Preparation and irradiation of Pluronic F127-based thermoreversible and mucoadhesive hydrogel for local delivery of naproxen.

To improve physical properties and modulate the mucoadhesive hydrogel formulation via cross-linking by radiation, hydrogels were prepared using thermoreversible polymer Pluronic F127 (PF127) and mucoadhesive polymer carbopol 934P (C934P). As a model drug, naproxen was loaded in the hydrogel formulation. Sol-gel transition temperatures of hydrogels were measured by the tube-inversion method. The mucoadhesive potential of each formulation was determined by measuring the force required to detach the formulation from oral mucosal tissue. To strengthen the mechanical properties, the formulations were irradiated using an electronic beam. Drug release from the hydrogels and the cytotoxicity of each formulation were investigated. Sol-gel transition temperatures of the formulations were decreased by the addition of carbopol and were close to body temperature. The mucoadhesive force of the PF127 formulation was increased by addition of carbopol. In vitro release was sustained and the release rate was reduced by the addition of carbopol. After irradiation, the mucoadhesive force was increased about five-fold especially in the case of PF127 23% (9.7 kPa) and in vitro release was not sustained further. In conclusion, the use of a PF127 formulation incorporating a mucoadhesive polymer could effectively and safely improve oral residence time and absorption of naproxen. Irradiated formulations showed permanent cross-linking and improved properties.

Characterization and antimicrobial property of poly(acrylic acid) nanogel containing silver particle prepared by electron beam.

In this study, we developed a one step process to synthesize nanogel containing silver nanoparticles involving electron beam irradiation. Water-soluble silver nitrate powder is dissolved in the distilled water and then poly(acrylic acid) (PAAc) and hexane are put into this silver nitrate solution. These samples are irradiated by an electron beam to make the PAAc nanogels containing silver nanoparticles (Ag/PAAc nanogels). The nanoparticles were characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). In addition, the particle size and zeta-potential were confirmed by a particle size analyzer (PSA). The antibacterial properties of the nanogels were evaluated by paper diffusion test. The Ag/PAAc nanogels had an antibacterial effect against Escherichia coli and Staphylococcus aureus. The nanogels also demonstrated a good healing effect against diabetic ulcer. The size of the Ag/PAAc nanogels decreased with increasing irradiation doses, and the absolute value of the zeta potential increased with increasing irradiation doses. Also, the Ag/PAAc nanogels exhibited good antibacterial activity against both Gram-negative and Gram-positive bacteria. In in vivo wound healing, the Ag/PAAc nanogels have a good healing effect.

Characterization of silver nanoparticle in the carboxymethyl cellulose hydrogel prepared by a gamma ray irradiation.

In this study, carboxymethyl cellulose (CMC) hydrogels were traditionally prepared by gamma-ray with an absorbed dose of 50 kGy from a 60Co source. The CMC hydrogels were absorbed and swelled in silver nitrate aqueous solution (0.01 M) by dipping for 1 hour, and then irradiated by gamma-ray at various doses to form silver nanoparticles (Ag NPs). The UV-Vis analysis indicated that the concentration of Ag NPs was enhanced by increasing of absorbed dose from 1 to 5 kGy in this situ reducing system. The FE-SEM and XPS measurements provided further evidence for the successful formation of Ag NPs. These CMC hydrogels stabilized Ag NPs also have been investigated for inhibiting the growth of Staphylococcus aureus and Escherichia coli strains in liquid as well as on solid growth media. The antibacterial tests indicated that the hydrogels containing Ag NPs have antibacterial activity.

Patterning of TiO2 particles on poly(dimethyl siloxane) films by using proton irradiation and liquid-phase deposition process.

Micropatterning of titanium dioxide (TiO2) on the surface of thin poly(dimethyl siloxane) (PDMS) films was described by means of proton irradiation and liquid-phase deposition (LPD) techniques. The surface of thin PDMS films was irradiated with accelerated proton ions through a pattern mask in the absence or presence of oxygen in order to create hydrophilically/hydrophobically patterned surfaces. The results of the surface analysis revealed that the PDMS films irradiated at the fluence of 1 x 10(15) ions cm-2 in the presence of oxygen showed the highest hydrophilicity. The LPD of TiO2 particles on the patterned PDMS film surface showed a selective deposition of TiO2 on the irradiated regions, leading to well defined TiO2 micropatterns. The crystal structure of the formed TiO2 films was found to be in an anatase phase by X-ray diffraction analysis. This process can be applied for patterning various metal and metal oxide particles on a polymer substrate.

High density polyethylene membrane filled with alumina prepared by a gamma ray irradiation.

High density polyethylene (HDPE) membrane filled with alumina particles was prepared by a wet process for a Li-ion secondary battery. Soybean oil and dibutyl phthalate (DBP) were premixed as the co-diluents. Gamma ray irradiation was used for crosslinking of HDPE. The HDPE membrane filled with alumina particles had excellent mechanical property and thermal stability due to the alumina particles and irradiation crosslinking. The tensile strength of the membrane increased with an increased amount of alumina up to 15 wt%. The thermal shrinkage of the membrane decreased with an increased amount of alumina up to 15 wt%. The electrochemical stability of the irradiated membrane after extraction was improved with irradiation dose up to 50 kGy.

Patterned immobilization of biomolecules on a polymer surface functionalized by radiation grafting.

Patterned graft polymerization of a functional monomer on a hydrophobic polymer surface was proposed for biomolecule patterning. A poly(vinylidene fluoride) (PVDF) film surface was selectively activated by ion implantation through a pattern mask and acrylic acid (AA) was then graft polymerized onto the activated regions of the PVDF surfaces. The peroxide concentration on the implanted surface depended on the fluence, which had a considerable effect on the grafting degree of AA. Afterwards, amine-functionalized biotin and probe DNA were immobilized on the poly(acrylic acid)-grafted regions of the PVDF surfaces. Specific binding of biotin with streptavidin and hybridization of probe DNA with complimentary DNA proved successful protein and DNA patterning and well-defined 50 microm dot-type patterns of the streptavidin and DNA were obtained. These results confirmed the potential of this strategy for patterning of various biomolecules.

Simple and biocompatible micropatterning of multiple cell types on a polymer substrate by using ion implantation.

A noncytotoxic procedure for the spatial organization of multiple cell types remains as a major challenge in tissue engineering. In this study, a simple and biocompatible micropatterning method of multiple cell types on a polymer surface is developed by using ion implantation. The cell-resistant Pluronic surface can be converted into a cell-adhesive one by ion implantation. In addition, cells show different behaviors on the ion-implanted Pluronic surface. Thus this process enables the micropatterning of two different cell types on a polymer substrate. The micropatterns of the Pluronic were formed on a polystyrene surface. Primary cells adhered to the spaces of the bare polystyrene regions separated by the implanted Pluronic patterns. Secondary cells then adhered onto the implanted Pluronic patterns, resulting in micropatterns of two different cells on the polystyrene surface.

Micropatterning of polymer-embedded metal nanoparticles by an ion beam contact lithography.

A convenient and effective method to pattern polymer-embedded metal nanoparticles by ion irradiation has been developed. The thin Pluronic films containing silver nitrate as a precursor of silver nanoparticles were irradiated through a pattern mask with accelerated proton (H+) ions. It was found from the UV-Vis measurement that the formation of silver nanoparticles in the Pluronic matrix was dependant on the amount of silver nitrate. The 50 microm line (pitch 150 microm) patterns of the Pluronic containing silver nanoparticles were obtained with the thin film irradiated to 1 x 10(16) ions/cm2. The heat treatment effect on the morphology of the patterns was investigated by using a scanning electron microscope with an energy dispersive X-ray spectrometer. The results confirmed that the silver nanoparticles were successfully embedded in the Pluronic patterns and the patterns were changed into large silver particles by a heat treatment above 350 degrees C.

Functionalization of carbon nanotubes by radiation-induced graft polymerization.

Multi-walled carbon nanotubes (MWCNTs) were functionalized by radiation-induced graft polymerization of acrylic acid onto the surface of MWCNTs in order to improve their dispersibility in water. 1H NMR, Raman spectroscopy, TEM, and TGA techniques were used to characterize the resulting functionalized MWCNTs. The grafting degree was dependent on the grafting conditions such as the absorbed dose and the monomer concentration. The experimental results confirmed that poly(acrylic acid) chains were successfully grafted onto the surface of the MWCNTs. The poly(acrylic acid)-grafted MWCNTs showed a much better water dispersibility than the pristine MWCNTs.

Micropatterning of poly(vinyl pyrrolidone)/silver nanoparticle thin films by ion irradiation.

This study describes a new patterning method of poly(vinyl pyrrolidone) (PVP) containing silver nanoparticles by using ion irradiation. The thin films prepared from PVP/silver nanoparticle solutions were irradiated through a mask with accelerated H+ ions. Well-defined 50 microm line (pitch 150 microm) patterns were generated from the film irradiated at 1 x 10(16) ions/cm2. The heat treatment effect on the morphology of the patterns was investigated by using a scanning electron microscope with an energy dispersive X-ray spectrometer. The results confirmed that the silver nanoparticles were successfully immobilized in the PVP patterns and the patterns were changed into silver particles by heat treatment above 300 degrees C.

Modulation of spreading, proliferation, and differentiation of human mesenchymal stem cells on gelatin-immobilized poly(L-lactide-co--caprolactone) substrates.

Controlled adhesion and continuous growth of human mesenchymal stem cells (hMSCs) are essential for scaffold-based delivery of hMSCs in tissue engineering applications. The main goal of this study is to develop biofunctionalized synthetic substrates to actively control adhesion, spreading, and proliferation of hMSCs. gamma-Ray irradiation was employed to graft acrylic acid (AAc) to biodegeradable poly(L-lactide-co--caprolactone) (PLCL) films. Gelatin, a natural polymer, was then immobilized on the AAc grafted PLCL film (AAc-PLCL) to induce biomimetic interactions with the cells. The graft yield of AAc increased as the irradiation dose and AAc concentration increased, and the presence of gelatin (gelatin-AAc-PLCL) following immobilization was confirmed using ESCA. To investigate cell responses, hMSCs isolated from a human mandible were cultured on the various substrates and their adhesion, spreading, and proliferation were examined. After three days of culture, the DNA concentration from the cells cultured on gelatin-AAc-PLCL film was 2.9-fold greater than that on the PLCL film. Immunofluorescent staining of hMSCs cultured on the gelatin-AAc-PLCL films demonstrated homogeneous localization of F-Actin and vinculin in their cytoplasm, while mature adhesive structure was not observed from the cells cultured on other substrates. Furthermore, the ratio of projected area of adherent single cells on gelatin-AAc-PLCL films was significantly larger (116.80 +/- 12.78%) than that on the PLCL films (30.11 +/- 5.07%). Our results suggest that gelatin-immobilized PLCL substrates may be potentially used in tissue engineering, particularly as a stem cell delivery carrier for the regeneration of target tissue.

Chestnut Honey Impregnated Carboxymethyl Cellulose Hydrogel for Diabetic Ulcer Healing.

Honey-based wound dressings have attracted a lot of attention from modern scientists owing to their anti-inflammatory and antibacterial effects without antibiotic resistance. Such dressings also promote moist wound healing, and have been considered natural, abundant, and cheap materials for folk marketing. This study investigated the various behaviors and characteristics of chestnut honey-impregnated carboxymethyl cellulose sodium hydrogel paste (CH⁻CMC) as a therapeutic dressing, such as its moist retention, antibacterial activity for inhibiting the growth of Staphylococcus aureus and Escherichia coli, and the rate of wound healing in db/db mice. The results provide good evidence, suggesting that CH⁻CMC has potential as a competitive candidate for diabetic ulcer wound healing.

Radiation-Induced Grafting with One-Step Process of Waste Polyurethane onto High-Density Polyethylene.

The recycling of waste polyurethane (PU) using radiation-induced grafting was investigated. The grafting of waste PU onto a high-density polyethylene (HDPE) matrix was carried out using a radiation technique with maleic anhydride (MAH). HDPE pellets and PU powders were immersed in a MAH-acetone solution. Finally, the prepared mixtures were irradiated with an electron beam accelerator. The grafted composites were characterized by Fourier transformed infrared spectroscopy (FT-IR), surface morphology, and mechanical properties. To make a good composite, the improvement in compatibility between HDPE and PU is an important factor. Radiation-induced grafting increased interfacial adhesion between the PU domain and the HDPE matrix. When the absorbed dose was 75 kGy, the surface morphology of the irradiated PU/HDPE composite was nearly a smooth and single phase, and the elongation at break increased by approximately three times compared with that of non-irradiated PU/HDPE composite.

Preparation of High Density Polyethylene/Waste Polyurethane Blends Compatibilized with Polyethylene-Graft-Maleic Anhydride by Radiation.

Polyurethane (PU) is a very popular polymer that is used in a variety of applications due to its good mechanical, thermal, and chemical properties. However, PU recycling has received significant attention due to environmental issues. In this study, we developed a recycling method for waste PU that utilizes the radiation grafting technique. Grafting of waste PU was carried out using a radiation technique with polyethylene-graft-maleic anhydride (PE-g-MA). The PE-g-MA-grafted PU/high density polyethylene (HDPE) composite was prepared by melt-blending at various concentrations (0-10 phr) of PE-g-MA-grafted PU. The composites were characterized using fourier transform infrared spectroscopy (FT-IR), and their surface morphology and thermal/mechanical properties are reported. For 1 phr PU, the PU could be easily introduced to the HDPE during the melt processing in the blender after the radiation-induced grafting of PU with PE-g-MA. PE-g-MA was easily reacted with PU according to the increasing radiation dose and was located at the interface between the PU and the HDPE during the melt processing in the blender, which improved the interfacial interactions and the mechanical properties of the resultant composites. However, the elongation at break for a PU content >2 phr was drastically decreased.

Hyaluronic acid/chondroitin sulfate-based hydrogel prepared by gamma irradiation technique.

Gamma-ray irradiation of novel hydrogels was used to develop a biocompatible hydrogel system for skin tissue engineering. These novel hydrogels are composed of natural polymers including hyaluronic acid (HA) and chondroitin sulfate (CS), and the synthetic polymer, poly(vinyl alcohol) (PVA). The γ-ray irradiation method has advantages, such as relatively simple manipulation without need of any extra reagents for polymerization and cross-linking. We synthesized HA and CS derivatives with polymerizable residues. The HA/CS/PVA hydrogels with various compositions were prepared by using γ-ray irradiation technique and their physicochemical properties were investigated to evaluate the feasibility of their use as artificial skin substitutes. HA/CS/PVA hydrogels showed an 85-88% degree of gelation under 15 kGy radiation. All HA/CS/PVA hydrogels exhibited more than 90% water content and reached an equilibrium swelling state within 24h. Hydrogels with higher concentrations of hyaluronidase solution and HA/CS content had proportionally higher enzymatic degradation rates. The drug release behaviors from HA/CS/PVA hydrogels were influenced by the composition of the hydrogel and drug properties. Exposure of human keratinocyte (HaCaT) culture to the extracts of HA/CS/PVA hydrogels did not significantly affect the cell viability. All HaCaT cell cultures exposed to the extracts of HA/CS/PVA hydrogels exhibited greater than 92% cell viability. The HaCaT growth in HA/CS/PVA hydrogels gradually increased as a function of culture time. After 7 days, the HaCaT cells in all HA/CA/PVA hydrogels exhibited more than 80% viability compared to the control group HaCaT culture on a culture plate.

Topical treatment of the buccal mucosa and wounded skin in rats with a triamcinolone acetonide-loaded hydrogel prepared using an electron beam.

In this study, a triamcinolone acetonide-loaded hydrogel was prepared by electron beam irradiation and evaluated for use as a buccal mucoadhesive drug delivery system. A poloxamer was modified to have vinyl end groups for preparation of the hydrogel via an irradiation cross-linking reaction. Carbopol was introduced to improve the mucoadhesive properties of the hydrogel. The in vitro release of triamcinolone acetonide from the hydrogel was examined at 37 °C. To investigate the topical therapeutic effect of triamcinolone acetonide on wounded rat skin and buccal mucosa, the appearance and histological changes were evaluated for 15 days after treatment with saline, triamcinolone acetonide solution, triamcinolone acetonide hydrogel, and blank hydrogel, respectively. Triamcinolone acetonide was released constantly from the gel formulation at 37 °C and reach 100% at about 48 h. After 15 days, in the skin of the group treated with the triamcinolone acetonide-loaded hydrogel, the wound was almost completely free of crust and a number of skin appendages, including hair follicles, had formed at the margins of the tissue. Moreover, the inflammatory response in the buccal mucosa was milder than that in the other groups, and the wound surface was completely covered with regenerating, hyperkeratotic, thickened epithelial cells. Our results indicate that the triamcinolone-acetonide hydrogel showed sustained drug release behavior, while causing no significant histopathological changes in buccal and skin tissues. Therefore, this hydrogel system may be a powerful means of drug delivery for buccal administration with controlled release and no tissue irritation.

Efficient immobilization and patterning of biomolecules on poly(ethylene terephthalate) films functionalized by ion irradiation for biosensor applications.

The surface of a poly(ethylene terephthalate) (PET) film was selectively irradiated with proton beams at various fluences to generate carboxylic acid groups on the surface; the resulting functionalized PET surface was then characterized in terms of its wettability, chemical structure, and chemical composition. The results revealed that (i) carboxylic acid groups were successfully generated in the irradiated regions of the PET surface, and (ii) their relative amounts were dependent on the fluence. A capture biomolecule, anthrax toxin probe DNA, was selectively immobilized on the irradiated regions on the PET surface. Cy3-labeled DNA as a target biomolecule was then hybridized with the probe DNA immobilized on the PET surface. Liver-cancer-specific α-fetoprotein (AFP) antigen, as a target biomolecule, was also selectively immobilized on the irradiated regions on the PET surface. Texas Red-labeled secondary antibody was then reacted with an AFP-specific primary antibody prebound to the AFP antigen on the PET surface for the detection of the target antigen, using an indirect immunoassay method. The results revealed that (i) well-defined micropatterns of biomolecules were successfully formed on the functionalized PET surfaces and (ii) the fluorescence intensity of the micropatterns was dependent mainly on the concentrations of the target DNA hybridized to the probe DNA and the target AFP antigen immobilized on the PET films. The lowest detectable concentrations of the target DNA and target AFP antigen in this study were determined to be 4 and 16 ng/mL, respectively, with the PET film prepared at a fluence of 5 × 10(14) ions/cm(2).

Surface morphology control of polymer films by electron irradiation and its application to superhydrophobic surfaces.

A simple and controllable one-step method to fabricate superhydrophobic surfaces on poly(tetrafluoroethylene) (PTFE) films is developed on the base of electron irradiation. When the thickness of PTFE films is higher than the penetration depth of electron beams, electrical charging occurs at the surface of the films because of the imbalance between the accumulation of incident electrons and the emission of secondary electrons. Local inhomogeneity of charge distribution due to this electrical charging results in the nonuniform decomposition of PTFE molecular bonds. As electron fluence increases, surface morphology and surface roughness of the films are dramatically changed. An extremely rough surface with micrometer-sized pores is produced on the surface of PTFE films by electron irradiation at a fluence higher than 2.5 × 10(17) cm(-2).Because of high surface roughness, the irradiated PTFE films exhibit superhydrophobic property with a water contact angle (CA) greater than 150° at fluences ranging from 4 × 10(17) to 1 × 10(18) cm(-2). The surface morphology and corresponding water CA can be controlled by simply changing the electron fluence. This electron irradiation method can be applicable to the fabrication of superhydrophobic surfaces using other low-surface-energy materials including various fluoropolymers.

Patterning of biomolecules on a poly(epsilon-caprolactone) film surface functionalized by ion implantation.

Biomolecule patterning is important due to its potential applications in biodevices, tissue engineering, and drug delivery. In this study, we developed a new method for a biomolecular patterning on poly(epsilon-caprolactone) (PCL) films based on ion implantation. Ion implantation on a PCL film surface resulted in the formation of carboxylic acid groups. The generated carboxylic acid groups were used for the covalent immobilization of amine-functionalized p-DNA, followed by hybridization with fluorescently tagged c-DNA. Biotin-amine was also covalently immobilized on the carboxylic acid generated PCL surfaces. Successful biotin-specific binding of streptavidin further confirmed the potential of this strategy for patterning of various biomolecules.

Development of electroactive and elastic nanofibers that contain polyaniline and poly(L-lactide-co-epsilon-caprolactone) for the control of cell adhesion.

In this work, electrically conductive polyaniline (PAni) doped with camphorsulfonic acid (CPSA) is blended with poly(L-lactide-co-epsilon-caprolactone) (PLCL), and then electrospun to prepare uniform nanofibers. The CPSA-PAni/PLCL nanofibers show a smooth fiber structure without coarse lumps or beads and consistent fiber diameters (which range from 100 to 700 nm) even with an increase in the amount of CPSA-PAni (from 0 to 30 wt.-%). However, the elongation at break decreases from 391.54 +/- 9.20% to 207.85 +/- 6.74% when 30% of CPSA-PAni is incorporated. Analysis of the surface of the nanofibers demonstrates the presence of homogeneously blended CPSA-PAni. Most importantly, a four-point probe analysis reveals that electrical properties are maintained in the nanofibers where the conductivity is significantly increased from 0.0015 to 0.0138 S x cm(-1) when the nanofibers are prepared with 30% CPSA-PAni. The cell adhesion tests using human dermal fibroblasts, NIH-3T3 fibroblasts, and C2C12 myoblasts demonstrate significantly higher adhesion on the CPSA-PAni/PLCL nanofibers than pure PLCL nanofibers. In addition, the growth of NIH-3T3 fibroblasts is enhanced under the stimulation of various direct current flows. The CPSA-PAni/PLCL nanofibers with electrically conductive properties may potentially be used as a platform substrate to study the effect of electrical signals on cell activities and to direct desirable cell function for tissue engineering applications.