• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.101-101
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• 2006

We have studied the micellisation of poly(n-butyl acrylate)-block-poly(acrylic acid) and poly(n-butyl acrylate)-graft-poly(acrylic acid) in aqueous solution. The size and structure of the formed micelles was elucidated by scattering and imaging techniques. The micelle structure depends on pH, composition, and topology: graft copolymers form much smaller micelles that block copolymers of similar composition. We have also synthesized block copolymers of acrylic acid and N-isopropylacrylamide (NIPAAm) or N,N-diethylacrylamide (DEAAm). Due to the LCST of polyNIPAAm and polyDEAAm, these block copolymers spontaneously form micelles upon heating and they form inverse micelles upon decreasing pH below 4. If the LCST block is much longer than the PAA one, this presents a very convenient way to prepare crew-cut micelles. The polymers have been successfully used as stabilizers in emulsion polymerization. They also have been conjugated to streptavidin. The conjugates reversibly form mesoscopic particles on heating.

• Biomaterials and Biomechanics in Bioengineering
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• v.1 no.2
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• pp.105-116
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• 2014

Synthesis of interpenetrating polymer network (IPN) of chitosan-gelatin (Cs-Ge) (as a primary network) and N-isopropylacrylamide (NIPAAm) monomer (as the secondary network) was carried out with different ratio. Its structure was characterized by FT-IR, which indicated that the IPN was formed. The memberanes were studied by swelling, weight loss with time. The interior morphology of the IPN hydrogels was revealed by scanning electron microscopy (SEM); the IPN hydrogels showed a interpenetrated network of NIPAAm/chitosan has layers with more minute stoma and canals compared to interpenetrated network of NIPAAm/gelatin. Lower critical solution temperature (LCST), equilibrium swelling ratio (ESR) and deswelling kinetics were measured. The DSC results noticed that LCST of IPN hydrogels with different ratio of Cs/Ge/PNIPAAm are around $33{\pm}2^{\circ}C$. The ESR obtained results showed that with a ratio of Cs/Ge/NIPAAm: 1/1/6, the swelling ratio increased drastically from room temperature to $36^{\circ}C$ but with a ratio of Cs/Ge/PNIPAAm: 1/3/6, decrease significantly at the same condition. Therefore the hydrogels have been changed from a hydrophilic structure to a hydrophobic structure. Furthermore with an increase in temperature from room to the LCST, the ESR of IPN with higher concentration of (PNIPAAm) and (Ge) decreases but de-swelling kinetics of them are faster. Due to the suitable and different kinetics of de-swelling and the equilibrium swelling ratio (ESR) in various proportions, and because of the morphology inside the mass which confirms other tests, these hydrogels are very appropriate as a smart thermosensitive hydrogels with rapid response.

• Journal of Adhesion and Interface
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• v.16 no.2
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• pp.76-82
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• 2015

W/O emulsions were prepared from the aqueous solution containing NIPAAm, MBA, and APS in the continuous phase of toluene and mineral oil mixture with HMP and Span80 by using SPG membrane emulsification, and followed by the formation of PNIPAAm hydrogel microspheres through UV photopolymerization. As the ratio of mineral oil to toluene increased in the continuous phase, both particle size of the hydrogel increased and density of PNIPAAm polymer in the hydrogel particle increased, and which significantly affected swelling/deswelling ratio ($V/V_o$) with temperature change around VPTT. When the polymerization temperature was below LCST ($20^{\circ}C$), PNIPAAm hydrogel showed filled particle morphology; however, it was turned out to hollow particle morphology with thick shell layer with $40^{\circ}C$. Both density of PNIPAAm and gel content of the hydrogel increased with the increase in MBA concentration.

• Journal of the Korean Chemical Society
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• v.47 no.1
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• pp.59-66
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• 2003

The comb-type grafted polymer hydrogels, which composed of N-isopropylacrylamide monomer and oligo(N-isopropylacrylamide-co-tert-butylacrylamide) [oligo(NIPAAm-co-t-BAM)], were synthesized by redox polymerization in 5~10% methanol aqueous solution using ammonium peroxodisulfate (APS) at 4 oC for 24h. The lower critical solution temperatures (LCSTs) of the comb-type grafted hydrogels were decreased with increase of t-BAM content in the grafted copolymer. We observed the effect of crosslinker and concentration of oligo(NIPAAm-co-t-BAM) on the shrinking/swelling ratio of hydrogels. Changes of shrinking/swelling ratio were decreased with increase of concentration of crosslinker. The increase of grafted oligo(NIPAAm-co-t-BAM) in the hydrogel shows an fast changes of shrinking/ swelling rate. The comb-type grafted hydrogels are expected to be valuable for the sensing materials of time-temperature labels(TTLs).

• Elastomers and Composites
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• v.39 no.4
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• pp.318-323
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• 2004

Cloud-point and bubble-point curves for poly(ethylene-co-13.8 mol% octene) ($PEO_{13.8}$) and Poly(ethylene-co-15.3 mol% octene) ($PEO_{15.3}$) were determined up to $150^{\circ}C$ and 450 bar in hydrocarbons which have different molecular size and structure. Whereas ($PEO_{15.3}$+ n-pentane) system has cloud-point and bubble-point type transitions, ($PEO_{15.3}$+ n-propane) and ($PEO_{15.3}$+ n-butane) systems do only cloud-point type transition. In cyclo-pentane, -hexane, -heptane, and -octane, $PEO_{15.3}$ has a bubble-point transition. ($PEO_{13.8}$+ n-butane) mixture has a critical mixture concentration at 5 wt% PEO. (PEO + hydrocarbon) mixtures exhibit LCST type behavior. Solubility of PEO increases with hydrocarbon size due to increasing dispersion interaction which is favorable to dissolve PEO.

• 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.

• Polymer(Korea)
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• v.39 no.1
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• pp.165-168
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• 2015

Thermoresponsive polymers were successfully synthesized by a combination of atom transfer radical polymerization (ATRP) and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide and alkynes (click chemistry). Poly(2-hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, followed by introduction of alkyne groups using pentynoic acid, leading to HEMA-alkyne. Homopolymers having secondary amine groups, tertiary amines with hydroxyethyl and hydroxypropyl groups were synthesized by adding 2-azido-N-ethyl-ethanamine, 2-[(2-azidoethyl)amino]ethanol, and 2-[(2-azidoethyl)amino]propanol, respectively, to the PHEMA-alkyne backbone using click chemistry. Molecular weight (MW), molecular weight distribution (MWD), and click reaction efficiency were determined by gel permeation chromatography (GPC) and $^1H$ NMR spectroscopy. The transmission spectra of the 1.0 wt% aqueous solutions of the resulting polymers at 650 nm were measured as a function of temperature. Results showed that the lower critical solution temperature (LCST) could be easily controlled by the length of the hydroxyalkyl groups.

• 한국생물공학회:학술대회논문집
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• 2000.04a
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• pp.562-565
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• 2000

pH- and thermo-sensitive hydrogels containing maleilated chitosan(MC) and N-isopropylacrylamide(NIPAAm) were prepared and characterized for their swelling behavior, biodegradability and drug release profiles. The hydrogels exhibited a typical pH-sensitivity due to the carboxylic acid groups of maleilated chitosan. The change of ratio of NIPAAm to MC in weight did not affect on either lower critical solution temperature(LCST) or EWC significantly. The pH sensitivity of the hydrogel, however, depended on the amounts of carboxylic acid groups of MC. MC was degradable up to 80% weight reduction in 2 hours. The in vitro drug relase profiles were established both in buffer solution pH 1.4 and pH 7.4. Only a negligible amount of indomethacin was released at pH 1.4 in 6 hours, while at pH 7.4 more than 90% of the total drug in the hydrogel was gradually released over ca. 5 hours.

• Biotechnology and Bioprocess Engineering:BBE
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• v.6 no.4
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• pp.274-278
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• 2001

Polymer membranes composed of N, N-dimethylaminoethyl methaccrylate(DMAEMA) and acrylamide(AAm)(or ethyl acrylamide(EAAm) were prepared to demonstrated the thermo-control of solute permeation. Poly DMEMA has a lower critical solution temperature(LCST) at around 50$\^{C}$ in water, With the copolymerization of DMAEMA with AAm (or EAAm) a shift in the LCST to a lowere temperature was observed, probably due to the formation of hydrogen bonds between the amide and N-N-dimethylamino groups. However, the temperature-induced phase transition of poly(DMAEMA-co-EAAm) did not show a similar trend to that of poly(DMAEMA- co-AAm) in the gel state. The hydrogen bonds in poly(DMAEMA-co-EAAm) were significantly disrupted with the formation a gel network, which led to a difference in the swilling behavior of polymer gels in response to temperature. To apply these polymers to temperature-sensitive sol-ute permeation, polymer membranes were prepared. The permeation pattern of hydrocortisone, used as the model solute, was explained based on the temperature-sensitive swelling behavior of the polymer membranes.

• Macromolecular Research
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• v.17 no.4
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• pp.265-270
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• 2009

Noble thermosensitive nanoparticles, based on a PNIPAAm-co-AA core and a chitosan shell structure, were designed and synthesized for the controlled release of the loaded drug. PNIPAAm nanoparticles containing a carboxylic group on their surface were synthesized using emulsion polymerization. The carboxylic groups were conjugated with the amino group of a low molecular weight, water soluble chitosan. The particle size of the synthesized nanoparticles was decreased from 380 to 25 nm as the temperature of the dispersed medium was increased. Chitosan-conjugated nanoparticles with $2{\sim}5$ wt% MBA, a crosslinking monomer, induced a stable aqueous dispersion at a concentration of 1mg/1mL. The chitosan-conjugated nanoparticles showed thermo sensitive behaviors such as LCST and size shrinkage that were affected by the PNIPAAm core and induced some particle aggregation around LCST, which was not shown in the NIPAAm-co-AA nanoparticles. These chitosan-conjugated nanoparticles are also expected to be more biocompatible than the PNIPAAm core itself through the chitosan shell structures.