• Macromolecular Research
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• v.14 no.2
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• pp.205-208
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• 2006

A polymeric film of a biodegradable poly(1,5-dioxepan-2-one) (PDXO) was formed on a gold surface by a combination of the formation of self-assembled monolayers (SAMs) presenting hydroxyl groups and the surface-initiated, ring-opening polymerization (SI-ROP) of 1,5-dioxepan-2-one (DXO). The SI-ROP of DXO was achieved by heating a mixture of $Sn(Oct)_2$, DXO, and the SAM-coated substrate in anhydrous toluene at $55^{\circ}C$. The resulting PDXO film was quite uniform. The PDXO film was characterized by polarized infrared external reflectance spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, atomic force microscopy, ellipsometry, and contact angle goniometry.

• Macromolecular Research
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• v.13 no.5
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• pp.446-452
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• 2005

The interactions between the surface of scaffolds and specific cells play an important role in tissue engineering applications. Some cell adhesive ligand peptides including Arg-Gly-Asp (RGD) have been grafted into polymeric scaffolds to improve specific cell attachment. In order to make cell adhesive scaffolds for tissue regeneration, biodegradable nonporous poly(L-lactic acid) (PLLA) films were prepared by using a solvent casting technique with chloroform. The hydrophobic PLLA films were surface-modified by Argon plasma treatment and in situ direct acrylic acid (AA) grafting to get hydrophilic PLLA-g-PAA. The obtained carboxylic groups of PLLA-g-PAA were coupled with the amine groups of Gly-Arg-Asp-Gly (GRDG, control) and GRGD as a ligand peptide to get PLLA-g-GRDG and PLLA-g-GRGD, respectively. The surface properties of the modified PLLA films were examined by various surface analyses. The surface structures of the PLLA films were confirmed by ATR-FTIR and ESCA, whereas the immobilized amounts of the ligand peptides were 138-145 pmol/$cm^2$. The PLLA surfaces were more hydrophilic after AA and/or RGD grafting but their surface morphologies showed still relatively smoothness. Fibroblast adhesion to the PLLA surfaces was improved in the order of PLLA control

• Polymer(Korea)
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• v.30 no.2
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• pp.168-174
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• 2006

To utilize as highly functional scaffolds for tissue engineering by improving hydrophobicity and cell compatibility of the exist polymer scaffolds, the biodegradable poly(L-lactic acid) (PLLA) films and scaffolds having the optimal hydrophilicity were prepared by in situ plasma treatment and grafting of a carboxyl acid-containing monomer, acrylic acid (AA) in the chamber. From the results of surface analyses, surface-modified nonporous PLLA film and dual pore scaffold surfaces showed high hydrophilicity due to the decrease in contact angle and the increase in carboxylic groups as compared with untreated PLLA control. In particular, among various surface modification methods, Ar(argon)+AA+AA sample prepared by Ar plasma and then acrylic acid treatments displayed lower contact angle and more carboxylic groups thar Ar/AA and Ar+TP(thermal polymerization) samples, indicating that Ar+AA+AA sample was optimally treated for improving its hydrophilicity. In the cases of surface modified nonporous PLLA films and dual pore scaffolds, the adhesion and proliferation of chondrocytes increased with increasing their hydrophilicity.

• Polymer(Korea)
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• v.24 no.2
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• pp.141-148
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• 2000

Polycaprolactone (PCL) was blended with corn starch to produce biodegradable compost films and the biodegradability and mechanical properties were investigated. As the compatibilizer for the immiscible PCL/starch blend, 2-hydroxyethylmethacrylate (HEMA)-PCL macromer was grafted onto starch by initially grafting HEMA to starch and then grafting of PCL onto HEMA via ring opening polymerization of $\varepsilon$-caprolactone. When biodegradability of the PCL grafted starch-g-DEMA copolymers was compared with that of starch by the modified Sturm test, graft copolymers degraded at much slower rates due to the presence of the non-degradable HEMA. With the addition of the graft copolymer up to 5 wt% to the blend, the elongation-at-break of the starch/PCL blend increased substantially, while the tensile strength and modulus did not change much. SEM observation of the blend containing 2 wt% copolymer clearly indicated that the interfacial adhesion between the starch and PCL was strengthened by the copolymer.

• Macromolecular Research
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• v.14 no.5
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• pp.552-558
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• 2006

Biodegradable nanofibrous poly(L-lactic acid) (PLLA) scaffold was prepared by an electrospinning process for use in tissue regeneration. The nanofiber scaffold was treated with oxygen plasma and then simultaneously in situ grafted with hydrophilic acrylic acid (AA) to obtain PLLA-g-PAA. The fiber diameter, pore size, and porosity of the electrospun nanofibrous PLLA scaffold were estimated as $250\sim750nm,\;\sim30{\mu}m$, and 95%, respectively. The ultimate tensile strength was 1.7 MPa and the percent elongation at break was 120%. Although the physical and mechanical properties of the PLLA-g-PAA scaffold were comparable to those of the PLLA control, a significantly lower contact angle and significantly higher ratio of oxygen to carbon were notable on the PLLA-g-PAA surface. After the fibroblasts were cultured for up to 6 days, cell adhesion and proliferation were much improved on the nanofibrous PLLA-g-PAA scaffold than on either PLLA film or unmodified nanofibrous PLLA scaffold. The present work demonstrated that the applications of plasma treatment and hydrophilic AA grafting were effective to modify the surface of electrospun nanofibrous polymer scaffolds and that the altered surface characteristics significantly improved cell adhesion and proliferation.

• Journal of Radiation Industry
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• v.5 no.4
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• pp.365-370
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• 2011

Electrospun nanofibers prepared with synthetic biodegradable polymer have some limitations in regulating adhesion, proliferation, and spreading of cells because of their surface hydrophobicity and absence of cell-interaction. In this study, we functionalized the electrospun poly(L-lactide-co-${\varepsilon}$-caprolactone) (PLCL) nanofibers with acrylic acid (AAc) to modulate their surface hydrophilicity using electron-beam irradiation method and then measured grafting ratio of AAc, water contact angle, and ATR-FTIR of AAc-grafted nanofibers. A grafting ratio of AAc on the nanofibers was increased as irradiation dose and AAc concentration were increased. AAc-grafted nanofibers also have higher wettability than non-modified nanofibers. In conclusion, those surface-modified nanofibers may be an essential candidate to regulate cell attachment in tissue engineering applications.

• Macromolecular Research
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• v.14 no.5
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• pp.565-572
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• 2006

Recombinant human bone morphogenic protein-2 (rhBMP-2), which is known as one of the major local stimuli for osteogenic differentiation, was immobilized on the surface of hyaluronic acid (HA)-modified poly$(\varepsilon-caprolactone)$ (PCL) (HA-PCL) scaffolds to improve the attachment, proliferation, and differentiation of human bone marrow stem cells (hBMSCs) for bone tissue engineering. The rhBMP-2 proteins were directly immobilized onto the HA-modified PCL scaffolds by the chemical grafting the amine groups of proteins to carboxylic acid groups of HA. The amount of covalently bounded rhBMP-2 was measured to 1.6 pg/mg (rhBMP/HA-PCL scaffold) by using a sandwich enzyme-linked immunosorbant assay. The rhBMP-2 immobilized HA-modified-PCL scaffold exhibited the good colonization, by the newly differentiated osteoblasts, with a statistically significant increase of the rhBMP-2 release and alkaline phosphatase activity as compared with the control groups both PCL and HA-PCL scaffolds. We also found enhanced mineralization and elevated osteocalcin detection for the rhBMP-2 immobilized HA-PCL scaffolds, in vitro.

• Macromolecular Research
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• v.16 no.2
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• pp.139-148
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• 2008

Biodegradable and elastic poly(L-lactide-co-$\varepsilon$-caprolactone) (PLCL) was electrospun to prepare nanofibers, and N-isopropylacrylamide (NIPAAm) was then grafted onto their surfaces under aqueous conditions using $^{60}Co-{\gamma}$ irradiation. The graft yield increased with increasing irradiation dose from 5 to 10 kGy and the nanofibers showed a greater graft yield compared with the firms. SEM confirmed that the PLCL nanofibers maintained an interconnected pore structure after grafting with NIPAAm. However, overdoses of irradiation led to the excessive formation of homopolymer gels on the surface of thc PLCL nanofibers. The equilibrium swelling and deswelling ratio of the PNIPAAm-g-PLCL nanofibers (prepared with 10 kGy) was the highest among the samples, which was consistent with the graft yield results. The phase-separation characteristics of PNIPAAm in aqueous conditions conferred a unique temperature-responsive swelling behavior of PNIPAAm-g-PLCL nanofibers, showing the ability to absorb a large amount of water at < $32^{\circ}C$, and abrupt collapse when the temperature was increased to $40^{\circ}C$. In accordance with the temperature-dependent changes in swelling behavior, the release rate of indomethacin and FITC-BSA loaded in PNIPAAm-g-PLCL nanofibers by a diffusion-mediated process was regulated by the change in temperature. Both model drugs demonstrated greater release rate at $40^{\circ}C$ relative to that at $25^{\circ}C$. This approach of the temperature-controlled release of drugs from PNIPAAm-g-PLCL nanofibers using gamma-ray irradiation may be used to design drugs and protein delivery carriers in various biomedical applications.

• Polymer(Korea)
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• v.36 no.3
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• pp.357-363
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• 2012

Surface-modified poly(L-lactic acid) (PLLA) films and scaffolds were treated with plasma discharge in oxygen gas and subsequently subjected to $in$ $situ$ grafting of acrylic acid (AA) in order to increase the cell compatibility. The surface of AA-grafted PLLA was converted to hydroxyapatite (HA)-deposited PLLA in stimulated body fluid (SBF). After the samples were immersed in phosphate-buffered saline (PBS), fetal bovine serum (FBS), normal saline, or cell medium, the water contact angles were significantly reduced on the surface of HA-deposited PLLA. Chondrocyte and osteoblast showed a higher attachment and cell proliferation on HA-deposited surfaces and in particular, it was confirmed that chondrocyte was considerably influenced by HA. However, osteoblast showed better cell proliferation on the surfaces immersed in FBS, cell medium or HA-deposited surface. In addition, the cell proliferation in 3D scaffolds was much higher than that on film type, irrespective of chondrocyte and osteoblast. Therefore, such surface-modified PLLAs are expected to be useful as organic-inorganic hybrid scaffolds in the regeneration of cartilage and bone.