• Title/Summary/Keyword: diols

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Synthesis and Characterization of Biodegradable Elastic Hydrogels Based on Poly(ethylene glycol) and Poly(${\varepsilon}-caprolactone$) Blocks

  • Im, Su-Jin;Choi, You-Mee;Subramanyam, Elango;Huh, Kang-Moo;Park, Ki-Nam
    • Macromolecular Research
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    • v.15 no.4
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    • pp.363-369
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    • 2007
  • Novel biodegradable elastic hydrogels, based on hydrophilic and hydrophobic polymer blocks, were synthesized via the radical crosslinking reaction of diacrylates of poly(ethylene glycol) (PEG) and poly(${\varepsilon}-caprolactone$) (PCL). PEG and PCL diols were diacrylated with acryloyl chloride in the presence of triethylamine, with the reaction confirmed by FT-IR and $^1H-NMR$ measurements. The diacrylate polymers were used as building-blocks for the syntheses of a series of hydro gels, with different block compositions, by simply varying the feed ratios and molecular weights of the block components. The swelling ratio of the hydrogels was controlled by the balance between the hydrophilic and hydrophobic polymer blocks. Usually, the swelling ratio increases with increasing PEG content and decreasing block length within the network structure. The hydrogels exhibited negative thermo-sensitive swelling behavior due to the coexistence of hydrophilic and hydrophobic polymer components in their network structure, and such thermo-responsive swelling/deswelling behavior could be repeated using a temperature cycle, without any significant change in the swelling ratio. In vitro degradation tests showed that degradation occurred over a 3 to 8 month period. Due to their biodegradability, biocompatibility, elasticity and functionality, these hydrogels could be utilized in various biomedical applications, such as tissue engineering and drug delivery systems.

Benzo(a)pyrene-Triglyceride Adduct: a Potential Molecular Biomarker for Carcinogen Exposure

  • Lee, Byung-Mu
    • Proceedings of the Korean Society of Toxicology Conference
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    • 2002.05b
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    • pp.20-45
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    • 2002
  • In this study, we demonstrated the in vitro and in vivo formation of carcinogen-lipid adduct and its correlation with DNA or protein adducts. The lipids from serum or hepatocyte membranes of Spragu-Dawley rats. human serum, and standard major lipids were in vitro reacted with benzo[a]pyrene(BP) and BP metabolites. 7,8-Dihydroxy-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]-pyrene(BPDE-I), an ultimate carcinogenic form of BP, was covalently bound to triglyceride(TG). BPDE-I-TG adducts isolated by thin-layer chromatography (TLC) were further detected by high performance liquid chromatography(HPLC). TGs, including triolein, tripalmitin and tristearin, showed positive reactions with BPDE-I. However, cholesterol, phospholipids(Phosphatidylcholine, phosphatidyl-ethanolamine, phosphatidyl-inositol and sphingomyelin) and nonesterified fatty acids(palmitic acid, oleic acid, linoleic acid and stearic acid) did not react with BPDE-I. In addition, other BP metabolites (BP-phenols and -diols) did not react with TG, which TG appeared to be the most reactive lipid yet studied with respect to its ability to form an adduct with BPDE-I. There was a clear-cut dose-respect to its ability to form an adduct with BPDE-I-lipid adduct in vitro between TG and [1,3-3H]BPDE-I. In an animal study, BPDE-I-TG was also formed in the serum of rats orally treated with BP(25 mg/rat). Also, obvious correlations between [3H]BP related-biomolecule adducts (DNA, protein) or lipid damage and the BPDE-I-TG adduct were obtained in various tissues of mice i.p. treated with [3H]BP. These data suggest that TG can form an adduct with BPDE-I, as do other macromolecules (DNA, RNA, and protein). Therefore, a carcinogen-lipid adduct would be a useful biomarker for chemical carcinogenesis research and cancer risk assessment.

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Synthesis and Characterization of Waterborne Polyurethanes Based on Isophorone Diisocyanate and Mixed Polyols of Poly(tetramethylene glycol)/Polydimethylsiloxane Diol (이소포론 디이소시아네이트와 폴리(테트라메틸렌 글리콜)/폴리디메틸실록산 디올 혼합 폴리올을 사용한 수분산성 폴리우레탄의 합성과 특성 분석)

  • Lee, Ji Hye;Hong, Seongdon;Kim, Young Ho
    • Polymer(Korea)
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    • v.37 no.2
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    • pp.167-176
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    • 2013
  • Linear and cross-linked waterborne polyurethanes (WPUs) based on isophorone diisocyanate and mixed diols of poly(tetramethylene glycol)/hydroxyethyl-terminated polydimethylsiloxane (PDMS-OH) were synthesized with dimethylol propionic acid as an anionic component, trimethylolpropane as a cross-linking agent, and butanediol as a chain extender and characterized. The hydrophobicity, $T_g$, stress-strain behaviors of the linear or cross-linked siloxane-containing WPU (WPU-Si) films with different PDMS content were analyzed by using water contact shape analyzer, energy dispersive spectrometer, dynamic mechanical analyzer, and universal testing machine. The results reveal that as the PDMS content increased, the hydrophobicity of WPU-Si films increased, $T_g$ moved to higher temperature, the breaking stress increased, and the breaking strain decreased.

Synthesis of Novel Network Polyesters Containing Malonate Group in Main Chain and Their Fluorescence Image Patterning via Photodegradation (주사슬에 말로네이트기를 가지는 신규 폴리에스테르의 합성과 광분해 특성을 이용한 형광 이미지 패터닝)

  • Jeong, Seon-Ju;Kwak, Gi-Seop;Jung, In-Tae;Lee, Dong-Ho;Roh, Hyung-Jin;Yoon, Keun-Byoung
    • Polymer(Korea)
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    • v.32 no.1
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    • pp.56-62
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    • 2008
  • Three types of network polyesters have been newly synthesized by a two-step condensation reaction by the various combination of several diols and diacids. When these polymer films were thermally treated at $240^{\circ}C$, they exhibited absorptions in a visible range despite the forbidden transition of carbonyl group. When excited at wavelengths above 330 nm, the polymers showed fluorescences in a wide visible range from blue to near yellow. These fluorescence phenomena are due to the formation of certain conjugated structures by the Knoevenagel type self-condensation under the high-temperature thermal treatment. These polymers showed significant difference in the thermal properties as a function of the degrees of chemical crosslinking. They also underwent photodegradation. Highly resolved, fluorescent image patterns were successfully obtained by the photodegradation of malonate group under a strong UV-light irradiation.

Synthesis of Polyurethanes Containing Poly(dimethyl siloxane) and Their Thermal and Shape Memory Properties (폴리디메틸실록산 성분을 포함하는 폴리우레탄의 합성과 이들의 열적 및 형상기억 특성)

  • Ra, Sang Hee;Kim, Young Ho
    • Polymer(Korea)
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    • v.38 no.5
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    • pp.602-612
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    • 2014
  • Polyurethanes containing poly(dimethyl siloxane) (PDMS) unit, PU-Si, were synthesized and their thermal and shape memory properties were investigated. Various amounts of PDMS units were incorporated via a solution polymerization method using mixed diols of poly(tetramethylene ether glycol) (PTMEG) and PDMS-diol as the soft segment (SS) and methylene diphenyl diisocyanate and 1,4-butanediol as the hard segment (HS). Two series of PU-Si samples with an HS content of 23% or 32% were prepared and analyzed. For PU-Si with an HS content of 23%, both the cold crystallization temperature ($T_{cc}$) and melt crystallization temperature of the SS domain moved higher temperature with increasing PDMS content, while the melting temperature ($T_m$) of the SS domain remained unaffected. The increase in HS content from 23% to 32% resulted in the increased $T_m$ and disappearance of $T_{cc}$. The shape recovery of PU-Si flim with an HS content of 32% increased while its shape retention decreased as PDMS content increased.

Effect of Condensed Tannins Prepared from Banana (Musa Sapientum L.) fruit on Digestive Enzyme In vitro (바나나 과실 함유탄닌이 소화효소 작용에 미치는 영향)

  • Chung, Chung-Han;Ryu, Chung-Ho;Cho, Young-Su
    • Applied Biological Chemistry
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    • v.39 no.6
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    • pp.477-481
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    • 1996
  • It has been shown that tannins have adverse effects on growth of animals and feed utilization. Tannins are usually classified into hydrolyzable and condensed types but the adverse effects are more marked in condensed tannin in hydrolyzable tannin. Furthermore, the principle condensed tannins found in banana fruits are pro types by the polymerization of flavan-3, 4-diols either alone or in combination with other flavonoids such as catechins. Tannin of the investigated banana(Banana; Musa sapientum LINN)fruits was fractionated into four or five molecular forms, according to the degree of polymerization by chromatography on a column of Sephadex LH-20. The protein-precitating capacity of the fraction noted tannins increased in degree polymerzation. The inhibitory effect of tannins on trypsin(EC 3. 4. 21. 4), ${\alpha}-amylase$(EC 3. 2. 1. 1) and lipase(EC 3. 1. 1. 3) activities in vitro also increased with the incraesed in degree of polymerization.

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Reaction of Lithium Tris(diethylamino)aluminum Hydride in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

  • Jin Soon Cha;Jae Cheol Lee
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.469-475
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    • 1993
  • The approximate rates and stoichiometry of the reaction of excess lithium tris(diethylamino)aluminum hydride (LTDEA) with selected organic compounds containing representative functional groups under standardized condition (tetrahydrofuran, 0$^{\circ}C$) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of LTDEA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(dibutylamino)aluminum hydride (LTDBA). In general, the reactivity toward organic functionalities is in order of LAH${\gg}$LTDEA${\geq}$LTDBA. LTDEA shows a unique reducing characteristics. Thus, benzyl alcohol and phenol evolve hydrogen slowly. The rate of hydrogen evolution of primary, secondary, and tertiary alcohols is distinctive: 1-hexanol evolves hydrogen completely in 6 h, whereas 3-hexanol evolves hydrogen very slowly. However, 3-ethyl-3-pentanol does not evolve any hydrogen under these reaction conditions. Primary amine, such as n-hexylamine, evolves only 1 equivalent of hydrogen. On the other hand, thiols examined are absolutely inert to this reagent. LTDEA reduces aldehydes, ketones, esters, acid chlorides, and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly, where as tertiary amides are readily reduced. Finally, sulfides and sulfoxides are reduced to thiols and sulfides, respectively, without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent to convert esters, primary carboxamides, and aromatic nitriles into the corresponding aldehydes. Free carboxylic acids are also converted into aldehydes through treatment of acyloxy-9-BBN with this reagent in excellent yields.

Mesoporous Silica-Carbon Composite Membranes for Simultaneous Hydrolysis and Separation of Chiral Epoxide (카본/메조세공 실리카 복합 막을 응용한 키랄 에폭사이드의 가수분해반응과 동시 분리)

  • Choi, Seong Dae;Jeon, Sang Kwon;Park, Geun Woo;Yang, Jin Young;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.25 no.5
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    • pp.503-509
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    • 2014
  • The carbon/porous silica composite membrane was fabricated in a simple manner, which could be successfully for the simultaneous separation and production of chiral epoxides and 1,2-diols, based on their differences in hydrophilic/hydrophobic natures. The chiral Co(III)-$BF_3$ salen catalyst adopted in the membrane reactor system has given the very high enantioselectivity and recyclability in hydrolysis of terminal epoxides such as ECH, 1,2-EB, and SO. The optically pure epoxide and the chiral catalyst were collected in the organic phase after hydrolysis reaction. The hydrophilic water-soluble 1,2-diol product hydrolyzed by chiral salen diffused into the aqueous phase through the SBA-16 or NaY/SBA-16 silica composite layer during the reaction. The water acted simultaneously as a reactant and a solvent in the membrane system. One optical isomer was obtained with high purity and yield, and furthermore the catalysts could be recycled without observable loss in their activity in the continuous flow-type membrane reactor.

Synthesis of Long-Chain Unsaturated Acetates (장직쇄상(長直鎖狀) 불포화(不飽和) 초산화합물(醋酸化合物)의 합성(合成)에 관(關)한 연구(硏究))

  • Oh, Sung-Ki
    • Applied Biological Chemistry
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    • v.19 no.1
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    • pp.1-23
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    • 1976
  • The female moths of Lepidoptera comprising over 1,000,000 described species possess long-chain unsaturated alcohols or esters as the typical structure of potential sex attractants. In this experiment, various stereoisomers of $C_{16}-unsaturated$ acetates were synthesized for potential sex attractants; e.g., $CH_3(CH_2)_mCH=CH(CH_2)_nOR$ (m=0-12, n=1-13, R=H and $-COCH_3$). Seventeen acetates were spectrometrically examined so that the data would provide a ready catalog of gas chromatography and mass spectrometric data for comparison with natural insect sex attractants. Exclusively cis and trans isomers were obtained by the catalytic and chemical reduction methods, respectively. Commercially available $CH_3(CH_2)_mBr,\;CH_3(CH_2)_mC{\equiv}CH,\;HC{\equiv}C(CH_2)_nOH\;and\;HO(CH_2)_n\;OH$ were used for the synthetic starting material. 1-Alkynes, $CH_3(CH_2)_m\;C{\equiv}CH$ exceeding nine methylene groups did not condense with alkyl dihalides. The yield of coupling products was gradually decreased with increasing the molecular weight of diols. In the coupling reaction of $BrCH_2CH_2$ OTHP with acetylene gas, the tetrahydropyranyl ether of bromohydrin produced undesirable elimination product. In this experiment, it seems that p-toluenesulfonic acid is greatly favoured hydrolyzing agent over dilute sulfuric acid in the hydrolysis of the tetrahydropyranyl ether of long-chain alkynols.

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Low Formaldehyde Release D.P. Finish on Cotton Fabrics (면직물의 저$\cdot$Formaldehyde D.P. 가공)

  • Kim Sung Reon;Ryu Hyo Seon;Noh Hyung Eun
    • Journal of the Korean Society of Clothing and Textiles
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    • v.10 no.3
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    • pp.71-81
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    • 1986
  • In order to control the formaldehyde release from D.P. finished fabric, cotton fabric was padded in DMDHEU resin bath containing either $Zn(NO_3)_2$ or $MgCl_2$ catalyst and a form-aldehyde scavenger like Glycerol, Sorbitol, Formamide, Polyvinyl alcohol (PVA, n= 2000) or diols, then dried and cured. The results are as follows : 1. When Lewis acid catalyst like $Zn(NO_3)_2$ or $MgCl_2$ was added in pad bath, the fabric finished with $Zn(NO_3)_2$ catalyst released the lower formaldehyde than with $MgCl_2$. 2. When the effect of pad bath pH was examined with varying the kinds of catalyst and the scavenger, it was found that the pad bath pH influenced on the amount of formaldehyde release and the optimum pad bath pH is at 4.3. Especially, in case of finishing at pad bath pH 4.3 with adding Formamide, the amount of formaldehyde release was decreased by about $45\~$35\%$ with $Zn(NO_3)_2$, while by about $20\~$45\%$ with $MgCl_2$ catalyst. In case of varying the concentration of a scavenger (Formamide), $1\%$ concentration of a scavenger was found to be the optimum level ana the higher the curing temperature up to $180^{\circ}C$, the lesser the amount of formaldehyde release were observed. 3. When the diol was used as scavenger, the amount of formaldehyde release was decreased by about $40\~$50\%$, but the longer the intramolecular length between OH groups, the lessor the amount of decrease of formaldehyde release were observed. 4. When the mixture of scavengers (Formamide and Glycerol) was added in the pad bath, .synergistic effect on formaldehyde release between the two scavengers wasn't observed. 5. The tensile strength of the resin finished fabric was reduced with increasing the pad lath pH and was influenced by the kind of scavengers, and the tensile strength was severely reduced when scavengers, especially Formamide, was added. The wrinkle recovery property is generally improved by resin finish on cotton fabric. When Formamide was added, the wrinkle recovery property is slightly decreased compared with that of the fabrics resin finished without a scavenger, and when polyol was added, the wrinkle recovery property showed almost no change.

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