure lipid accumulation during the differentiation of 3T3-L1 preadipocytes. To verify cytotoxicity in 3T3-L1 cells, MTT assays were conducted. The expression levels of transcription factors in 3T3-L1 preadipocytes were measured through Western blotting analysis. Results: At 50 ㎍/mL, treatment of A. gmelinii extract and its solvent fractions during the differentiation of 3T3-L1 preadipocytes significantly diminished lipid accumulation with no noteworthy cytotoxicity on cell viability. Additionally, when investigating the biochemical pathways that underlie the prevention of lipid accumulation using solvent fractions, it was found that the n-BuOH and n-hexane fractions significantly decreased the expression of key transcription factors involved in the generation of fat, such as peroxisome proliferator-activated receptor γ (PPARγ), CCAAT/enhancer binding protein α (C/EBPα), and sterol regulatory element-binding protein-1c (SREBP1c). Conclusions: These findings indicate that A. gmelinii can effectively reduce the accumulation of fat in 3T3-L1 adipocytes, making it a potentially valuable material for mitigating and preventing obesity.

Effect of Solvents on the Photochromic Properties of Spiropyran in Hard Coating Films Prepared by Sol-Gel Method (Spiropyran의 분산용매가 Sol-Gel 하드 코팅 막의 광 변색 특성에 미치는 영향)

  • Kim, Dae Hyun;Shin, Yong Tak;Lee, Ju Yeon;Hong, Wongil;Lee, Bum Suk;Song, Ki Chang
    • Korean Chemical Engineering Research
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    • v.47 no.4
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    • pp.430-435
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    • 2009
  • Spiropyran-doped organic-inorganic hybrid coatings were prepared starting from glycidoxypropyl triethoxysilane and vinyltriethoxysilane by a sol-gel method. They were applied as a thin layer to polycarbonate sheets and their photochromic properties were investigated. The effect of polarity of solvents dissolving the spiropyran was investigated on the photochromic properties. The decoloration rate of the spiropyran decreased with increasing the polarity of solvents dissolving the spiropyran because the open form of the spiropyran was easily stabilized in the polar gel matrix.

Determination of Microviscosity and Location of 1,3-Di(1-pyrenyl) propane in Brain Membranes

  • Kang, Jung-Sook;Kang, In-Goo;Yun, Il
    • Archives of Pharmacal Research
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    • v.20 no.1
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    • pp.1-6
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    • 1997
  • We determined the microviscosity of synaptosomal plasma membrane vesicles (SPMV) isolated from bovine cerebral cortex and liposomes of total lipids (SPMTL) and phospholipids (SPMPL) extracted from SPMV. Changes in the microviscosity induced by the range and rate of lateral diffusion were measured by the intramolecular excimerization of 1, 3-di(1-pyrenyl)propane (Py-3-Py). The microviscosity values of the direct probe environment in SPMV, SPMTL and SPMPL were 38.17, 31.11 and 27.64 cP, respectively, at$37^{\circ}C$and the activation energies $(E_a)$ of the excimer formation of Py-3-Py in SPMV, SPMTL and SPMPL were 8.236, 7.448 amd 7.025 kcal/mol, respectively. Probe location was measured by polarity and polarizability parameters of the probe Py-3-Py and probe analogues, pyrene, 1-pyrenenonanol and 1-pyrenemethyl-3${\beta}$-hydroxy-22, 23-bisnor-5-cholenate (PMC), incorporated into membranes or solubilized in reference solvents. There existed a good linear relationship between the first absorption peak of the $^1_a$ band and the polarizability parameter $(n^{2}-1)/(2n^{2}+1)$.The calculated refractive index values for SPMV, SPMTL and SPMPL were close to 1.50, which is higher than that of liquid paraffin (n=l.475). The probe location was also determined by using a polarity parameter $(f-1/2f^{I})$. Here f=$({\varepsilon}-1)/(2{\varepsilon}+1)$ is the dielectric constant function and $f^I=(n^2-1)/(2n^2+1)$ is the refractive index function. A correlation existed between the monomer fluorescence intensity ratio and the solvent polarity parameter. The probes incorporated in SPMV, SPMTL, and SPMPL report a polarity value close to that of 1-hexanol $({\varepsilon}=13.29)$. In conclusion, Py-3-Py is located completely inside the membrane, not in the very hydrophobic core, but displaced toward the polar head groups of phospholipid molecules, e.g., central methylene region of aliphatic chains of phospholipid molecules.

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Solubilization and Photosensitizing Properties of Some Anthracene Derivatives in Aqueous Micellar Solutions (수용성 미셀용액에서 몇 가지 안트라센 유도체의 가용화 및 감광화 성질)

  • Jeong Soo Ko;Dong Sul Han;Hyung Sik Oh;Byung Kwan Park;Chong Hyun Kim;Se Woung Oh
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.452-460
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    • 1991
  • The chemical evidence for involvement of singlet oxygen during photoirradiation for 2-ethylanthracene [2-EA] and 9-phenylanthracene [9-PA] was based on the rapid decomposition of 1,3-diphenylisobenzofuran [DPBF] in methanol-water mixture and aqueous CTAB, and SDS micellar solutions. The average microenvironmental polarities of 2-EA and 9-PA were estimated by UV spectroscopic characteristics sensitive to the polarity of solvent. When 2-EA and 9-PA were solubilized in aqueous CTAB, SDS and Brij 35 solutions, their average microenvironmental polarities were polar, and their microenvironmental polarity parameter showed little dependence on the ionic properties of the micelles. The average microenvironmental polarity of 2-EA was similar to the polarity of 40% (w/w) aqueous ethanol, and that of 9-PA was similar to the polarity between 30 and 40% (w/w) aqueous ethanol. It was found that the greater part of these species might be distributed at the surface of micelles when they were solubilized in aqueous micellar solutions. The methanol-water mixture solution appeared to have characteristics more favorable for photooxidation reaction than aqueous micellar solutions.

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The hyperfine interaction in water-solvent system (물-용매계에서의 초미세 상호작용)

  • Lee, Mi-Nyeong;Kim, Tae-Kwan;Lee, Sung-Ki;Park, Yoon-Chang
    • Analytical Science and Technology
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    • v.18 no.3
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    • pp.194-200
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    • 2005
  • The N hyperfine coupling constants ($a_N$) of di-t-butyl nitroxide (DTBN) radicals in water-solvent system were measured with EPR spectroscopy. Various kinds of the solvents with different polarity such as acetone, dimethylsulfoxide (DMSO), methanol, ethanol and 1-propanol were applied and studied. Equilibrium constants for the solvation equilibrium and the solvent parameters ($E_T$, molar transition energy) of various water-solvent system were obtained from the experimental results and are presented. The $a_N$ values were plotted as a function of mole fraction of the solvent. In case of water-DMSO, water-ethanol and water-1-propanol system, slight negative deviations from the straight line were observed. In water-acetone system, the absorption wavelength (${\lambda}$) due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition increased linearly with the increase of mole fraction of acetone. The relationship between $a_N$ of DTBN and ${\lambda}$ due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition in water-acetone and water-DMSO system was examined. It was found that the electronic structure of the nitroxide radicals is stablized from the fact that the N hyperfine coupling constants of DTBN radicals are greatly unaffected in the environment of water-solvent system.