• Title/Summary/Keyword: Polymeric chain

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New Tridentate Ligands with Mixed Donor Atoms for Cu-Based Atom Transfer Radical Polymerization

  • Cho, Hong-Youl;Han, Byung-Hui;Kim, Il;Paik, Hyun-Jong
    • Macromolecular Research
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    • v.14 no.5
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    • pp.539-544
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    • 2006
  • 2-Furancarboxaldehyde-2-pyridinylhydrazone (FPH) and 5-methyl-2-furancarboxaldehyde-2-pyridinylhydrazone (MFPH) were synthesized and used as tridentate ligands of copper (I) bromide for the atom transfer radical polymerization of methyl methacrylate (MMA) and styrene. The polymerization of methyl methacrylate achieved high conversion and yielded polymers with a good control of molecular weight and low polydispersity (PDI=1.33). Higher PDI were observed in the polymerization of styrene. Using 1-phenyl ethylbromide (PEBr) and ethyl 2-bromoisobutyrate (EBiB) as model compounds for the polymeric chain ends, the activation rate constants of the new catalytic systems were measured. These results were correlated with the polymerization results and compared with another catalytic system previously reported.

Gas Permeable Membranes Composed of Carboxylated Poly(vinyl chloride) and Polyurethane

  • 임전원;김채균;김완영;정용섭;이윤식
    • Bulletin of the Korean Chemical Society
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    • v.20 no.6
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    • pp.672-676
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    • 1999
  • Gas-Permeable polymeric membranes containing carboxyl groups which are suitable for enzyme immobilization were investigated in order to use them as gas electrode membranes in biosensors. Carboxylated polyurethane (CPU) was synthesized via a reaciton between 2,2-bis(hydroxymethyl)propionic acid as a chain extender and prepolymers prepared from polycarprolactone(Mn=2,000) and 4,4'-diphenylmethane diisocynate. It was difficult to prepared membranes from the pure CPU because of its high elasticity and cohesion. However, transparent free-standing membranes were easily prepared from the blend solution of CPU and carboxylated poly(vinyl chloride)(CPVC) in tetrahydrofuran. Both elasticity and cohesion of the CPU/CPVC membranes were decreased with increasing the content of CPVC. DSC experiment suggests that CPU and CPVC may be well mixed. Permeability coefficients for O₂and CO₂(Po₂and Pco₂)in the membranes increased as the proportion of CPU increased. The addition of dioxtyl phthalate(DOP), a plasticizer, significantly enhanced the Po₂and Pco₂which were 4,4 and 30 barrer, respectively, in the CPU/CPVC(80/20 wt/wt) membranes containing 20% of DOP at 25℃ and 100psi. Thus this type of membranes may have a potential for the use as gas electrode membranes in biosensors.

Modification of Rubbers through Chemical Reactions including Controlled/"living" Radical Polymerization Techniques (리빙라디칼 중합법을 포함한 화학적 방법에 의한 고무의 개질)

  • Joo, Sang-Il;Cho, Hyun-Chul;Lee, Seong-Hoon;Hong, Sung-Chul
    • Elastomers and Composites
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    • v.44 no.2
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    • pp.122-133
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    • 2009
  • Rubbers, such as natural rubber, polybutadiene, styrene-butadiene rubber, nitrile-butadiene rubber, chlorinated rubber and EPDM, have been continuously improved in response to a heavy demand and a new property requirement from industry. One of the best ways to realize the improvement is the modification of rubbers through chemical reactions, which produce materials with novel properties. In this review, chemical modification reactions of rubbers that contain carbon-carbon double bond units either in their main backbone or as a side group were briefly summarized. The chemical reactions introduce functional groups or functional polymer chains to polymer backbone, which transform a classical rubber to a highly functional material. Especially, we focused on a controlled/"living" radical polymerization techniques, with which a revolutionary broadening of the spectrum of the materials with well defined molecular weight, molecular weight distribution, chain end-functionality and architectures become possible.

A Study on Texture of Jeung-pyun According the Kinds of Rice (쌀 품종에 따른 증편의 조직특성에 관한 연구)

  • 김효진;이숙미;조정순
    • Korean journal of food and cookery science
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    • v.13 no.1
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    • pp.7-15
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    • 1997
  • The composition and polymeric structure of starch are the most important factors to determine the functional properties of rice. In an effort to relate the structural characteristics and its functional properties of starch in rice, molecular structural properties of starch from 6 rice cultivars were analysed. To relate the structure and function of starch the texture of Jeung-pyun made of rice were analyzed during retrogradation. The polymeric structure of rice starch was analyzed by debranching with isoamylase after gelatinization and fractionated with Sephadex G-75 gel filteration. The size fractionated debranched starch was categorized into four groups such as Fraction I, II, III and Intermediate Fraction depending in their max, The fractions with the max higher than 620 nm were designated as Fraction I, while those in the range of 600-620 nm and 540-600 nm as the Intermediate Fraction and Fraction II, respectively. The Fractions with the max lower than 540 were described as Fraction III. The average degree of polymerization (DP) of the Fraction I was estimated to be higher than 200, and those of other fractions, i.e. the Intermediate Fraction I, Fraction II and III were 150,45 and 25, respectively. The levels of Fraction I were varied from II to 35% of total sugar. The Fraction I showed the linear relationship with the amylse contents, and the Intermediate Fraction, which might contain the mixture of short chain of amylose and debranched long chain of amylopectin, were measured to be in the range of 2.7∼8.4%. The levels of fraction II and III, both to be considered as the branches of amylopectin, were ranged 14.5∼23.6% and 39.7∼73.0%, respectively. The ratio of Fraction III to Fraction II describing the degree of branch or compactness of amylopectin was estimated to be around 4.0 for waxy varieties and around 2.0 for high amylose cultivars. With these results, it can be suggested that the degree of branch of the amylopectin may effect on amylose contents of starch or rice versa, To invertigate processing aptitude of different rice cultivars for the preparation of Jeung-pyun, its texture was analyzed by Instron, hardness, cohesiveness, elasticity, gumminess and chewiness of Jeung-pyun made of rice showed the significant relationship with the amylose content. Hardness was increased during retrogradation of product, but the relationship between hardness and amylose content due to not only difference in amylose content but also difference in structural characteristics of starch. In analysis of relationship between structure of rice starch and mechanical properties of Jeung-pyun during retrogradation elasticity did not show any relationship before retrogradation bur during retrogradation showed significant correlation. With these result, it can be suggested that the degree of branch of the amylopectin may effect on elasticity during retrogradation. However hardness, cohesiveness, gumminess and chewiness which were significant different before retrogradation, showed some correlation with structure of rice starch during retrigradation.

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Physiochemical Properties of Binary Pluronic Systems for Reversal of Multi-drug Resistant (MDR) Cancers

  • Yun, Jung-Min;Park, Ga-Young;Kim, Ha-Hyung;Lee, Jae-Hwi;Lee, Eun-Seong;Youn, Yu-Seok;Lee, Beom-Jin;Oh, Young-Taik;Oh, Kyung-Taek
    • Journal of Pharmaceutical Investigation
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    • v.40 no.4
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    • pp.255-261
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    • 2010
  • Pluronic as pharmaceutical excipients are listed in the US and British Pharmacopoeia. In particular, Pluronics exist as different compositions and display abundant phases as self-assembling into polymeric micelles with various morphologies depending on the aqueous solvent quality, the composition of structure, and hydrophilic-lipophilic balance (HLB). Pluronics were also known as a P-gp modulator, which was exploited as a reversal molecule of multi-drug resistant (MDR) cancers. We selected a lamella forming Pluronic L92 which has high hydrophobicity and relatively long PEO block among L series of Pluronics. The dispersion of L92 showed great size particles and low stability. To increase the stability and to decrease the particle size, secondary Pluronics (F68, F88, F98, F127, P85, P105, and P123) with relatively long PEO chain were added into 0.1 wt% Pluronic L92 dispersion. The stability of binary systems was increased due to incorporated long PEO chain. Their particle sizes slightly decreased to over 200~400 nm and their solubilization capacity of binary systems didn't change except Pluronic L92/P123 mixtures. The L92/P123 systems showed ca. 100 nm sizes and lowest turbidity among the all systems. The solubilization capacity of 0.1 wt% L92/0.1 wt% P123 was slightly increased compared to 0.1 wt% L92 mono system and other binary systems. These nano-sized binary systems may have potential as alternative drug delivery systems with simple preparation method and overcome the drawbacks of mono systems such as low stability and loading capacity.

Studies on the Polymeric Surface Active Agent(V) -The Synthesis of Anionic Oligomer Surfactant with α-Sulfo Alkanoic Acid- (고분자 계면활성제에 관한 연구(제5보) -알파 술폰 지방산 음이온성 올리고머 계면활성제의 합성-)

  • Jeong, N.H.;Park, S.S.;Jeong, H.K.;Cho, K.H.;Nam, K.D.
    • Applied Chemistry for Engineering
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    • v.4 no.2
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    • pp.381-392
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    • 1993
  • Anionic oligomer surfactants, dodecyl polyoxyethylene ${\alpha}-sulfa$ alkanoates, had been synthesized through the esterification of dodecyl polyoxyethylene glycol and ${\alpha}-sulfa$ alkanoic acid with straight chain alkyl group having from 10 to 18 carbon atoms to good yield. ${\alpha}-sulfa$ alkanoic acids were obtained by reaction with long chain alkanoic acids and sulfur trioxide-dioxane complex, and dodecyl polyoxyethylene glycols, by addition reaction with dodecyl alcohol and ethylene oxide(addition, 5, 10, 20mol) respectively. All the synthetic products could be separated by means of the thin layer and column chromatography, and their structure has characterized with IR, $^1HNMR$ and elemental analysis, respectively.

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Effect of Cosurfactant on Solubilization of Hydrocarbon Oils by Pluronic L64 Nonionic Surfactant Solution (보조계면활성제가 Pluronic L64 비이온 계면활성제에 의한 탄화수소 오일 가용화에 미치는 영향)

  • Bae, MinJung;Kim, DoWon;Cho, Seo-Yeon;Lim, JongChoo
    • Korean Chemical Engineering Research
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    • v.52 no.2
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    • pp.219-225
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    • 2014
  • In this study, effect of cosurfactant on the solubilization rate of n-octane, n-decane and n-dodecane oil was performed by micellar solutions of polymeric nonionic surfactant Pluronic L64($EO_{13}PO_{30}EO_{13}$) at room temperature. It has been found that the solubilization rate of a hydrocarbon oil was enhanced with an increase in both chain length and amount of alcohol added. In case of addition of a short chain alcohol such as 1-butanol, the solubilization rate of a hydrocarbon oil was slightly increased since most of alcohol molecules remained in an aqueous surfactant solution. On the other hand, the addition of a relatively long chain alcohol such as 1-hexanol and 1-octanol produced a big increase in solubilization rate of a hydrocarbon oil mainly due to incorporation of alcohol molecules into micelles and thus producing more flexible micellar packing density. Dynamic interfacial tension measurements showed the same trend found in solubilization rate measurement. Both interfacial tension value at equilibrium and time required to reach equilibrium decreased with an increase in chain length of an alcohol.

Preparation and Characterization of Water-Dispersible Silver Nanoparticles Stabilized by PEO-Conjugated Pro-Drugs

  • Kim, Tae-Hwan;Kim, Keun-Suk;Park, Geon-Hee;Choi, Jin-Hee;Lee, Sang-Mi;Kang, Ho-Jung;Lee, Jae-Yeol;Kim, Jung-Ahn
    • Macromolecular Research
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    • v.17 no.10
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    • pp.770-775
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    • 2009
  • $\omega$-Anhydride-functionalized poly(ethylene oxide) (PEO) obtained from chain-end functionalization and anionic ring-opening polymerization of ethylene oxide using n-butyllithium with potassium t-butoxide in the presence of dimethylsulfoxide (DMSO) was found to be an efficient material for the preparation of water-soluble, polymeric pro-drugs. The reaction of $\omega$-anhydride-functionalized PEO with sulfonamide or with vancomycin provided an efficient method to produce corresponding, water-soluble, PEO-conjugated sulfonamide or PEO-conjugated, vancomycin pro-drugs. These were used successfully to prepare water-dispersible, silver nanoparticles. In this study, the particle sizes were in the range of $5{\sim}40$ nm. The resulting products were characterized by $^1H$ NMR spectroscopy, transmission electron microscopy, electron and X-ray diffraction, size exclusion chromatography, and UV/Visible spectroscopy.

Second-order Nonlinear Optical Properties of Amorphous Molecules Based on 5-(4-Diethylamino-benzylidene)-1,3-dimethyl-pyrimidine-2,4,6-trione

  • Lee, Seung-Mook;Rhee, Bum-Ku;Lee, Sang-Ho;Lee, Chul-Joo;Park, Ki-Hong
    • Journal of Photoscience
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    • v.10 no.2
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    • pp.203-208
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    • 2003
  • Two coupled molecules were successfully synthesized by condensation of amine-donor-substituted barbituric acid derivativies as nonlinear optical chromophores. A flexible spacer of the alkyl chain with different lengths of carbon chains (5 and 6 carbons) was introduced between two chromophores, which prevented crystallization and aggregation of molecules. Two coupled molecules (B-Cn-B, n=5, 6) had glass-transition temperatures on a second heating around 81 and 76$^{\circ}C$ without melting points, respectively. To explore the linear optical properties, thin-films were prepared and examined by a photometry method using Nd:YVO$_4$ CW laser. Also, microscopic and macroscopic nonlinear optical properties were measured by Hyper-Rayleigh Scattering (HRS) and the Maker Fringes method using Nd:YAG ps pulse laser, respectively. In spite of the moderate hyperpolarizabilities of coupled molecules, the second order NLO coefficient (d$\_$33/) was larger than the conventional Disperse Red 1 doped PMMA polymeric system.

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Synthesis of Polyrotaxane-biotion Conjugates and Surface Plasmon Resonance Analysis of Streptavidin Recognition

  • Ooya, Tooru;Kawashima, Tomokatsu;Yui, Nobuhiko
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.6 no.4
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    • pp.293-300
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    • 2001
  • A polyrotaxane-biotin conjugate was synthesized and its interaction with streptavidin measured using surface plasmon resonance(SPR) detection. A biodegradable polyrotaxane in which ca, 22 molecules of ${\alpha}$-cyclodextrina(${\alpha}$-CDs) were threaded onto a poly(ethylene oxide) chain(M$\sub$n:4,000) capped with benzyloxycarbonyl-L-phenylalanine was conjugated with a biotin hydorazide and 2-aminoethanol after activing the hydroxyl groups of ${\alpha}$-CDs in the polyrotaxane using N, N'-carbonyldiimidazole. The results of the high-resolution $^1$H-nyclear lmagnetic resonance($^1$H-NMR)spectra and gel permeation chromatography of the conjugate showed that ca, 11 biotin molecules were actually introduced to the polyrotaxane scaffold. An SPR analysis showed that the binding curves of the biotin molecules in the conjugate on the streptavidin-deposited surface changed in a concentration dependent manner, indicating that the biotin in the conjugate was ac-tually recognized by streptavidin. The association equilibrium constant(K$\sub$a/) of the interaction be-tween the conjugate and steptavidin tetramer was of the order 10$\^$7/. These results suggest that polyrotaxane is useful for scaffolds as a polymeric ligand in biomedical fields.

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