• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.558-564
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• 2013

A simple and effective method is introduced to synthesize a series of polystyrene-b-poly(oligo(ethylene oxide) monomethyl ether methacrylate)-b-polystyrene (PSt-b-POEOMA-b-PSt) triblock copolymers. The structures of PSt-b-POEOMA-b-PSt copolymers were characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance ($^1H$ NMR) spectroscopy. The molecular weight and molecular weight distribution of the copolymer were measured by gel permeation chromatography (GPC). Furthermore, the self-assembling and drug-loaded behaviours of three different ratios of PSt-b-POEOMA-b-PSt were studied. These copolymers could readily self-assemble into micelles in aqueous solution. The vitamin E-loaded copolymer micelles were produced by the dialysis method. The micelle size and core-shell structure of the block copolymer micelles and the drug-loaded micelles were confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The thermal properties of the copolymer micelles before and after drug-loaded were investigated by different scanning calorimetry (DSC). The results show that the micelle size is slightly increased with increasing the content of hydrophobic segments and the micelles are still core-shell spherical structures after drug-loaded. Moreover, the glass transition temperature (Tg) of polystyrene is reduced after the drug loaded. The drug loading content (DLC) of the copolymer micelles is 70%-80% by ultraviolet (UV) photolithography analysis. These properties indicate the micelles self-assembled from PSt-b-POEOMA-b-PSt copolymers would have potential as carriers for the encapsulation of hydrophobic drugs.

• 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.

• 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.

• 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.

• Polymer(Korea)
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• v.27 no.1
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• pp.17-25
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• 2003

Using atom transfer radical polymerization (ATRP), polystyrene macroinitiators and polystyrene-b-poly(t-butyl acrylate) (PS-b-P(tBA) block copolymers were synthesized by CuBr/PMDETA catalyst system in solution. After hydrolysis, polystyrene-b-poly(acrylic acid), amphiphilic block copolymers, were formed. Subsequent neutralization of polyacid block led to the block ionomers. The molecular weight of the synthesized PS-b-P(tBA) block copolymers was easily-controlled to 5000-10000 and their distributions were less than 1.2. The chemical structures of the synthesized block copolymers were characterized by $^1$H-NMR and FT-IR. In the DSC thermograms, $T_g$ appeared in the vicinity of 100 $^{\circ}C$ because of higher styrene content. In addition, the phase separation of the block ionomers was observed by TEM.

• Polymer(Korea)
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• v.32 no.2
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• pp.143-149
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• 2008

We synthesized PEG-PLA (or PLGA) amphiphilic di-block copolymers, which consist of PEG as biocompatible and hydrophilic block and PLA (or PLGA) as biodegradable and hydrophobic block, by ring opening polymerization of LA in the presence of methoxy PEG as a macroinitiator. The compositions and the molecular weights of the copolymers were controlled by changing the feed ratio of LA (and GA) to PEG initiator. The di-block copolymers could self-assemble in aqueous media to form micellar structure. A hydrophobic model drug, pioglitazone, was loaded into the polymer micelle using solid dispersion and dialysis methods, and the drug-loaded micelles were characterized by AFM, DLS and HPLC measurements. The drug loading capacity and in vitro release studies were performed and evaluated under various conditions. These results indicated that the amphiphilic di-block copolymers of PEG-PLA (or PLGA) could solubilize pioglitazone by solid dispersion method and the drug release was modulated according to micellar chemical compositions.

• 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.

• Macromolecular Research
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• v.15 no.1
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• pp.39-43
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• 2007

The amphiphilic block copolymer (PEtOz-PCL) of poly(2-ethyl-2-oxazoline) (PEtOz) and poly(${\varepsilon}$-caprolactone) (PCL) formed spherical micellar structures with an average diameter of 26 nm in aqueous phase. Au and Pd nanoparticles with an average diameter of $2{\sim}3nm$ were prepared by using the PEtOz-PCL micelle consisting of a PEtOz shell and PCL core. The Au nanoparticles of PEtOz-PCL micelles in aqueous phase could be transferred into organic phase by using n-dodecanethiol. The use of the Pd-NP/PEtOz-PCL micelle as a nanoreactor for Suzuki cross-coupling reaction was investigated.

• Journal of the Korean Society of Visualization
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• v.4 no.2
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• pp.6-10
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• 2006

The functional spherical microcapsules were produced through the innovative conjunction of the well-defined amphiphilic block copolymer and the stable droplet phase flow in the micro chemical plant. The microcapsules were formed to have hollow inner cavity and outer surface wall with nano-pores. To examine the potential of encapsulating foreign biochemical molecules, Congo-red dye was loaded into the microcapsule. The release performance in the specific surroundings such as temperature, pH and time was evaluated quantitatively.

• Macromolecular Research
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• v.16 no.2
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• pp.155-162
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• 2008

We report the successful synthesis of poly(NBECOOH-b-NBEPOSS) copolymers, taking advantage of the sequential, living ring opening metathesis polymerization of NBETMS and NBEPOSS using the $RuCl_2(=CHPh)(PCY_3)_2$/$CH_2Cl_2$/$20^{\circ}C$ system, followed by the hydrolysis of trimethylsilyl groups in poly(NBETMS-b-NBEPOSS) copolymers. The living behavior of ROMP of NBETMS was first investigated using two diagnostic plots, a first order kinetic plot and a $\bar{M}_n$ vs. conversion plot. The plots confirmed that no termination and chain transfer reaction had occurred during polymerization. Poly(NBECOOH-b-NBEPOSS) copolymers were prepared using the sequential monomer addition of NBEPOSS to living poly(NBETMS) chain ends, followed by the hydrolysis of trimethylsilyl groups in the poly(NBETMS-b-NBEPOSS) copolymers. The high structural integrity of poly(NBE-COOH-b-NBEPOSS) copolymers was confirmed by $^1H$-NMR, $^{13}C$-NMR spcctroscopy and GPC.