• Macromolecular Research
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• v.8 no.1
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• pp.26-33
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• 2000

A series of pH/temperature sensitive polymers were synthesized by copolymerizing N-isopro-pyl acrylamide(NIPAAm) and acrylic acid(AAc) . The influence of polyelectrolyte between poly(allyl amine) (PAA) and poly(L-lysine)(PLL) on the lower critical solution temperature(LCST) of pH/temperature sensitive polymer was compared in the range of pH 2∼12. The LCST of PNIPAAm/water in aqueous poly(NIPAAm-co-AAc) solution was determined by cloud point measurements. A polyelectrolyte complex was prepared by mixing poly(NIPAAm-co-AAc) with poly(allyl amine) (PAA) or poly(L-lysine) (PLL) solutions as anionic and cationic polyelectrolytes, respectively. The effect of polyelectrolyte complex formation on the conformation of PLL was studied as a function of temperature by means of circular dichroism(CD). The cloud points of PNIPAAm in the aqueous copolymers solutions were stongly affected by pH, the presence of polyelectrolyte solute, AAc content, and charge density. The polyelectrolyte complex was formed at neutral condition. The influence of more hydrophobic PLL as a polyelectrolyte on the cloud point of PNIPAAm in the aqueous copolymer solution was stronger than that of poly(allyl amine)(PAA). Although polymer-polymer complex was formed between poly(NIPAAm-co-AAc) and PLL, the conformational change of PLL did not occur due to steric hinderance of bulky N-isopropyl groups of PNIPAAm.

• Macromolecular Research
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• v.14 no.2
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• pp.199-204
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• 2006

Remarkably high and stable separation performance for olefin/paraffin mixtures was previously reported by facilitated olefin transport through ${\pi}$-complex membranes consisting of silver ions dissolved in poly(hexamethylenevinylene) (PHMV). In this study, the ${\pi}$-complex formation of $AgBF_4,\;AgClO_4\;and\;AgCF_{3}SO_3$ with PHMV and their ionic interactions were investigated. FT-Raman spectroscopy showed that the C=C stretching bands of PHMV shifted to a lower frequency upon incorporation of silver salt, but the degree of peak shift depended on the counter-anions of salt due to different complexation strengths. The symmetric stretching modes of anions indicated the presence of only free ions up to [C=C]:[Ag]=1:1, demonstrating the unusually high solubility of silver salt in PHMV. Above the solubility limit, the ion pairs and higher-order ionic aggregates started to form. The coordination number of silver ion for C=C of PHMV was in the order $AgBF_4$ > $AgClO_4$ > $AgCF_{3}SO_3$, but became similar at [C=C]:[Ag]=1:1. The different coordination number was interpreted in terms of the different transient crosslinks of silver cations in the complex, which may be related to both the interaction strength of the polymer/silver ion and the bulkiness of the counteranion.

• Macromolecular Research
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• v.14 no.3
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• pp.267-271
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• 2006

Polyelectrolyte complex films were prepared with two compounds, chitosan and poly(ethylene glycol)-monosuccinate, using a casting in order to synthesize a polyelectrolyte complex film with various mole ratios of chitosan and poly(ethylene glycol)-monosuccinate. The solution properties of isolated PEC were investigated for the effects of FTIR, pH value, Brookfield viscosity and cell viability assay using MTT staining. The PEC films were evaluated for mechanical properties by typical stress-strain curve, far thermal properties by DSC and TGA and for surface morphology Properties by SEM. Furthermore, the surface resistance, moisture regain and water content of the films were characterized. The solution properties were affected by several factors including the chitosan content in the PEC, the mixing ratio of PEG and chitosan, and pH. Several PEC in acidic conditions exhibited film formation under appropriate conditions of mixing ratio and chitosan concentration in the mixing process. These PEC films were found to have sufficiently flexible and stable properties due to their hydrophilic structure, which was farmed by the oppositely charged interaction between PEG-MS and chitosan matrix. The results showed the potential applicability of chitosan and poly(ethylene glycol)-monosuccinate films as a biocompatible polymer.

• Macromolecular Research
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• v.15 no.6
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• pp.581-586
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• 2007

Cast DNA/polyethyleneimine (PEI) blend membranes containing different amounts of DNA were prepared using acid-base interaction and characterized with the aim of understanding the polymer electrolyte membrane properties. Two different molecular weights of PEI were used to provide the mechanical strength, while DNA, a polyelectrolyte, was used for the proton transport channel. Proton conductivity was observed for the DNA/PEI membrane and reached approximately $3.0{\times}10^{-3}S/cm$ for a DNA loading of 16 wt% at $80^{\circ}C$. The proton transport phenomena of the DNA/PEI complexes were investigated in terms of the complexation energy using the density functional theory method. In the case of DNA/PEI, a cisoid-type complex was more favorable for both the formation of the complex and the dissociation of hydrogen from the phosphate. Since the main requirement for proton transport in the polymer matrix is to dissociate the hydrogen from its ionic sites, this suggests the significant role played by the basicity of the matrix.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2000.07a
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• pp.265-269
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• 2000

Nowadays the hydrophilic polymeric networks (polymer hydrogels) due to the complex of benefit physico-chemical properties attract a wide attention of specialists working in various fields of science, medicine and technology. The special attention of chemists is aimed on so-called stimuli-sensitive or intelligent hydrogels, which can undergo a volume phase transition in response to change in environmental parameters such as temperature, pH, solvent composition, etc [1]. Scientific group of Kazak State National University, Department of Macromolecular Chemistry works in this field [2-5]. Here we report about our achievements on pH-sensitive hydrogens.

• Macromolecular Research
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• v.10 no.6
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• pp.297-303
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• 2002

We have investigated the microstructural properties of a weakly charged polyelectrolyte modeled with both Hookean spring and Debye-Huckel potential, by employing a novel hybrid scheme of molecular dynamics (MD) and Monte Carlo (MC) simulations. Although the off-lattice pivot step facilitates the earlier computations stage, it gives rise to oscillations and hinders the stable equilibrium state. In order to overcome this problem, we adopt the MC off-lattice pivot step in early stage only, and then switch the computation to a pure MD step. The result shows that the computational speed-up compared to the previous method is entirely above 10 to 50, without loss of the accuracy. We examined the conformations of polyelectrolyte in solvents in terms of the end-to-end distance, radius of gyration, and structure factor with variations of the screening effects of solvent and the monomer charges. The emphasis can favorably be given on the elongation behavior of a polyelectrolyte chain, with observing the simultaneous snapshots.

• Macromolecular Research
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• v.10 no.3
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• pp.135-139
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• 2002

Blends of the linear bisphenol-A polycarbonate (L-PC) and randomly branched bisphenol-A polycarbonate (Br-PC), prepared by co-rotating twin screw extrusion, were investigated using differential scanning calorimetry (DSC), sag resistance time tester, extensional rheometry, and advanced rheometric expansion system (ARES). From the DSC results, the glass transition temperature (T$_{g}$) of the L-PC/Br-PC blend was increased with the increase of Br-PC in the blend, and the blend showed a single T$_{g}$, which suggests a miscible blend. The sag resistance time of the L-PC/Br-PC blend was increased with the increase of Br-PC in the blends. From the results of rheological measurements of the L-PC/Br-PC blends, the extensional viscosity and the complex viscosity of the blends were found to increase with the increase of Br-PC in the blends. The increase of extensional viscosity and complex viscosity was related with the increase of sag resistance time with the Br-PC in the L-PC/Br-PC blends.nds.

• Macromolecular Research
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• v.16 no.4
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• pp.308-313
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• 2008

A simple strategy was developed based on polyelectrolyte/silver nanocomposite to obtain humidity-sensitive membranes. The major component of a humid membrane is the polyTEAMPS/silver nanocomposite obtained by thermal heating the mixture of a polyelectrolyte and silver isopropylcarbamate complex. Humidity sensors prepared from polyTEAMPS/silver (w/w=100/0 and 100/6) nanocomposites had an average impedance of 292, 8.83 and $0.86\;k{\Omega}$, and 5,327, 140 and $0.93\;k{\Omega}$ at 30,60 and 95% relative humidity (RH), respectively. Hysteresis, temperature dependence and response time were also measured. Activation energies and complex impedance spectroscopy of the various components of the polyelectrolyte/silver nanocomposite films were examined for the humidity-sensing membrane.

• Macromolecular Research
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• v.16 no.3
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• pp.247-252
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• 2008

Lithium gel electrolytes based on a mixed polymer matrix consisting of poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP) and cyanoresin type M (CRM) were prepared using an in situ blending process. The CRM used in this study was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) (PVA) with a mole ratio of 1:1. The mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) with a volume ratio of 1:1. In this study, the presence of PVDF in the electrolytes helps to form a dimensionally stable film over a broad composition range, and decreases the viscosity. In addition, it provides better rheological properties that are suitable for the extrusion of thin films. However, the presence of HFP has a positive effect on generating an amorphous domain in a crystalline PVDF structure. The ionic conductivity of the polymer electrolytes was investigated in the range 298-333 K. The introduction of CRM into the PVDF-HFP/$LiPF_6$, complex produced a PVDF-HFP/CRM/$LiPF_6$ complex with a higher ionic conductivity and improved thermal stability and dynamic mechanical properties than a simple PVDF-HFP/$LiPF_6$, complex.

• Macromolecular Research
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• v.14 no.1
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• pp.66-72
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• 2006

The purpose of this study is to develop novel nanoparticles based on polyion complex formation between low molecular weight water-soluble chitosan (LMWSC) and all-trans retinoic acid (atRA). LMWSC nanoparticles encapsulating atRA based on polyion complex were prepared by mixing of atRA into LMWSC aqueous solution using ultrasonication. In FTIR spectra, the carbonyl group of atRA at 1690 $cm^{-1}$ disappeared or decreased when ion complexes were formed between LMWSC and atRA. In ${1}^H$ NMR spectra, specific peaks of atRA disappeared when atRA-encapsulated LMWSC (RAC) nanoparticles were reconstituted into $D_{2}O$ while specific peaks both of atRA and LMWSC appeared in $D_{2}O$/DMSO (1/3, v/v) mixture. XRD patterns also showed that the crystal peaks of atRA were disappeared by encapsulation into LMWSC nanoparticles. LMWSC nanoparticles encapsulating atRA have spherical shapes with particle size below 200 nm. The mechanism of encapsulation of atRA into LMWSC nanoparticles was thought to be an ion complex formation between LMWSC and atRA. LMWSC nanoparticles showed high atRA loading efficiency over 90$\%$ (w/w). AtRA was continuously released from nanoparticles over 10 days. In in vitro cell cytotoxicity test, free atRA showed higher cytotoxic effect against CT 26 colon carcinoma cell line on 1 day. However, RAC nanoparticles showed similar cytotoxicity against CT 26 cells on 2 day. These results suggest the potential for the introduction of LMWSC nanoparticles into various biomedical fields such as drug delivery.