• Polymer(Korea)
• /
• v.37 no.4
• /
• pp.539-546
• /
• 2013

Amino group-terminated poly(N-isopropylacrylamide) (PNIPAAm-$NH_2$) was synthesized via a radical polymerization of N-isopropylacrylamide (NIPAAm) using 2-aminoethanethiol hydrochloride (AESH) as a chain transfer agent. The molecular weight of the PNIPAAm-$NH_2$ was controlled by changing the concentration of AESH. The LCST of the aqueous solution of PNIPAAm-$NH_2$ increased slightly with increasing the AESH concentration. Alginate-g-PNIPAAm copolymer was synthesized by grafting PNIPAAm-$NH_2$ onto sodium alginate using N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide and N-hydroxysuccinimide. The formation of the grafted copolymers was confirmed by FTIR spectroscopy, solubility in water, and SEM-EDS. Alginate-g-PNIPAAm also exhibited swelling-deswelling behavior. However, it showed a LCST at a slightly increased temperature compared to PNIPAAm. The swelling ratio of the alginate-g-PNIPAAm hydrogel increased with the increase of the grafted PNIPAAm content.

• Macromolecular Research
• /
• v.14 no.1
• /
• pp.87-93
• /
• 2006

Copolymers composed of hyaluronic acid (HA) and poly(N-isopropylacrylamide) (PNIPAAm) were prepared to create temperature-sensitive injectable gels for use in controlled drug delivery applications. Semi-telechelic PNIPAAm, with amino groups at the end of each main chain, was synthesized by radical polymerization using 2-aminoethanethiol hydrochloride (AESH) as the chain transfer agent, and was then grafted onto the carboxyl groups of HA using carbodiimide chemistry. The result of the thermo-optical analysis revealed that the phase transition of the PNIPAAm-grafted HA solution occurred at around 30$\∼$33$^{circ}C$. As the graft yield of PNIPAAm onto the HA backbone increased, the HA-g-PNIPAAm copolymer solution exhibited sharper phase transition. The short chain PNIPAAm-grafted HA ($M_{w}$=6,100) showed a narrower temperature range for optical turbidity changes than the long chain PNIPAAm-grafted HA ($M_{w}$=13,100). PNIPAAm-grafted HA exhibited an increase in viscosity above 35$^{circ}C$, thus allowing the gels to maintain their shape for 24 h after in vivo administration. From the in vitro riboflavin release study, the HA-g-PNIPAAm gel showed a more sustained release behavior when the grafting yield of PNIPAAm onto the HA backbone was increased. In addition, BSA released from the PNIPAAm-g-HA gels showed a maximum concentration in the blood 12 h after being injected into the dorsal surface of a rabbit, followed by a sustained release profile after 60 h.

• Journal of Adhesion and Interface
• /
• v.16 no.2
• /
• pp.76-82
• /
• 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
• /
• v.45 no.3
• /
• pp.230-235
• /
• 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.

• Macromolecular Research
• /
• v.13 no.1
• /
• pp.54-61
• /
• 2005

We prepared temperature-sensitive liposomes (TS-liposomes) modified with a thermo sensitive polymer, such as poly(N-isopropylacrylamide) (PNIPAAm), to increase the degree of drug release from liposomes at the hyperthermic temperature. A PNIPAAm hydrogel containing TS-Iiposomes was also prepared to obtain a hydrogel complex at body temperature. In addition, a depot system for local drug delivery using the polymer hydrogel was developed to enhance therapeutic efficacy and prevent severe side effects in the whole body. The PNIPAAm-mod­ified TS-liposome was fixed into the PNIPAAm hydrogel having a high temperature-sensitivity. The release behavior of calcein, a model drug, from TS-liposomes in the PNIPAAm hydrogel was then initiated by external hyperthermia; the results indicated that sustained release as a function of temperature and time was caused by the thermosensitivity of the liposome surface and diffusion of the drug into the PNIPAAm hydrogel. Our results indicated that TS-liposomes in a PNIPAAm hydrogel represented a plausible system for local drug delivery.

• Polymer(Korea)
• /
• v.35 no.3
• /
• pp.223-227
• /
• 2011

Stimuli-responsive polymers have been investigated as the materials playing the critical roles in various applications. Thermoresponsive graft copolymers, poly (N-isopropylacrylamide)-g-hyaluronic acid (PNIPAAm-g-HA) and elastin-like peptide-g-hyaluronic acid (ELP-g-HA), were synthesized by coupling carboxylic polymers (PNIPAAm-COOH or ELP) to biocompatible HA through amide linkages. Thermoresponsive behavior was observed in both the copolymers, and the results of turbidity measurement were consistent with the results of rheological examination. Among the two copolymers, the ELP graft copolymer shows less cooperative LCST transition than the PNIPAAm case. As the content of graft chains of PNIPAAm and ELP increases, viscosity increases, and the increase was larger in PNIPAAm case at a graft content. These results shows us that the introduction of grafts provides thermosensitivity to biocompatible HA, whose characteristics can be engineered.

• Polymer(Korea)
• /
• v.34 no.2
• /
• pp.166-171
• /
• 2010

Poly(N-isopropylacrylamide)(PNIPAAm) containing polydimethylsiloxane(PDMS) block and nano clay was obtained by the polymerization of NIPAAm and [3-(methacryloylamino)propyl]trimethyl ammonium montmorillonite(MAPTAC-MMT) with PDMS-macroinitiator. The polymer was characterized with FT-IR, XRD and DSC. The addition of PDMS in the polymers did not affect the value of the lower critical solution temperature(LCST) and the glass transition temperature($T_g$) of the PNIPAAm. However, the swelling ratio decreased with increasing PDMS contents. In the case of PNIPAAm containing nano clay, the content of MAPTAC-MMT did not affect swellability, but the $T_g$ of the PNIPAAm decreased with increasing nano clay contents.

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

• Polymer(Korea)
• /
• v.37 no.6
• /
• pp.784-793
• /
• 2013

A two-step method for obtaining poly(N-isopropylacrylamide) (PNIPAAm) from poly(acrylonitrile) (PAN) was investigated in order to find a feasibility of imparting thermo-responsive property onto textile fiber materials. PAN was converted to poly(acrylic acid) (PAA) by hydrolysis at a first-step, and then PAA was converted to PNIPAAm at a second step via an amidation reaction of PAA with isopropylamine (IPA) in DMF medium using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as catalysts. High content of carboxylic groups at the first step was obtained by the successive alkaline and acid hydrolysis of PAN. The degree of conversion of PAA to PNIPAAm at the second step was dependent on the amount of catalysts EDC and NHS. PNIPAAm converted from PAA through amidation reaction showed a lower critical solution temperature (LCST) behavior when the conversion was higher than about 53%.

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