|
|
Synthesis and Characterization of Multifunctionalized Biodegradable Copolymers
Michlovská, Lenka ; Petrůj, Jaroslav (oponent) ; Lehocký,, Marián (oponent) ; Vojtová, Lucy (vedoucí práce)
This dissertation summarizes the current state-of-the-art in the field of biodegradable thermosensitive copolymers, which in the form of aqueous sol at room temperature change to gel at body temperature. These polymer materials are useful in medicine for injection application as drug carriers or resorbable implants for tissue regeneration. In experimental work, thermosensitive amphiphilic triblock copolymers based on hydrophobic biodegradable polylactide and polyglycolide and biocompatible hydrophilic polyethylene glycol (PLGA–PEG–PLGA) were synthesized using vacuum line apparatus. Prepared PLGA–PEG–PLGA copolymer with two phase transitions from sol-gel and gel-suspension was subsequently modified with itaconic anhydride. The resulting functionalized ITA/PLGA–PEG–PLGA/ITA copolymer contains at both ends of chains reactive double bonds suitable for further polymerization or crosslinking and functional carboxyl group for possible modification by biological active substances. Physical and chemical crosslinking were also investigated in terms of the ratio of hydrophilic and hydrophobic chains and with a view of the amount of bounded itaconic acid. Prepared aqueous solutions of synthesized ITA/PLGA–PEG–PLGA/ITA copolymer change to a gel at the temperature between 33 and 43 °C. The evaluated critical gel concentration and the critical gel temperature was 6 % w/v and 34 °C, respectively, for the copolymer with PLGA/PEG ratio equal to 2.5. When the copolymer was more hydrophobic, then start of gelation became earlier and gel was more hydrolytically stable. Gel stiffness increased with increasing PLGA/PEG ratio and it depends on methods and type of solvent used during purification of copolymer. Prepared ITA/PLGA–PEG–PLGA/ITA copolymers were crosslinked using blue light without further crosslinker. Hydrolytical stability of ITA modified samples was significantly improved and increased in direct proportion with the both increasing time of crosslinking and the amount of double bonds attached to polymer chains. Sample having 63 % of ITA crosslinked for 40 mins fully degraded in water after 32 days. By proton NMR relaxometry it was found that while the sample has been swelled in water (after 12 hours) the amount of unbonded water reduces and gradually diffuses into cavities on the surface of sample and slowly changed to both weakly bonded water and strongly bonded water to polymer chains. Weakly bonded water began release from sample and changed back to the free water, when sample start to degrade and nodes and gel network begin to break. However, the thermal stability of chemically crosslinked samples increased only up to 20 minutes of crosslinking time where approximately 57 % of double bonds of itaconic acid (at 1640 cm-1) were transformed to the new single RR'C–CHR'' bonds at 795 cm-1ones by making crosslinks proved by ATR-FTIR. Longer crosslinking time (above 30 minutes) led to changes in chemical structure by beta-scission of chain and partially by recombination of double bonds. Rediscovery of new double bonds in different place of the chain reduced both the thermal stability and glass transition temperature from 242 °C to 237 °C and from -2.2 to -5.8 °C, respectively. The proposed thesis shows how the polymer composition, modification by functional groups and physical conditions affect either the physical or the chemical crosslinking of prepared amphiphilic copolymers.
|
|
|
Optimalizace optických a transportních vlastností hydrogelů na bázi PVA
Zahrádka, Jan ; Kalina, Michal (oponent) ; Sedláček, Petr (vedoucí práce)
Hlavním cílem této bakalářské práce je navrhnout a optimalizovat vhodnou metodu přípravy transparentních, fyzikálně síťovaných hydrogelů s manipulovatelnými transportními vlastnostmi. Jako modelový gelotvorný materiál byl zvolen polyvinylalkohol (PVA) síťovaný metodou cyklického mražení a rozmražování. Z původně navržených tří mechanismů ovlivnění optických vlastností takto připravených PVA gelů byl na základě pilotních skríningových experimentů pro hlubší navazující analýzu vybrán vliv rychlosti mražení. Mechanické vlastnosti připravených hydrogelů byly analyzovány prostřednictvím reologie metodou amplitudového (strain sweep) testu. Vnitřní struktura byla vizualizována pomocí skenovací elektronové mikroskopie (SEM). Optimalizovaná technika přípravy transparentních PVA gelů byla následně využita pro přípravu gelů s interpenetrovanou polyelektrolytovou komponentou (poly(styren sulfonát)). Metodou difúzního páru s metylenovou modří jako difúzní sondou bylo poté experimentálně ověřeno, že hybridní hydrogelová síť disponuje modifikovanými transportními vlastnostmi.
|
|
|
Optimalizace optických a transportních vlastností hydrogelů na bázi PVA
Zahrádka, Jan ; Kalina, Michal (oponent) ; Sedláček, Petr (vedoucí práce)
Hlavním cílem této bakalářské práce je navrhnout a optimalizovat vhodnou metodu přípravy transparentních, fyzikálně síťovaných hydrogelů s manipulovatelnými transportními vlastnostmi. Jako modelový gelotvorný materiál byl zvolen polyvinylalkohol (PVA) síťovaný metodou cyklického mražení a rozmražování. Z původně navržených tří mechanismů ovlivnění optických vlastností takto připravených PVA gelů byl na základě pilotních skríningových experimentů pro hlubší navazující analýzu vybrán vliv rychlosti mražení. Mechanické vlastnosti připravených hydrogelů byly analyzovány prostřednictvím reologie metodou amplitudového (strain sweep) testu. Vnitřní struktura byla vizualizována pomocí skenovací elektronové mikroskopie (SEM). Optimalizovaná technika přípravy transparentních PVA gelů byla následně využita pro přípravu gelů s interpenetrovanou polyelektrolytovou komponentou (poly(styren sulfonát)). Metodou difúzního páru s metylenovou modří jako difúzní sondou bylo poté experimentálně ověřeno, že hybridní hydrogelová síť disponuje modifikovanými transportními vlastnostmi.
|
|
|
Synthesis and Characterization of Multifunctionalized Biodegradable Copolymers
Michlovská, Lenka ; Petrůj, Jaroslav (oponent) ; Lehocký,, Marián (oponent) ; Vojtová, Lucy (vedoucí práce)
This dissertation summarizes the current state-of-the-art in the field of biodegradable thermosensitive copolymers, which in the form of aqueous sol at room temperature change to gel at body temperature. These polymer materials are useful in medicine for injection application as drug carriers or resorbable implants for tissue regeneration. In experimental work, thermosensitive amphiphilic triblock copolymers based on hydrophobic biodegradable polylactide and polyglycolide and biocompatible hydrophilic polyethylene glycol (PLGA–PEG–PLGA) were synthesized using vacuum line apparatus. Prepared PLGA–PEG–PLGA copolymer with two phase transitions from sol-gel and gel-suspension was subsequently modified with itaconic anhydride. The resulting functionalized ITA/PLGA–PEG–PLGA/ITA copolymer contains at both ends of chains reactive double bonds suitable for further polymerization or crosslinking and functional carboxyl group for possible modification by biological active substances. Physical and chemical crosslinking were also investigated in terms of the ratio of hydrophilic and hydrophobic chains and with a view of the amount of bounded itaconic acid. Prepared aqueous solutions of synthesized ITA/PLGA–PEG–PLGA/ITA copolymer change to a gel at the temperature between 33 and 43 °C. The evaluated critical gel concentration and the critical gel temperature was 6 % w/v and 34 °C, respectively, for the copolymer with PLGA/PEG ratio equal to 2.5. When the copolymer was more hydrophobic, then start of gelation became earlier and gel was more hydrolytically stable. Gel stiffness increased with increasing PLGA/PEG ratio and it depends on methods and type of solvent used during purification of copolymer. Prepared ITA/PLGA–PEG–PLGA/ITA copolymers were crosslinked using blue light without further crosslinker. Hydrolytical stability of ITA modified samples was significantly improved and increased in direct proportion with the both increasing time of crosslinking and the amount of double bonds attached to polymer chains. Sample having 63 % of ITA crosslinked for 40 mins fully degraded in water after 32 days. By proton NMR relaxometry it was found that while the sample has been swelled in water (after 12 hours) the amount of unbonded water reduces and gradually diffuses into cavities on the surface of sample and slowly changed to both weakly bonded water and strongly bonded water to polymer chains. Weakly bonded water began release from sample and changed back to the free water, when sample start to degrade and nodes and gel network begin to break. However, the thermal stability of chemically crosslinked samples increased only up to 20 minutes of crosslinking time where approximately 57 % of double bonds of itaconic acid (at 1640 cm-1) were transformed to the new single RR'C–CHR'' bonds at 795 cm-1ones by making crosslinks proved by ATR-FTIR. Longer crosslinking time (above 30 minutes) led to changes in chemical structure by beta-scission of chain and partially by recombination of double bonds. Rediscovery of new double bonds in different place of the chain reduced both the thermal stability and glass transition temperature from 242 °C to 237 °C and from -2.2 to -5.8 °C, respectively. The proposed thesis shows how the polymer composition, modification by functional groups and physical conditions affect either the physical or the chemical crosslinking of prepared amphiphilic copolymers.
|
host ::
RSS.