• Asian Pacific Journal of Cancer Prevention
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• v.15 no.1
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• pp.49-54
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• 2014

Background: Hydrogels are a class of polymers that can absorb water or biological fluids and swell to several times their dry volume, dependent on changes in the external environment. In recent years, hydrogels and hydrogel nanocomposites have found a variety of biomedical applications, including drug delivery and cancer treatment. The incorporation of nanoparticulates into a hydrogel matrix can result in unique material characteristics such as enhanced mechanical properties, swelling response, and capability of remote controlled actuation. Materials and Methods: In this work, synthesis of hydrogel nanocomposites containing magnetic nanoparticles are studied. At first, magnetic nanoparticles ($Fe_3O_4$) with an average size 10 nm were prepared. At second approach, thermo and pH-sensitive poly (N-isopropylacrylamide -co-methacrylic acid-co-vinyl pyrrolidone) (NIPAAm-MAA-VP) were prepared. Swelling behavior of co-polymer was studied in buffer solutions with different pH values (pH=5.8, pH=7.4) at $37^{\circ}C$. Magnetic iron oxide nanoparticles ($Fe_3O_4$) and doxorubicin were incorporated into copolymer and drug loading was studied. The release of drug, carried out at different pH and temperatures. Finally, chemical composition, magnetic properties and morphology of doxorubicin-loaded magnetic hydrogel nanocomposites were analyzed by FT- IR, vibrating sample magnetometry (VSM), scanning electron microscopy (SEM). Results: The results indicated that drug loading efficiency was increased by increasing the drug ratio to polymer. Doxorubicin was released more at $40^{\circ}C$ and in acidic pH compared to that $37^{\circ}C$ and basic pH. Conclusions: This study suggested that the poly (NIPAAm-MAA-VP) magnetic hydrogel nanocomposite could be an effective carrier for targeting drug delivery systems of anti-cancer drugs due to its temperature sensitive properties.

• Polymer(Korea)
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• v.32 no.2
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• pp.163-168
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• 2008

Biomedical scaffold for tissue regeneration was fabricated by one of rapid prototyping processes, bioplotting system, with a biodegradable and biocompatible poly($\varepsilon$-carprolactone)(PCL). Through dynamic mechanical test, it was observed that the PCL scaffold manufactured by the bioplotting process has the superior mechanical properties compared to the conventional scaffold fabricated by a salt-leaching process, and the plotted scaffold could be employed as a potential scaffold to regenerating hard and soft tissue. The plotted scaffold was consisted of porous structures. which were interconnected with each pore to help cells be easily adhered and proliferated in the wall of pore tunnels, and metabolic nutrients can be transported within the matrix. By using the plotting system, we could adjust the pore size, porosity, strand pitch, and, strand diameter of PCL scaffolds, which were important parameters to control mechanical properties of the scaffolds, and consequently we could determine that the mechanically controlled scaffolds could be used as a matching scaffold for any required mechanical properties of the target organ. The fabricated 3D PCL scaffold showed enough possibility as a 3D biomedical scaffold, which was cell-cultured with chondrocytes.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.749-757
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• 2019

Methyltrimethoxysilane (MTMS) and trimethylethoxysilane (TMES) as starting materials were dissolved in various types of solvents, and hydrolysis with water and polycondensation reaction were carried out using various types of catalysts to prepare non-fluorinated water-repellent coating solutions. The coating solutions were spin-coated on cold-rolled steel sheets, and thermally cured to prepare water-repellent coating films. The effect of types of catalysts and solvents on the water repellency of the resulting coating films was investigated during this process. When hydrochloric acid and nitric acid, which are strong acids, were used as catalysts, the solutions showed a white opaque state due to the aggregation of siloxane polymers. On the other hand, when acetic acid, phosphoric acid, and oxalic acid, which are weak acids, were used, they were in a stable and transparent state without precipitation. As a result, the contact angles of the coated films, prepared from hydrochloric acid and nitric acid, were $58^{\circ}$ and $92^{\circ}$, respectively, showing low water repellency. On the other hand, when acetic acid, phosphoric acid, and oxalic acid were used, the contact angles of the coated films were $101^{\circ}$, $103^{\circ}$ and $116^{\circ}$, respectively, showing high water repellency. In addition, when isopropanol and ethanol were used as solvents, phase separation occurred in the solutions due to the aggregation of siloxane polymers. On the other hand, when methanol, ethyl acetate, and methyl ethyl ketone were used as solvents, the solutions were transparent and showed a stable state without sedimentation.

• Macromolecular Research
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• v.16 no.1
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• pp.57-61
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• 2008

Chitosan is normally acylated and subsequently conjugated with drugs for biomedical applications. This study examined the relationship between the succinylation and gelation behaviors of glycol chitosan. Glycol chitosan was acylated with succinic anhydride under a wide variety of reaction conditions, such as different molar ratios of succinic anhydride to glucosamine, different methanol content in the reaction media, and different reaction temperatures. Among these reaction parameters, the methanol content in the solvent played an important role in determining the regioseletive succinylating site. N-succinylation and N-N cross-linking occurred regardless of the reaction conditions. However, O-succinylation was observed under specific conditions, i.e. a methanol content> 0.6 (v/v) and a reaction temperature> $25^{\circ}C$. O-succinylation accelerated the N-O cross-linking of glycol chitosan, and led to gelation. The N-succinylated glycol chitosans were water-soluble, whereas the N-and O-succinylated glycol chitosans fonned a gel. These physico-chemical structural differences in the succinylated glycol chitosans would definitely influence subsequent drug-conjugation reactions and consequently the drug loading and release kinetics.

• Biomaterials and Biomechanics in Bioengineering
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• v.2 no.1
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• pp.23-32
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• 2015

Facile immobilization of growth factors in hyaluronic acid (HA) hydrogels using dual enzymes is reported in the paper. The hydrogels were formed by using horseradish peroxidase (HRP) and hydrogen peroxide ($H_2O_2$) and transforming growth factor-${\beta}3$ (TGF-${\beta}3$) was covalently conjugated on the hydrogels in situ using tyrosinase (Ty) without any modifications. For the preparation of hydrogels, HA was grafted with poly(ethylene glycol) (PEG), which was modified with a tyrosine. The gelation times of the HA hydrogels were ranging from 415 to 17 s and the storage moduli was dependent on the concentration of $H_2O_2$ and Ty (470-1600 Pa). A native TGF-${\beta}3$ (200 ng/mL) was readily encapsulated in the HA hydrogels and 17% of the TGF-${\beta}3$ was released over 1 month at the Ty concentration of 0.5 KU/mL, while the release was faster when 0.3 KU/mL of Ty was used for the encapsulation (27%). It can be suggested that the growth factors resident in the hydrogels for a long period of time may lead cells proliferating and differentiating, whereas the growth factors that are initially released from the hydrogels can induce the ingrowth of cells into the matrices. Therefore, the dual enzymatic methods as facile gel forming and loading of various native growth factors or therapeutic proteins could be highly promising for tissue regenerative medicines.

• Macromolecular Research
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• v.16 no.6
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• pp.517-523
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• 2008

A RGD (Arg-Gly-Asp) conjugated chitosan hydrogel was used as a cell-supporting scaffold for articular cartilage regeneration. Thermosensitive chitosan-Pluronic (CP) has potential biomedical applications on account of its biocompatibility and injectability. A RGD-conjugated CP (RGD-CP) copolymer was prepared by coupling the carboxyl group in the peptide with the residual amine group in the CP copolymer. The chemical structure of RGD-CP was characterized by $^1H$ NMR and FT IR. The concentration of conjugated RGD was quantified by amino acid analysis (AAA) and rheology of the RGD-CP hydrogel was investigated. The amount of bound RGD was $0.135{\mu}g$ per 1 mg of CP copolymer. The viscoelastic parameters of RGD-CP hydrogel showed thermo-sensitivity and suitable mechanical strength at body temperature for cell scaffolds (a> 100 kPa storage modulus). The viability of the bovine chondrocyte and the amount of synthesized glycosaminoglycans (GAGs) on the RGD-CP hydrogels were evaluated together with the alginate hydrogels as a control over a 14 day period. Both results showed that the RGD-CP hydrogel was superior to the alginate hydrogel. These results show that conjugating RGD to CP hydro gels improves cell viability and proliferation, including extra cellular matrix (ECM) expression. Therefore, RGD conjugated CP hydrogels are quite suitable for a chondrocyte culture and have potential applications to the tissue engineering of articular cartilage tissue.

• Macromolecular Research
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• v.17 no.3
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• pp.174-180
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• 2009

Chemical modification of titanium/titanium oxide (Ti/$TiO_2$) substrates has recently gained a great deal of attention because of the applications of Ti/$TiO_2$-based materials to biomedical areas. The reported modification methods generally involve passive coating of Ti/$TiO_2$ substrates with protein-resistant materials, and poly(ethylene glycol) (PEG) has proven advantageous for bestowing a nonbiofouling property on the surface of Ti/$TiO_2$. However, the wider applications of Ti/$TiO_2$ based materials to biomedical areas will require the introduction of biologically active moieties onto Ti/$TiO_2$, in addition to nonbiofouling property. In this work, we therefore utilized surface-initiated polymerization to coat the Ti/$TiO_2$ substrates with polymers presenting the nonbiofouling PEG moiety and subsequently conjugated biologically active compounds to the PEG-presenting, polymeric films. Specifically, a Ti/$TiO_2$ surface was chemically modified to present an initiator for atom transfer radical polymerization, and poly(ethylene glycol) methacrylate (pEGMA) was polymerized from the surface. After activation of hydroxyl groups of poly(pEGMA) (pPEGMA) with N,N'-disuccinimidyl carbonate, biotin, a model compound, was conjugated to the pPEGMA films. The reactions were confirmed by infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle goniometry, and ellipsometry. The biospecific binding of target proteins was also utilized to generate micropatterns of proteins on the Ti/$TiO_2$ surface.

• Journal of Biomedical Engineering Research
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• v.34 no.3
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• pp.111-116
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• 2013

Finite element analysis(FEA) has been extensively applied in the analyses of biomechanical properties of stents. Geometrically, a closed-cell stent is an assembly of a number of repeated unit cells and exhibits periodicity in both longitudinal and circumferential directions. This study concentrates on various parameters of the FEA models for the analysis of drug-eluting biodegradable polymeric stents for application to the treatment of coronary artery disease. In order to determine the mechanical characteristics of biodegradable polymeric stents, FEA was used to model two different types of stents: tubular stents(TS) and helicoidal stents(HS). For this modeling, epigallocatechin-3-O-gallate (EGCG)-eluting poly[(L-lactide-co-${\varepsilon}$-caprolactone), PLCL] (E-PLCL) was chosen as drug-eluting stent materials. E-PLCL was prepared by blending PLCL with 5% EGCG as previously described. In addition, the effects of EGCG blending on the mechanical properties of PLCL were investigated for both types of stent models. EGCG did not affect tensile strength at break, but significantly increased elastic modulus of PLCL. It is suggested that FEA is a cost-effective method to improve the design of drug-eluting biodegradable polymeric stents.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.335-335
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• 2011

Instability of a thin film attached to a compliant substrate often leads to emergence of exquisite wrinkle patterns with length scales that depend on the system geometry and applied stresses. However, the patterns that are created using the current techniques in polymer surface engineering, generally have low aspect ratio of undulation amplitude to wavelength, thus, limiting their application. Here, we present a novel and effective method that enables us to create wrinkles with a desired wavelength and high aspect ratio of amplitude over wavelength as large as to 2.5:1. First, we create buckle patterns with high aspect ratio of amplitude to wavelength by deposition of an amorphous carbon film on a surface of a soft polymer poly(dimethylsiloxane) (PDMS). Amorphous carbon films are used as a protective layer in structural systems and biomedical components, due to their low friction coefficient, strong wear resistance against, and high elastic modulus and hardness. The deposited carbon layer is generally under high residual compressive stresses (~1 GPa), making it susceptible to buckle delamination on a hard substrate (e.g. silicon or glass) and to wrinkle on a flexible or soft substrate. Then, we employ glancing angle deposition (GLAD) for deposition of a high aspect ratio patterns with amorphous carbon coating on a PDMS surface. Using this method, pattern amplitudes of several nm to submicron size can be achieved by varying the carbon deposition time, allowing us to harness patterned polymers substrates for variety of application. Specifically, we demonstrate a potential application of the high aspect wrinkles for changing the surface structures with low surface energy materials of amorphous carbon coatings, increasing the water wettability.