• Title/Summary/Keyword: Concentration Transition

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Synthesis and Properties of Cholesteric Liquid Crystalline Polymers with Isosorbide Group (아이소소바이드기를 갖는 콜레스테릭 액정고분자의 합성 및 성질)

  • Gu, Su-Jin;Yoon, Doo-Soo;Bang, Moon-Soo
    • Applied Chemistry for Engineering
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    • v.28 no.2
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    • pp.230-236
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    • 2017
  • We synthesized liquid crystalline polymers containing isosorbide group as a cholesteric derivative and methylene group for controlling the transition temperature to the liquid crystal phase. Effects of the concentration of the isosorbide group and the position of the methylene group on the properties of the liquid crystalline polymer were investigated. Among all the synthesized polymers, polymers (MnHI-x) with a methylene group in the main chain showed higher melting transition temperature and thermal stability than those (SnBI-x) with a methylene group in the side chain. All the synthesized polymers showed an enantiotropic liquid crystal phase. The polymers having 10 mol% isosorbide as a cholesteric liquid crystal phase derivative showed nematic phase, and those having 20 mol% or more isosorbide showed a cholesteric or chiral smectic phase. Thus, we can conclude that the isosorbide group plays a role as a cholesteric liquid crystal phase derivative.

Unfolding of Ervatamin C in the Presence of Organic Solvents: Sequential Transitions of the Protein in the O-state

  • Sundd, Monica;Kundu, Suman;Dubey, Vikash Kumar;Jagannadham, Medicherla V.
    • BMB Reports
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    • v.37 no.5
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    • pp.586-596
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    • 2004
  • The folding of ervatamin C was investigated in the presence of various fluorinated and non-fluorinated organic solvents. The differences in the unfolding of the protein in the presence of various organic solvents and the stabilities of O-states were interpreted. At pH 2.0, non-fluorinated alkyl alcohols induced a switch from the native $\alpha$-helix to a $\beta$-sheet, contrary to the $\beta$-sheet to $\alpha$-helix conversion observed for many proteins. The magnitude of ellipticity at 215 nm, used as a measure of $\beta$-content, was found to be dependent on the concentration of the alcohol. Under similar conditions of pH, fluorinated alcohol enhanced the intrinsic a-helicity of the protein molecule, whereas the addition of acetonitrile reduced the helical content. Ervatamin C exhibited high stability towards GuHCl induced unfolding in different O-states. Whereas the thermal unfolding of O-states was non-cooperative, contrary to the cooperativity seen in the absence of the organic solvents under similar conditions. Moreover, the differential scanning calorimetry endotherms of the protein acquired at pH 2.0 were deconvoluted into two distinct peaks, suggesting two cooperative transitions. With increase in pH, the shape of the thermogram changed markedly to exhibit a major and a minor transition. The appearance of two distinct peaks in the DSC together with the non-cooperative thermal transition of the protein in O-states indicates that the molecular structure of ervatamin C consists of two domains with different stabilities.

Study on the micellization of cetyltrimethyl ammonium bromide in 4-biphenyl acetate solution (4-biphenyl acetate 수용액에서 Cetyltrimethyl Ammonium Bromide의 미셀화에 관한 연구)

  • Oh, Jung Hee
    • Analytical Science and Technology
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    • v.8 no.2
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    • pp.107-116
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    • 1995
  • The critical micelle concentration(CMC) of CTAB was determined with changes in absorbance at 202nm band of 4-biphenyl acetate($BPA^-$). With $BPA^-$ as a probe, the effect of temperature on CMC of CTAB has been observed between $30^{\circ}C{\sim}70^{\circ}C$. In this range of temperature the values of CMC are $1.18{\times}10^{-4}{\sim}2.02{\times}10^{-4}M$. The free energy(${\Delta}G^{\circ}m$) and enthalpy(${\Delta}H^{\circ}m$)for the micellization of CTAB was negative and the entropy(${\Delta}S^{\circ}m$) was a large positive value. The micellization of CTAB is considered as a spontaneous process and to involve a phase transition. The orientational binding of 4-biphenyl acetate anion to the CTAB micelle interface has been studied with $300MHz\;H^1-NMR$ data. The change in chemical shift of proton in CTAB as well as those of the protons in $BPA^-$ have been investigated by increasing the mole fraction of the anion in the mixed solutions. The changes in chemical shift with increasing mole fraction of anion($BPA^-$) indicate the formation of mixed micelle between CTAB and $BPA^-$. The changes in chemical shifts of methylene protons in CTAB, demonstrate the penetration of $BPA^-$ into the palisade layer of the CTAB micelle.

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Preparation of Thermo-Responsive and Injectable Hydrogels Based on Hyaluronic Acid and Poly(N-isopropylacrylamide) and Their Drug Release Behaviors

  • Ha Dong In;Lee Sang Bong;Chong Moo Sang;Lee Young Moo;Kim So Yeon;Park Young Hoon
    • Macromolecular Research
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    • v.14 no.1
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    • pp.87-93
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    • 2006
  • Copolymers composed of hyaluronic acid (HA) and poly(N-isopropylacrylamide) (PNIPAAm) were prepared to create temperature-sensitive injectable gels for use in controlled drug delivery applications. Semi-telechelic PNIPAAm, with amino groups at the end of each main chain, was synthesized by radical polymerization using 2-aminoethanethiol hydrochloride (AESH) as the chain transfer agent, and was then grafted onto the carboxyl groups of HA using carbodiimide chemistry. The result of the thermo-optical analysis revealed that the phase transition of the PNIPAAm-grafted HA solution occurred at around 30$\∼$33$^{circ}C$. As the graft yield of PNIPAAm onto the HA backbone increased, the HA-g-PNIPAAm copolymer solution exhibited sharper phase transition. The short chain PNIPAAm-grafted HA ($M_{w}$=6,100) showed a narrower temperature range for optical turbidity changes than the long chain PNIPAAm-grafted HA ($M_{w}$=13,100). PNIPAAm-grafted HA exhibited an increase in viscosity above 35$^{circ}C$, thus allowing the gels to maintain their shape for 24 h after in vivo administration. From the in vitro riboflavin release study, the HA-g-PNIPAAm gel showed a more sustained release behavior when the grafting yield of PNIPAAm onto the HA backbone was increased. In addition, BSA released from the PNIPAAm-g-HA gels showed a maximum concentration in the blood 12 h after being injected into the dorsal surface of a rabbit, followed by a sustained release profile after 60 h.

Development of Lecithin Organogel to Improve Solubility of Genistein (레시틴 오가노겔을 이용한 난용성 제니스테인의 용해도 향상)

  • Lee, Su Jin;Kim, Jung A;Kang, Nae Gyu;Park, Sun Gyoo;Lee, Cheon Koo
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.41 no.3
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    • pp.201-208
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    • 2015
  • Organogels are semi-solid systems that consist of an apolar solvent as the liquid phase within a three-dimensional networked structure. In this study, we developed a stable and skin penetration-enhanced Lecithin Organogel (LO) containing genistein, which is one of the poorly soluble active ingredients in both polar and apolar phase. After screening of various components (type of gelators, organic and aqueous phase), hydrogenated lecithin (HL), sunflower oil (SO), dipropylene glycol (DPG), and polyethylene glycol (PEG) were mainly used in this formulation. Phase ternary diagram was employed for optimization of the composition in the LO. The formulated LO were evaluated for its organoleptic characteristics, stability, pH, rheology, phase transition temperatures, microscopic analysis and skin penetration. The optimized stable LO system can be utilized as an effective and stable cosmetic formulation that can carry poorly soluble active ingredients at high concentration for topical dermal delivery.

Electrochemical Reduction of Thionyl Chloride by Tetradentate Schiff Base Transition Metal(II) Complexes : Catalytic Effects (네자리 Schiff Base 전이금속(II) 착물들에 의한 SOCl$_2$의 전기화학적 환원 : 촉매 효과)

  • Woo-Seong Kim;Yong-Kook Choi;Chan-Young Kim;Ki-Hyung Chjo;Jong-Soon Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.702-710
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    • 1993
  • Electrochemical reduction of thionyl chloride has been carried out at glassy carbon and molybdenum electrodes, the surface of which is modified by binuclear tetradentate schiff base Co(II), Ni(II),Cu(II) and Fe(II) complexes. The catalyst molecules of transition metal(II) complexes were adsorbed on the electrode surface and reduced thionyl chloride resulting in a generation of oxidized catalyst molecules. There was an optimum concentration for each catalyst compound. The catalytic effects of SOCl$_2$ reduction were larger on glassy carbon electrodes compared to molybdenum electrodes and enhancements in reduction current of up to 120${\%}$ at the glassy carbon electrodes. The reduction currents of thionyl chloride were increased and the reduction potentials were shifted to the negative potential when scan rates became faster. The reduction of thionyl chloride was proceed to diffusion controlled reaction.

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Effect of Resveratrol on Oral Cancer Cell Invasion Induced by Lysophosphatidic Acid

  • Kim, Jin Young;Cho, Kyung Hwa;Lee, Hoi Young
    • Journal of dental hygiene science
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    • v.18 no.3
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    • pp.188-193
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    • 2018
  • The aim of the current study was to demonstrate the potential therapeutic efficacy of resveratrol in oral cancer patients. Lysophosphatidic acid (LPA) intensifies cancer cell invasion and metastasis, whereas resveratrol, a natural polyphenolic compound, possesses antitumor activity, suppressing cell proliferation and progression in various cancer cell lines (ovarian, gastric, oral, pancreatic, colon, and prostate cancer cells). In addition, resveratrol has been identified as an inhibitor of LPA-induced proteolytic enzyme expression and ovarian cancer invasion. Furthermore, resveratrol was shown to inhibit oral cancer cell invasion by downregulating hypoxia-inducible factor $1{\alpha}$ and vascular endothelial growth factor expression. Recently, we demonstrated that LPA is important for the expression of transcription factors TWIST and SLUG during epithelial-mesenchymal transition (EMT) in oral squamous carcinoma cells. In this study, we treated serum-starved cultures of oral squamous carcinoma cell line YD-10B with resveratrol for 24 hours prior to stimulation with LPA. To identify an optimal resveratrol concentration that does not induce apoptosis in oral squamous carcinoma cells, we determined the toxicity of resveratrol in YD-10B cells by assessing their viability using the MTT assay. Another assay was performed using Matrigel-coated cell culture inserts to detect oral cancer cell invasion activity. Immunoblotting was applied for analyzing protein expression of SLUG, TWIST1, E-cadherin, and GAPDH. We demonstrated that resveratrol efficiently inhibited LPA-induced oral cancer cell EMT and invasion by downregulating SLUG and TWIST1 expression. Therefore, resveratrol may potentially reduce oral squamous carcinoma cell invasion and metastasis in oral cancer patients, improving their survival outcomes. In summary, we identified new targets for the development of therapies against oral cancer progression and characterized the therapeutic potential of resveratrol for the treatment of oral cancer patients.

Cationic Cure of Epoxy Resin by an Optimum Concentration of N-benzylpyrazinium Hexafluoroantimonate

  • Lee, Jong-Keun;Park, Yusong;Jae-Rock lee;Park, Jaekyeung
    • Macromolecular Research
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    • v.10 no.1
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    • pp.34-39
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    • 2002
  • Cure behavior of an epoxy resin was investigated at different cure temperatures (110, 120, 130, 140, and 150 $^{\circ}C$) and cure times in the presence of 2 wt% of an N-benzylpyrazinium hexafluoroantimonate (BPH) cationic catalyst by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The glass transition temperature ( $T_{g}$) and chemical conversion (x) at the different temperatures were determined from DSC thermograms. The $T_{g}$ and x vs. In time data were superposed up to $T_{g}$ = 10$0^{\circ}C$ and x = 0.70 by shifting horizontally at a reference temperature of $T_{g}$ = 13$0^{\circ}C$. It is interesting that the $T_{g}$ and x of the superposed data increase rather slowly in the early stage of cure and rapidly thereafter. Therefore, the increase of the $T_{g}$ and x can be divided into two regions; $R_{I}$= -18.4(= $T_{go}$ ) ~5$^{\circ}C$ and $R_{II}$ = 5 ~ 10$0^{\circ}C$ in $T_{g}$, and $R_{I}$ : 0~0.24 and $R_{II}$ : 0.24~0.70 in x. The $R_{I}$ is closely related to the initiation reactions between BPH and epoxy and between hydroxy group and epoxy in this epoxy/catalyst system. From the kinetic analysis of the $T_{g}$-shift, activation energy was 12.5 kcal/mol. The relationship between $T_{g}$ and x was also considered. The gelation and vitrification times for different cure temperatures were obtained from DMA curves.urves. DMA curves.urves.

Quenching of Ofloxacin and Flumequine Fluorescence by Divalent Transition Metal Cations

  • Park, Hyoung-Ryun;Oh, Chu-Ha;Lee, Hyeong-Chul;Choi, Jae-Gyu;Jung, Beung-In;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • v.27 no.12
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    • pp.2002-2010
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    • 2006
  • This study examined the quenching of ofloxacin (OFL) and flumequine (FLU) fluorescence by $Cuj^{2+}$, $Ni^{2+}$, $Co^{2+}$ and $Mn^{2+}$ in an aqueous solution. The change in the fluorescence intensity and lifetime was measured at various temperatures as a function of the quencher concentration. According to the Stern-Volmer plots, the fluorescence emission was quenched by both collisions (dynamic quenching) and complex formation (static quenching) with the same quencher but the effect of static quenching was larger than that of dynamic quenching. Large static and dynamic quenching constants for both OFL and FLU support significant ion-dipole and orbital-orbital interactions between fluorophore and quencher. For both molecules, the static and dynamic quenching constants by $Cu^{2+}$ were the largest among all the metal quenchers examined in this study. In addition, both the static and dynamic quenching mechanisms by $Cu^{2+}$ were somewhat different from the quenching caused by other metals. Between $Ni^{2+}$ and FLU, a different form of chemical interaction was observed compared with the interaction by other metals. The change in the absorption spectra as a result of the addition of a quencher provided information on static quenching. With all these metals, the static quenching constant of FLU was larger than those of OFL. The fluorescence of OFL was quite insensitive to both the dynamic and static quenching compared with FLU. This property of OFL can be explained by the twisted intramolecular charge transfer in the excited state.

Molecular Dynamics Simulations on β Amyloid Peptide (25-35) in Aqueous Trifluoroethanol Solution

  • Lee, Sang-Won;Kim, Yang-Mee
    • Bulletin of the Korean Chemical Society
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    • v.25 no.6
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    • pp.838-842
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    • 2004
  • Amyloid peptide (A${\beta}$) is the major component of senile plaques found in the brain of patient of Alzheimer's disease. ${\beta}$-amyloid peptide (25-35) (A${\beta}$25-35) is biologically active fragment of A${\beta}$. The three-dimensional structure of A${\beta}$25-35 in aqueous solution with 50% (vol/vol) TFE determined by NMR spectroscopy previously adopts an ${\alpha}$-helical conformation from $Ala^{30}$ to $Met^{35}$. It has been proposed that A${\beta}$(25-35) exhibits pH- and concentration-dependent ${\alpha}-helix{\leftrightarrow}{\beta}$sheet transition. This conformational transition with concomitant peptide aggregation is a possible mechanism of plaque formation. Here, in order to gain more insight into the mechanism of ${\alpha}$-helix formation of A${\beta}$25-35 peptide by TFE, which particularly stabilizes ${\alpha}$-helical conformation, we studied the secondary-structural elements of A${\beta}$25-35 peptide by molecular dynamics simulations. Secondary structural elements determined from NMR spectroscopy in aqueous TFE solution are preserved during the MD simulation. TFE/water mixed solvent has reduced capacity for forming hydrogen bond to the peptide compared to pure water solvent. TFE allows A${\beta}$25-35 to form bifurcated hydrogen bonds to TFE as well as to residues in peptide itself. MD simulation in this study supports the notion that TFE can act as an ${\alpha}$-helical structure forming solvent.