• Title/Summary/Keyword: Amphiphilic polymer

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Tumoral Accumulation of Long-Circulating, Self-Assembled Nanoparticles and Its Visualization by Gamma Scintigraphy

  • Cho, Yong-Woo;Kim, Yoo-Shin;Kim, In-San;Park, Rang-Woon;Oh, Seung-Jun;Moon, Dae-Hyuk;Kim, Sang-Yoon;Kwon, Ick-Chan
    • Macromolecular Research
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    • v.16 no.1
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    • pp.15-20
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    • 2008
  • The enhanced permeability and retention (EPR) effect is used extensively for the passive targeting of many macromolecular drugs for tumors. Indeed, the EPR concept has been a gold standard in polymeric anticancer drug delivery systems. This study investigated the tumoral distribution of self-assembled nanoparticles based on the EPR effect using fluorescein and radio-labeled nanoparticles. Self-assembled nanoparticles were prepared from amphiphilic chitosan derivatives, and their tissue distribution was examined in tumor-bearing mice. The size of the nanoparticles was controlled to be 330 run, which is a size suited for opening between the defective endothelial cells in tumors. The long-circulating polymer nanoparticles were allowed to gradually accumulate in the tumors for 11 days. The amount of nanoparticles accumulated in the tumors was remarkably augmented from 3.4%ID/g tissue at 1 day to 25.9%ID/g tissue at 11 days after i.v. administration. The self-assembled nanoparticles were sustained at a high level throughout the 14 day experimental period, indicating their long systemic retention in the blood circulation. The ${\gamma}$-images provided clear evidence of selective tumor localization of the $^{131}I$-labeled nanoparticles. Confocal microscopy revealed the fluorescein-labeled nanoparticles to be preferentially localized in the perivascular regions, suggesting their extravasation to the tumors through the hyperpermeable angiogenic tumor vasculature. This highly selective tumoral accumulation of nanoparticles was attributed to the leakiness of the blood vessels in the tumors and their long residence time in the blood circulation.

Use of Amphiphilic Graft Copolymer as Dispersant for Carbon Nanotubes (양친성 그래프트 공중합체의 탄소나노튜브 분산제로의 이용)

  • Jeon, Ha-Rim;Ahn, Sung-Hoon;Chi, Won-Seok;Kim, Jong-Hak
    • Polymer(Korea)
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    • v.35 no.6
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    • pp.615-618
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    • 2011
  • Carbon nanotubes (CNTs) draw attention as promising materials due to their excellent electrical and mechanical properties. However, the intrinsic strong interaction between CNTs presents a challenge to their use in various applications. Here, we present a facile method to disperse single-walled carbon nanotubes (SWCNTs) in a polar solution using a graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), PVC-g-POEM. The graft copolymer was synthesized via atom transfer radical polymerization (ATRP), as confirmed by gel permeation chromatography (GPC) and $^1H$ NMR spectroscopy. The SWCNTs were uniformly dispersed in a polar solvent such as dimethylsiloxane (DMSO) using PVC-g-POEM as a dispersant, due to interaction between CNT and the graft copolymer, as revealed by transmission electron microscopy (TEM) analysis. Upon removal of the solvent, free standing nanocomposite films with good homogeneity were obtained.

Olefin Separation Membranes Based on PEO/PDMS-g-POEM Blends Containing AgBF4/Al(NO3)3 Mixed Salts (AgBF4/Al(NO3)3 혼합염이 포함된 PEO/PDMS-g-POEM 블렌드 기반의 올레핀 분리막)

  • Kim, Sang Jin;Jung, Jung Pyu;Park, Cheol Hun;Kim, Jong Hak
    • Membrane Journal
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    • v.25 no.6
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    • pp.496-502
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    • 2015
  • Facilitated transport is one of the possible solutions to simultaneously improve permeability and selectivity, which is challenging in conventional polymer-based membranes. Olefin/paraffin separation using facilitated transport membrane has received much attention as an alternative solution to the conventional distillation process. Herein, we report olefin separation composite membranes based on the polymer blends containing $AgBF_4/Al(NO_3)_3$ mixed salts. Free radical polymerization process was used to synthesize an amphiphilic graft copolymer of poly(dimethyl siloxane)-graft- poly(ethylene glycol) methyl ether methacrylate (PDMS-g-POEM). In addition, poly(ethylene oxide) (PEO) was introduced to the PDMS-g-POEM graft copolymer to form polymer blends with various ratios. The propylene/propane mixed-gas selectivity and permeance reached up to 5.6 and 10.05 GPU, respectively, when the PEO loading was 70 wt% in polymer blend. The improvement of olefin separation performance was attributed to the olefin facilitating silver ions as well as the highly permeable blend matrix. The stabilization of silver ions in the composite membrane was achieved through the introduction of $Al(NO_3)_3$ which suppressed the reduction of silver ions to silver particles.

Synthesis and characterization of hydrophobic and hydrophilic cellulose derivative by esterification (친수성과 소수성을 동시에 가지는 아세틸화 셀룰로스 에테르의 합성 및 특성 평가)

  • Kim, Taehong;Lee, Sangku;Son, Byunghee;Paik, Hyun-Jjong;Yoon, Sanghyeon;Lee, Heesoo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.23 no.1
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    • pp.31-36
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    • 2013
  • Acetylated Cellulose Ether (ACE), cellulose-based amphiphilic polymer with hydrophilic and hydrophobic, was synthesized and investigated in terms of its solubility and wettability for organic solvents and water. Acetyl group was substituted to the cellulose ether in a hydrophilic polymer by esterification. As a result of FT-IR, the peak corresponding to the hydroxyl group decreased and carboxyl acid peak increased with increasing reaction time and temperature, which signified the increase in the degree of acetylation of the ACE. There were similar thermal decomposition behaviors before and after esterification reaction until $800^{\circ}C$ so that the reaction occurred without significant structural changes of cellulose backbones. The solubility parameter of the ACE had a range of 18.5~26.4, and its viscosity and turbidity were controlled according to the solubility parameter of organic solvents. The ACE showed the hydrophilicity because the contact angle of the ACE was higher than the cellulose ether. These results confirmed that the ACE had the hydrophobicity and hydrophilicity due to the ether which was glucosidic bonding between the glucose units and un-reacted hydroxyl functional groups in the ACE.

Interactions and Ionic Conductivities of Poly(epichlorohydrin) Graft Copolymer Electrolyte Membranes (Poly(epichlorohydrin) 가지형 공중합체 전해질막의 상호작용 및 이온 전도도)

  • Koh, Joo-Hwan;Lee, Kyung-Ju;Park, Jung-Tae;Ahn, Sung-Hoon;Kim, Jong-Hak
    • Membrane Journal
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    • v.20 no.3
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    • pp.203-209
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    • 2010
  • Amphiphilic graft copolymers based on poly(epichlorohydrine) (PECH) were synthesized using atom transfer radical polymerization (ATRP). Successful graft polymerization of poly(methyl methacrylate)(PMMA) and poly(butyl methacrylate) (PBMA) from PECH was confirmed by nuclear magnetic resonance ($^1H$ NMR) and FT-IR spectroscopy. Upon the introduction of KI or LiI to the graft copolymers, the ether stretching bands were shifted to a lower wavenumber due to coordinative interactions. Ionic conductivities of PECH-g-PBMA complexes were always higher than those of PECH-g-PMMA complexes, resulting from higher mobility of rubbery PBMA chains. The maximum ionic conductivity of $2.7{\times}10^{-5}\;S/cm$ was obtained at 10 wt% of KI for PECH-g-PBMA electrolytes.

Preparation of Ag Nanoparticles by Templating Poly(vinyl chloride)-g-poly(styrene sulfonic acid) Graft Copolymer Membrane (Poly(vinyl chloride)-g-poly(styrene sulfonic acid) 가지형 공중합체막을 이용한 은 나노입자 제조)

  • Byun, Su-Jin;Seo, Jin-Ah;Chi, Won-Seok;Shul, Yong-Gun;Kim, Jong-Hak
    • Membrane Journal
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    • v.21 no.1
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    • pp.39-45
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    • 2011
  • An amphiphilic graft copolymer consisting of a poly(vinyl chloride) (PVC) backbone and poly(styrene sulfonic acid) (PSSA) side chains (PVC-g-PSSA) was synthesized via atom transfer radical polymerization (ATRP). This polymer electrolyte membrane was ion-exchanged to Ag ions by immersing in 10 wt% $AgNO_3$ aqueous solution and templated the growth of Ag nanoparticles by a reducing agent. The formation of Ag nanoparticles was confirmed using UV-visible spectroscopy and X-ray diffraction (XRD). Transmission electron microscopy (TEM) revealed that utilization of $NaBH_4$ was the most effective in the formation of Ag nanoparticles with 10~15 nm in size. The formation of Ag nanoparticles was also strongly affected by the concentration of reducing agent and reduction time.

Effects of Molecular Weight of Poly(4-vinylpyridine) on the Order-Disorder Transition of Molecular Bottle-brush Composed of Poly(4-vinylpyridine) and 3-Pentadecylphenol (P4VP과 PDP로 이루어진 Molecular Bottle-brush의 Order-Disorder Transition에 미치는 P4VP 분자량의 영향에 관한 연구)

  • 최종렬;조항규;전현애;노시태
    • Polymer(Korea)
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    • v.24 no.4
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    • pp.488-498
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    • 2000
  • Molecular bottle-brush was prepared by hydrogen-bonding between poly(4-vinylpyridine)(P4VP) as main chain and 3-pentadecylphenol (PDP) as amphiphilic side chain. Variation of long period ( $L_{p}$), order-disorder transition temperature ( $T_{ODT}$) and mesomorphic structure of bottle-brush were investigated by changing various mole ratio (x) of pyridine group in P4VP and PDP and molecular weight of P4VP. Upper critical solution temperature (UCST) behaviour was observed. For x 0.8-0.9, maximum critical temperature was found. As molecular weight of P4VP was increased, phase transition occurred at higher temperature. It was found that phase behaviour of the bottle-brush was affected by mobility of P4VP as well as size and regularity of lamellar structure. The $L_{p}$ determined from analysis of crystal structure was in the range of 35 $\AA$ and 40 $\AA$ and was more affected by the molecular weight of P4VP than by mole ratio (x). However, if the molecular weight of P4VP was high, LP value was little affected.ted.d.

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Synthesis of Organized $TiO_2$ Electrodes Using Graft Copolymer and Their Applications to Dye-Sensitized Solar Cells (가지형 공중합체를 이용한 나노구조 $TiO_2$ 제조 및 염료감응 태양전지 응용)

  • Ahn, Sung Hoon;Koh, Joo Hwan;Park, Jung Tae;Kim, Jong Hak
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.64.1-64.1
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    • 2010
  • The morphology of mesoporous $TiO_2$ films plays an important role in the operation of a DSSC. For example, the energy conversion efficiency of DSSCs with well-organized mesoporous $TiO_2$ films is much higher than those with traditional films possessing a random morphology. In previous research, well-organized mesoporous $TiO_2$ films have mainly been synthesized using an amphiphilic block copolymer, e.g., a poly(ethylene oxide) (PEO)-based template. A graft copolymer is more attractive than a block copolymer due to its low cost and the ease with which it can be synthesized. In this work, we provide the first report on the successful synthesis of well-organized mesoporous $TiO_2$ films templated by an organized graft copolymer as a structure directing agent. Well-organized mesoporous $TiO_2$ films with excellent channel connectivities were developed via the sol gel processusing an organized PVC-g-POEM graft copolymer synthesized by one-pot ATRP. The careful adjustment of copolymer composition and solvent affinity using a THF/$H_2O$/HCl mixture was used to systematically vary the material structure. The influence of the material structure on solar cell performance was then investigated. A solid-state DSSC employing both the graft copolymer templated organized 700 nm-thick $TiO_2$ films and graft copolymer electrolytes exhibited a solar conversion efficiency of 2.2% at 100 $mW/cm^2$. This value was approximately two-fold higher than that attained from a DSSC employing a random mesoporous $TiO_2$ film. The solar cell performance was maximized at 4.6% when the film thickness was increased to $2.5{\mu}m$. We believe that this graft copolymer-directed approach introduces a new and simple route toward the synthesis of well-organized metal oxide films as an alternative to a conventional block copolymer-based template.

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Synthesis of Porous $TiO_2$ Thin Films Using PVC-g-PSSA Graft Copolymer and Their Use in Dye-sensitized Solar Cells (PVC-g-PSSA 가지형 공중합체를 이용한 다공성 $TiO_2$ 박막의 합성 및 염료감응 태양전지 응용)

  • Byun, Su-Jin;Seo, Jin-Ah;Chi, Won-Seok;Shul, Yong-Gun;Kim, Jong-Hak
    • Membrane Journal
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    • v.21 no.2
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    • pp.193-200
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    • 2011
  • An amphiphilic graft copolymer comprising a poly(vinyl chloride) (PVC) backbone and poly (styrene sulfonic acid) (PSSA) side chains (PVC-g-PSSA) was synthesized via atom transfer radical polymerization (ATRP). Mesoporous titanium dioxide $(TiO_2)$ films with crystalline anatase phase were synthesized via a sol-gel process by templating PVC-g-PSSA graft copolymer. Titanium isopropoxide (TTIP), a $TiO_2$ precursor was selectively incorporated into the hydrophilic PSSA domains of the graft copolymer and grew to form mesoporous $TiO_2$ films, as confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The performances of dye-sensitized solar cell (DSSC) were systematically investigated by varying spin coating times and the amounts of P25 nanoparticies. The energy conversion efficiency reached up to 2.7% at 100 mW/$cm^2$ upon using quasi-solid-state polymer electrolyte.