• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.29-30
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• 2006

• Macromolecular Research
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• v.13 no.6
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• pp.529-532
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• 2005

A novel amphiphilic, symmetric rod-coil, triblock copolymer (denoted as PHEMA-b-PF-b-PHEMA) of poly(9,9-didodecylfluorene-2,7-diyl) (PF) and poly(hydroxyl ethyl methacrylate) (PHEMA) was synthesized. A $\pi$-conjugated poly(9,9-didodecylfluorene-2,7-diyl) (PF) was used as a rodlike midblock segment and connected with hydrophilic end blocks of poly(hydroxyl ethyl methacrylate) (PHEMA) by using an ATRP technique. The chemical structure of PHEMA-b-PF-b-PHEMA was confirmed by $^{1}H$-NMR and GPC, and its PL properties were investigated in selected solvents. Due to the dissimilarities in molecular conformation and solubility between PHEMA and PF blocks, both block segments were segregated to display a phase-separated morphology on a Si wafer.

• 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.17 no.11
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• pp.926-930
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• 2009

A new method for encapsulating nanomaterials within intermediary layer cross-linked (ILCL) polymeric micelles using a bifunctional photo-cross-linking agent was developed. For ILCL polymeric micelles, an amphiphilic triblock copolymer of poly(ethylene glycol)-b-poly(2-hydroxyethyl methacrylate)-b-poly(methyl methacrylate) (PEG-PHEMA-PMMA) was synthesized via consecutive atom transfer radical polymerization (ATRP), Di(4-hydroxyl benzophenone) dodecanedioate (BPD) was used as a bifunctional photo-cross-linking agent. The PMMA-tethered Au nanoparticles and BPD, or pyrene and BPD were encapsulated in the PEG-PHEMA-PMMA micelles, and their intermediary layers were photo-cross-linked by UV irradiation for 1 h. The HEMA units donated labile hydrogens to the excited-state benzophenone groups in BPD, and they were subsequently cross-linked by BPD through radical-radical combination. The spherical structures of the PEG-PHEMA-PMMA micelles containing the Au nanoparticles or pyrene were unaffected by the photo-cross-linking process.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.469-469
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• 2011

고효율 염료감응형 태양전지(DSSC, Dye-Sensitized Solar Cell)의 구현을 위해서 유용한 방법중 하나는 정렬된 기공 (pore)을 $TiO_2$막 내에 형성시키는 것이다. 메조포러스 (mesoporous) $TiO_2$막은 dip coating이나 spin coating과 같은 방법으로 주로 증착되고 있으며, P123이나 F127과 같은 amphiphilic triblock copolymer를 메조포러스 구조를 만들기 위한 뼈대로 사용하고 있다. 또한, 이렇게 생성된 구조에서 amphiphilic triblock copolymer는 열처리 공정을 통하여 쉽게 제거될 수 있다. 고효율 태양전지를 구현하는 또 다른 방법으로는 패턴 된 기판을 사용하는 것이다. 패턴 된 기판은 빛의 반사를 억제하여 흡수율을 높이는 역할을 한다. 그러나 패턴 된 기판 위에서 메조포러스 $TiO_2$막의 형성에 관한 연구는 부족한 실정이다. 본 연구에서는 spin coating 방법으로 패턴 된 Si (111) 기판 위에 메조포러스 $TiO_2$를 성장하고 그 미세구조를 분석하였다. 패턴 된 기판은 nanosphere lithography(NSL) 법으로 mask를 증착한 후 건식 식각 (dry etching) 공정을 통해서 제작되었으며, 마스크와 불순물 등 은 초음파 세척 등으로 제거되었다. 메조포러스 $TiO_2$막은 1-propanol, P123, titanium isopropoxide와 HCl을 섞어 만든 용액으로 1 cm${\times}$1 cm 기판 위에 3000 rpm과 4000 rpm으로 각각 증착하였으며, 5일 동안 4도에서 에이징한 후 350도에서 3시간 열처리하였다. 이렇게 형성한 메조포러스 막의 형상과 미세구조적 특성이 주사전자현미경(SEM, scanning electron microscope), X-선 회절(XRD, X-ray diffraction) 등을 이용하여 연구되었다. 특히, 증착 조건에 따른 메조포러스 $TiO_2$박막의 형성 기구에 관한 고찰이 진행되었다. 나아가, $TiO_2$박막과 패턴 사이에 형성되는 계면 구조에 관한 연구를 투과전자현미경을 이용하여 진행하였다.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1653-1668
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• 2005

Assembly of hybrid mesophases through the combination of amphiphilic block copolymers, acting as structuredirecting agents, and silicon sources using low acid catalyst concentration regimes is a versatile strategy to produce large quantities of high-quality ordered large-pore mesoporous silicas in a very reproducible manner. Controlling structural and textural properties is proven to be straightforward at low HCl concentrations with the adjustment of synthesis gel composition and the option of adding co-structure-directing molecules. In this account, we illustrate how various types of large-pore mesoporous silica can easily be prepared in high phase purity with tailored pore dimensions and tailored level of framework interconnectivity. Silica mesophases with two-dimensional hexagonal (p6mm) and three-dimensional cubi (Fm$\overline{3}$m, Im$\overline{3}$m and Ia$\overline{3}$d) symmetries are generated in aqueous solution by employing HCl concentrations in the range of 0.1−0.5 M and polyalkylene oxide-based triblock copolymers such as Pluronic P123 $(EO_{20}-PO_{70}-EO_{20})$ and Pluronic F127 $(EO_{106}-PO_{70}-EO_{106})$. Characterizations by powder X-ray diffraction, nitrogen physisorption, and transmission electron microscopy show that the mesoporous materials all possess high specific surface areas, high pore volumes and readily tunable pore diameters in narrow distribution of sizes ranging from 4 to 12 nm. Furthermore, we discuss our recent advances achieved in order to extend widely the phase domains in which single mesostructures are formed. Emphasis is put on the first synthetic product phase diagrams obtained in $SiO_2$-triblock copolymer-BuOH-$H_2O$ systems, with tuning amounts of butanol and silica source correspondingly. It is expected that the extended phase domains will allow designed synthesis of mesoporous silicas with targeted characteristics, offering vast prospects for future applications.