• Bulletin of the Korean Chemical Society
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• v.24 no.7
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• pp.901-905
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• 2003

The lower critical solution temperature (LCST) of thermosensitive poly(organophosphazenes) with methoxypoly(ethylene glycol) (MPEG) and amino acid esters as side groups was studied as a function of saccharide concentration in aqueous solutions of mono-, di-, and polysaccharides. Most of the saccharides decreased the LCST of the polymers, and the LCST decrease was more prominently observed by saccharides containing a galactose ring, such as D-galactose, D-galactosamine and D-lactose, and also the polysacccharide, 1-6-linked D-dextran effectively decreased the LCST of the polymers. Such an effect was discussed in terms of intramolecular hydrogen bonding of saccharides in polymer aqueous solution. The saccharide effect was found to be almost independent on the kinds of the amino acid esters and MPEG length of the polymers. Such a result implies that the polymer-saccharide interaction in aqueous solution is clearly influenced by the structure of sacchardes rather than by that of the polymers. The acid saccharides such as D-glucuronic and D-lactobionic acid increased the LCST, which seems to be due to their pH effect.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.501-504
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• 2014

A thermoresponsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), was successfully synthesized by atom transfer radical polymerization (ATRP). Different amounts of 1,3-propanesultone were used as quaternization agent to transit the PDMAEMA into partially modified poly(zwitterions), resulting in p[DMAEMA-co-3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate] (PDMAEMA-co-PDMAPS). Molecular weight, molecular weight distribution, and degree of quarternization 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) and the upper critical solution temperature (UCST) could be easily controlled by the different composition of dimethylamino and zwitterion groups. The effect of partial quaternization on thermoresponsive properties was also studied by dynamic light scattering (DLS) with the same aqueous concentration (1.0 wt %) as employed for turbidimetry studies. The LCST and UCST values measured by DLS correlated well with those determined by turbidimetry.

• KSBB Journal
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• v.15 no.6
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• pp.548-555
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• 2000

A hydrogel, poly(N-isopropylacrylamide-co-N, N-dimethylaminopropylmethacrylamide), sensitive to both pH and temperature, was synthesized and characterized at $^13∼23{\circ}C$ and pH of 10.3∼12.3. The gel was more transparent and mechanically stronger at lower preparation temperature and pH. Large pores observed in scanning electron microscope seem to be responsible for the lower biomolecular separation efficiency. The lower critical solution temperature (LCST) decreased at a higher polymerization temperature. At $25^{\circ}C$, which is lower than the LCST, the gel was swollen regardless of the solution pH. At $40^{\circ}C$, however, the gel was swollen at neutral and acidic pHs even though the temperature was higher than the LCST. The gel collapse pH, defined as the point at which the gel made its largest volume decrease per unit pH increment, increased as the gel preparation temperature increased.

• Journal of the Korean Chemical Society
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• v.45 no.3
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• pp.230-235
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• 2001

Poly(N-isopropylacrylamide) (PNIPAAm) containing polydimethylsiloxane (PDMS) was synthesized using PDMS as crosslinking agent, and characterized by IR and DSC. It seems that the copolymer has separated phases, PNIPAAm and PDMS. The $T_g$ of PNIPAAm was decreased in accordance with the increase of PDMS-contents. The swelling behavior of polymer in water was examined with the function of temperature and PDMS-contents as well. The equilibrium swelling ratio of polymer in water was decreased with increasing PDMS-contents, but lower critical solution temperature (LCST) was not significantly affected by the incorporated PDMS-contents.

• Biomaterials and Biomechanics in Bioengineering
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• v.2 no.1
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• pp.15-22
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• 2015

Poly(ethylene glycol) end-capped with pentafluorophenyl group(s) in ABA (FP-PEG-FP) and AB (mPEG-FP) types were prepared. Even though they were similar in composition, the lower critical solution temperature (LCST) of FP-PEG-FP was observed at $23^{\circ}C$, whereas that of mPEG-FP was observed at $65^{\circ}C$. To understand the large difference in solution behaviour of the two polymers, UV-VIS spectroscopy, microcalorimetry, 1H-NMR spectroscopy, and dynamic light scattering were used. FP-PEG-FP has two hydrophobic pentafluorophenyl groups at the ends of hydrophilic PEG (1000 Daltons), whereas mPEG-PF has a highly dynamic PEG (550 Daltons) block that are anchored to a hydrophobic pentafluorophenyl group. PF-PEG-PF not only has a smaller conformational degree of freedom than mPEG-PF but also can form extensive intermolecular aggregates, therefore, PF-PEG-PF exhibits a significantly lower LCST than mPEG-PF. This paper suggests that topological control is very important in designing a temperature-sensitive polymer.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.1981-1984
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• 2006

Novel amphiphilic, thermo-responsive polyaspartamides which showed both LCST (lower critical solution temperature), and sol-gel transition were prepared and characterized. The polyaspartamide derivatives were synthesized from polysuccinimide, the polycondensate of aspartic acid monomer, via successive nucleophilic ring-opening reaction by using dodecylamine and N-isopropylethylenediamine (NIPEDA). At the intermediate composition ranges, the dilute aqueous solution exhibited a thermally responsive phase separation due to the presence of LCST. The phase transition temperature was controllable by changing the content of pendent groups. In addition, a physical gelation, i.e. the sol-gel transition was observed from the concentrated solutions, which was elucidated by dynamic viscoelastic measurements. These novel injectable and thermo-responsive hydrogels have potential for various biomedical applications such as tissue engineering and current drug delivery system.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1521-1525
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• 2009

Thermosensitive block copolymers of ethylene oxide and N-isopropylacrylamide (NIPAM) were synthesized. A five armed star shape oligo(ethylene oxide) initiator with a cyclotriphosphazene core was prepared and used for the atom transfer radical polymerization (ATRP) of NIPAM. The lower critical solution temperatures (LCSTs) of the copolymers were 36 to 46 ${^{\circ}C}$, higher than that of PNIPAM (32 ${^{\circ}C}$), depending on their molecular weights. The copolymers were soluble in water below the LCSTs but formed micelles above the LCSTs. The thermosensitive micellization behaviors of the polymers were investigated by fluorescence spectroscopy. With increasing the temperature of an aqueous solution of P2 and pyrene above the LCST, the peak of 333 nm red-shifted to appear around 339 nm and its intensity increased significantly, indicating the micelle formation. The transfer of pyrene into the micelles was also confirmed by a confocal laser scanning microscope. The fluorescence image obtained from P2 in an aqueous pyrene solution exhibited a green emission resulting from the pyrene transferred into the micelles. Salt effects on the solubility of the copolymers in an aqueous solution were investigated. The LCST of P2 decreased sharply as the concentration of sodium chloride increased, while decreased slowly with potassium chloride.

• KSBB Journal
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• v.14 no.1
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• pp.58-65
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• 1999

A hydrogel, poly(N-isopropylacrylamide-co-N,N'-dimethylaminopropyl methacrylamide), sensitive to both pH and temperature was synthesized and characterized for its welling behavior, lower critical solution temperature (LCST), and its appearance. The hydrogel with 5 mol% of N,N'-diemthylaminopropyl methacrylamide (DMAPMAAm) increased its volume phenomenonally in a lower pH range (ph 1~8) even at temperature ($37^{\circ}C$ and $40^{\circ}C$) higher than LCST. This behavior was unique compared to the temperature -sensitive hydrogel which did not exhibit any swelling in the same pH range. The hydrogel with 20 mol% of DMAPMAAm was swollen significantly at a higher pH of 12. With pH decrease from 12 to 2 water content in the gel increased from 38.8 wt% and 60.6 wt%, and 90.8 wt% for 5 mol% and 20 mol% gel, respectively. The transition pH that pH effect overwhelmed temperature effect occurred at a lower pH for a higher temperature ($40^{\circ}C$) and a lower mol% (5 mol%) of DMAPMAAm. Transparency and LCST of the gel increased with higher DMAPMAAm mol%.

• Journal of the Korean Chemical Society
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• v.42 no.1
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• pp.84-91
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• 1998

Random copolymers of N-isopropyl acrylamide (NIPAAm) and acrylic acid (AAc) which exhibit temperature- and pH-responsive behavior were synthesized by free-radical polymerization. The copolymers were characterized by means of FT-IR spectrometry and titration. The influence of polyelectrolyte on the lower critical solution temperature (LCST) of pH/temperature-sensitive polymers was investigated in the pH range of 2-12. The LCSTs of PNIPAAm/water in poly(NIPAAm-co-AAc) were determined by cloud-point measurements. A polyelectrolyte complex was prepared by mixing poly(NIPAAm-co-AAc) with poly(allylamine) (PAA) or poly(L-lysine) (PLL) solutions as anionic and cationic polyelectrolytes, respectively. Back titration was performed to determine the content of AAc and to study the effect of comonomer ionization on the LCST. The LCSTs of PNIPAAm/water in the copolymers were strongly affected by pH, presence of polyelectrolyte, AAc content, and charge density on the polymer. The polyelectrolyte complexes were formed at neutral condition. The influence of more hydrophobic PLL as polyelectrolyte on the cloud-point of PNIPAAm/water in the copolymer was stronger than that of poly(allylamine) (PAA).

• Proceedings of the Korean Fiber Society Conference
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• 2003.10b
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• pp.193-194
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• 2003

전기활성 고분자인 poly(vinylidene fluoride)(PVDF)를 전기 비활성 고분자와 블렌드시키는 경우 어떤 블렌드계에서는 용융 온도 이상에서 LCST(lower critical solution temperature) 상분리 거동을 나타내는데[1,2], 이때 외부 전장을 가해주면 이들의 상분리 거동에 영향을 미칠 수 있다[3]. PVDF와 블렌딩시켰을 때 LCST 상분리 거동을 나타내는 고분자로는 poly(methyl methacrylate), poly(ethyl methacrylate), poly(1,4-butylene adipate) (PBA) 등이 있다[l,3]. (중략)