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Crosslinking of thermosensitive functionalized copolymers by blue light
Křivánková, Nikola ; Michlovská, Lenka (oponent) ; Vojtová, Lucy (vedoucí práce)
The aim of this thesis was to prepare a hydrogel with a hybrid network of only one type of biodegradable copolymer. The new degradable hydrogel, containing both physical interactions (arising at physiological temperature of 37 °C) and chemical bonds initiated by blue light could be used as a resorbable wound dressing or as an injectable carrier with a gradual and well controlled drug release. Thermosensitive PLGA–PEG–PLGA copolymer synthesized by living ring-opening polymerization was subsequently functionalized with itaconic anhydride to form ITA/PLGA–PEG–PLGA/ITA light-sensitive and temperature-sensitive macromonomer. At 37 °C, the copolymer forms a micellar network due to hydrophobic interactions. Itaconic acid double bonds, which are attached to the ends of the copolymer chain, allow photochemical crosslinking of micelles with a view to increase the hydrolytic stability of novel hydrogel. The synthesized copolymers were characterized by GPC and 1H NMR methods. The formation of a physical network at physiological temperature was confirmed by rheological analysis. The physically crosslinked ITA/PLGA–PEG–PLGA/ITA hydrogel was then irradiated with blue light (430 – 490 nm) in the presence of a water soluble biocompatible photoinitiator LiTPO and chemically characterized by ATR-FTIR. The resulting hydrogel was transparent, flexible, absorbed up to 1176 % water, and was stable for 20 days in saline at 37 °C. The ITA/PLGA–PEG–PLGA/ITA hydrogel with hybrid network was also prepared in the presence of a crosslinker PEGDA, that significantly reduced the time required for crosslinking the hydrogel, but further analyses are needed to more fully understand the principles of the novel hydrogel types.
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The effect of biopolymers on adhesive and rheological properties of calcium phosphate bone cements
Scholz, David ; Michlovská, Lenka (oponent) ; Vojtová, Lucy (vedoucí práce)
This thesis deals with bone cement composed of tricalcium phosphate and thermosensitive copolymer. The main aim was to improve especially the adhesive properties of the cement by adding polysaccharide. The theoretical part of the thesis deals with the characterization of bone cements and their application and also a description of polymeric additives used in bone cements mainly focused on polysaccharides. In the experimental part, the prepared cements were characterized using rheology, powder X-ray diffraction and static mechanical tests on the cured cement alone and glued bones. Rheology was used to measure the setting time of the cements as a function of time and temperature. Furthermore, rheology was also intended to measure the adhesive properties of copolymer solutions, but this was not possible due to the nonreproducible results caused by inhomogeneity of the copolymer solutions with polysaccharide. Powder X-ray diffraction was used to measure the effect of polysaccharide on the conversion of tricalcium phosphate to calcium deficient hydroxyapatite. It was found out that polysaccharide does not significantly affect the conversion of tricalcium phosphate. Static mechanical tests were used to measure maximal compressive strength for the cured cement samples and also to measure the adhesion strength of glued bone samples. Cured samples with low polysaccharide concentration showed higher compressive strength compared to control samples. Inconclusive results were obtained during testing of the bone samples due to the complexity of the measurement. In particular, it concerns the preparation of bone samples and their gluing with bone cement.
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Crosslinking of thermosensitive functionalized copolymers by blue light
Křivánková, Nikola ; Michlovská, Lenka (oponent) ; Vojtová, Lucy (vedoucí práce)
The aim of this thesis was to prepare a hydrogel with a hybrid network of only one type of biodegradable copolymer. The new degradable hydrogel, containing both physical interactions (arising at physiological temperature of 37 °C) and chemical bonds initiated by blue light could be used as a resorbable wound dressing or as an injectable carrier with a gradual and well controlled drug release. Thermosensitive PLGA–PEG–PLGA copolymer synthesized by living ring-opening polymerization was subsequently functionalized with itaconic anhydride to form ITA/PLGA–PEG–PLGA/ITA light-sensitive and temperature-sensitive macromonomer. At 37 °C, the copolymer forms a micellar network due to hydrophobic interactions. Itaconic acid double bonds, which are attached to the ends of the copolymer chain, allow photochemical crosslinking of micelles with a view to increase the hydrolytic stability of novel hydrogel. The synthesized copolymers were characterized by GPC and 1H NMR methods. The formation of a physical network at physiological temperature was confirmed by rheological analysis. The physically crosslinked ITA/PLGA–PEG–PLGA/ITA hydrogel was then irradiated with blue light (430 – 490 nm) in the presence of a water soluble biocompatible photoinitiator LiTPO and chemically characterized by ATR-FTIR. The resulting hydrogel was transparent, flexible, absorbed up to 1176 % water, and was stable for 20 days in saline at 37 °C. The ITA/PLGA–PEG–PLGA/ITA hydrogel with hybrid network was also prepared in the presence of a crosslinker PEGDA, that significantly reduced the time required for crosslinking the hydrogel, but further analyses are needed to more fully understand the principles of the novel hydrogel types.
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