• Title/Summary/Keyword: amphiphilic polymer

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Patterned Surfaces in Self-Organized Block Copolymer Films with Hexagonally Ordered Microporous Structures

  • Hayakawa Teruaki;Kouketsu Takayuki;Kakimoto Masa-alki;Yokoyama Hideaki;Horiuchi Shin
    • Macromolecular Research
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    • v.14 no.1
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    • pp.52-58
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    • 2006
  • A novel fabrication of the patterned surfaces in the polymer films was demonstrated by using the self-organizing character of the block copolymers of polystyrene-b-oligothiophenes and polystyrene-b-aromatic amide dendron. Hexagonally arranged open pores with a micrometer-size were spontaneously formed by casting the polymer solutions under a moist air flow. The amphiphilic character of the block copolymers played the crucial role as a surfactant to stabilize the inverse emulsion of water in the organic solvent, and subsequently the aggregated structure of the hydrophilic oligothiophene or aromatic amide dendron segments remained on the interiors of the micropores. The chemical composition on the top of the surface of the microporous films was characterized by energy-filtering transmission electron microscopy (EFTEM) or a time-of-flight secondary ion mass spectrometer (ToF-SIMS). The characterizations clearly indicated that the patterned surfaces in the self-organized block copolymer films with the hexagonally ordered microporous structures were fabricated in a single step.

Synthesis and pH-Dependent Micellization of a Novel Block Copolymer Containing s- Triazine Linkage

  • Pal Ravindra R.;Lee Doo Sung
    • Macromolecular Research
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    • v.13 no.5
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    • pp.373-384
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    • 2005
  • Novel pH-sensitive moieties containing an s-triazine ring were synthesized with sulfonamide and secondary amino groups. The synthesized pH-sensitive moieties were used for the synthesis of a pH-sensitive amphiphilic ABA triblock copolymer. The pH-sensitive triblock copolymer was composed of diblock copolymers, methoxy poly(ethylene glycol)-poly ($\varepsilon$-caprolactone-co-D,L-lactide) (MPEG-PCLA), and pH-sensitive moiety. These copolymers could be dissolved molecularly in both acidic and basic aqueous media at room temperature due to secondary amino and sulfonamide groups. The synthesized s-triazine rings containing pH-sensitive compounds were characterized by ${^1}H-NMR,\;{^13}C-NMR$, and LC/MSD spectral data. The synthesized diblock and triblock copolymers were also characterized by ${^1}H-NMR$ and GPC analyses. The critical micelle concentrations at various pH conditions were determined by fluorescence technique using pyrene as a probe. Furthermore, the micellization and demicellization study of the triblock copolymer was done with pH-sensitive groups. The sensitivity towards pH change was further established by acid-base titration.

Stability Studies of Biodegradable Polymersomes Prepared by Emulsion Solvent Evaporation Method

  • Lee Yu-Han;Chang Jae-Byum;Kim Hong-Kee;Park Tae-Gwan
    • Macromolecular Research
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    • v.14 no.3
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    • pp.359-364
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    • 2006
  • Di-block copolymers composed of two biocompatible polymers, poly(ethylene glycol) and poly(D,L-lactide), were synthesized by ring-opening polymerization for preparing polymer vesicles (polymersomes). Emulsion solvent evaporation method was used to fabricate the polymersomes. Scanning electron microscope (SEM) images confirmed that polymersomes have a hollow structure inside. Confocal laser microscope and optical microscope were also used to verify the hollow structure of polymersomes. Polymersomes having various sizes from several hundred nanometers to a few micrometers were fabricated. The size of the polymersomes could be readily controlled by altering the relative hydrodynamic volume fraction ratio between hydrophilic and hydrophobic blocks in the copolymer structure, and by varying the fabrication methods. They showed greatly enhanced stability with increased molecular weight of PEG. They maintained their physical and chemical structural integrities after repeated cycles of centrifugation/re-dispersion, and even after treatment with surfactants.

Preparation of Polymeric Self-Assembly and Its Application to Biomaterials

  • Cho, Chong-Su;Park, In-Kyu;Nah, Jae-Woon;Toshihiro Akaike
    • Macromolecular Research
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    • v.11 no.1
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    • pp.2-8
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    • 2003
  • The self-assembly of polymers can lead to supramolecular systems and is related to the their functions of material and life sciences. In this article, self-assembly of Langmuir-Blodgett (LB) films, polymer micelles, and polymeric nanoparticles, and their biomedical applications are described. LB surfaces with a well-ordered and layered structure adhered more cells including platelet, hepatocyte, and fibroblast than the cast surfaces with microphase-separated domains. Extensive morphologic changes were observed in LB surface-adhered cells compared to the cast films. Amphiphilic block copolymers, consisting of poly(${\gamma}$-benzyl L-glutamate) (PBLG) as the hydrophobic part and poly(ethylene oxide) (PEO) [or poly(N-isopropylacrylamide) (PNIPAAm)] as the hydrophilic one, can self-assemble in water to form nanoparticles presumed to be composed of the hydrophilic shell and hydrophobic core. The release characteristics of hydrophobic drugs from these polymeric nanoparticles were dependent on the drug loading contents and chain length of the hydrophobic part of the copolymers. Achiral hydrophobic merocyanine dyes (MDs) were self-assembled in copolymeric nanoparticles, which provided a chiral microenvironment as red-shifted aggregates, and the circular dichroism (CD) of MD was induced in the self-assembled copolymeric nanoparticles.

Self-Organization of Dendron-Poly(ethylene glycol) Conjugates in an Aqueous Phase

  • Kim, Kyoung-Taek;Lee, Im-Hae;Park, Chiyoung;Song, Yu-Mi;Kim, Chul-Hee
    • Macromolecular Research
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    • v.12 no.5
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    • pp.528-533
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    • 2004
  • We have prepared amide dendrons having alkyl peripheral units and various focal moieties through a convergent synthetic approach. The amphiphilic properties, due to hydrophilic amide branches and the hydrophobic peripheral units, provide an opportunity for the amide dendrons to self-organize in water. The dendritic architecture itself is also one of the critical factors in the self-organization of the amide dendrons in water. In particular, function-alization was performed at the focal point to elucidate the relationship between the focal functionality and the self-organized structures of the dendritic building blocks in the aqueous phase. The dendron having a short poly(ethylene glycol) monomethyl ether (MeO-PEG) unit (M$\_$n/ =750) as the focal moiety formed a vesicular organization in water. As the size of the hydrophilic focal MeO-PEG increased to M$\_$n/ =2,000 and 5,000, the self-organized structures became rod-type and spherical micelles, respectively. Our observation of multiple morphologies for amide dendrons is in good agreement with previous reports that indicated that the micellar structures changed from vesicles to rod-types and then to spheres upon increasing the size of the hydrophilic moiety of the amphiphiles.

Enhanced Hydrophilicity of Polyethersulfone Membrane by Various Surface Modification Methods (다양한 표면개질을 이용한 폴리에테르설폰 막의 친수성 향상)

  • Park, So Jung;Hwang, Jun Seok;Choi, Won-Kil;Lee, Hyung Keun;Huh, Kang Moo
    • Polymer(Korea)
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    • v.38 no.2
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    • pp.205-212
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    • 2014
  • Polyethersulfone (PES) membranes were modified by various physico-chemical modification methods to enhance the surface hydrophilicity for application as a separation membrane to separate and collect water vapor from the flue gas. Homogeneous PES flat-sheet membranes were prepared and modified by acid treatment, blending and plasma treatment for hydrophilic surface modification. The surface characteristics of the modified PES membranes were evaluated by ATR-FTIR, XPS, SEM and contact angle measurements. No significant change in hydrophilicity was observed for the PES membranes modified by acid treatment with sulfuric acid or blending with various compositions of poloxamer as an amphiphilic PEO-PPO-PEO tri-block copolymer. On the other hand, Ar plasma treatment led to a significant increase in the hydrophilicity of the surface, depending on the plasma treatment time. As a result, the PES membrane could be the most efficiently surface-treated by applying the plasma treatment for enhancing their surface hydrophilicity.

Hydrogen-Bonding Induced Alternating Thin Films of Dendrimer and Block Copolymer Micelle

  • Park, Chi-Young;Rhue, Mi-Kyo;Im, Min-Ju;Kim, Chul-Hee
    • Macromolecular Research
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    • v.15 no.7
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    • pp.688-692
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    • 2007
  • The hydrogen-bonding induced alternating multilayer thin films of dendrimers and block copolymer micelles were demonstrated. The block copolymer micelles derived from amphiphilic poly(2-ethyl-2-oxazoline)block-$poly({\varepsilon}-carprolactone)$ (PEtOz-PCL) in aqueous phase have a core-shell structure with a mean hydrodynamic diameter of 26 nm. The hydrogen bonding between the PEtOz outer shell of micelle and the carboxyl unit of poly(amidoamine) dendrimer of generation 4.5 (PAMAM-4.5G) at pH 3 was utilized as a driving force for the layerby-layer alternating deposition. The multilayer thin film was fabricated on the poly(methyl methacrylate) (PMMA) thin film spin-coated on silicon wafer or glass substrate by the alternate dipping of PEtOz-PCL micelles and PAMAM dendrimers in aqueous solution at pH 3. The formation of multilayer thin film was characterized by using ellipsometry, UV-vis spectroscopy, and atomic force microscopy. The PEtOz outer shell of PEtOz-PCL micelle provided the pH-responsive hydrogen bonding sites with peripheral carboxylic acids of PAM AM dendrimer. The multilayer thin film was reversibly removed after dipping in aqueous solution at $pH{\geq}5.6$ due to dissociation of the hydrogen bonding between PEtOz shell of PEtOz-PCL micelle and peripheral carboxyl units of PAMAM dendrimer.

Propylene/Nitrogen Separation Membranes Based on Amphiphilic Copolymer Grafted from Poly(1-trimethylsilyl-1-propyne) (양친성 고분자가 그래프팅된 Poly(1-trimethylsilyl-1-propyne) 기반의 프로필렌/질소 분리막)

  • Park, Cheol Hun;Lee, Jae Hun;Park, Min Su;Kim, Jong Hak
    • Membrane Journal
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    • v.29 no.2
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    • pp.88-95
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    • 2019
  • Hydrocarbons containing carbon double bonds are generally called olefins and it is extensively used in petro-chemical industry as essential base material. Especially, olefins are essential in polymer synthesis and thus the effective separation and purification of olefins from gas mixture are very important and it gives significant positive effect on the future industrial development. In this study, we fabricated polymeric composite membrane based on poly(1-trimethylsilyl-1-propyne) (PTMSP) for propylene/nitrogen separation and enhancement of its separation performance by grafting amphiphilic copolymer. Furthermore, to accelerate facilitated transport for propylene molecules, Ag salt ($AgBF_4$) and ionic liquid ($EMIM-BF_4$) was incorporated to polymer composite membranes. The neat PTMSP membrane exhibited extremely high gas permeance and low gas selectivity due to its high free volume. To address this issue, PTMSP was grafted with poly(oxyethylene glycol methacrylate) (POEM) and poly(ethylene glycol) behenyl ether methacrylate (PEGBEM). Additionally, the additives such as $AgBF_4$ and $EMIM-BF_4$ further increased the propylene permeance, resulting in increment of propylene/nitrogen selectivity.

Novel Gene Delivery Carrier Using Chitosan-Lipoic Acid Comb-Type Copolymer (키토산-리포산 빗살형 공중합체를 이용한 유전자 전달체 개발)

  • Kwon, Sang-Kyoo;Kim, Sung-Wan;Kim, Young-Jin
    • Polymer(Korea)
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    • v.34 no.6
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    • pp.501-506
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    • 2010
  • Natural chitosan has high molecular weight and the poor solubility in water. Water-soluble chitosan with low molecular weight was prepared by the hydrolysis method. In order to develop an efficient gene delivery carrier, chitosan was conjugated with lipoic acid to form the comb-type copolymer. The copolymer with the amphiphilic property formed the self-assembled nanoparticles in the aqueous solution. The average size of nanoparticles was 217.6 nm and the average size of nanoparticles/DNA complex was 170 nm. New chitosan-lipoic acid copolymer showed the low cytotoxicity and 10 times higher transfection efficiency than that of the pure chitosan.

Nonionic Amphiphilic Surfactant Conjuncted Polyethyleneimine as a New and Highly Efficient Non-viral Gene Carrier

  • Yin, Dongfeng;Chu, Cang;Ding, Xueying;Gao, Jing;Zou, Hao;Gao, Shen
    • Macromolecular Research
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    • v.17 no.1
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    • pp.19-25
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    • 2009
  • In order to enhance the gene delivery efficiency and decrease the cytotoxicity of polyplexes, we synthesized Solutol-g-PEI by conjugating polyethyleneimine (PEI) to Solutol (polyoxyethylene (10) stearate), and evaluated its efficiency as a possible nonviral gene carrier candidate. Structural analysis of synthesized polymer was performed by using $^1H$-NMR. Gel retardation assay, particle sizes and zeta potential measurement confirmed that the new gene carrier formed a compact complex with plasmid DNA. The complexes were smaller than 150 nm, which implicated its potential for intracellular delivery. It showed lower cytotoxicity in three different cell lines (Hela, MCF-7, and HepG2) than PEI 25 kDa. pGL3-lus was used as a reporter gene, and the transfection efficiency was in vitro measured in Hela cells. Solutol-g-PEI showed much higher transfection efficiency than unmodified PEI 25 kDa.