Publication: Dopamin aşılanmış blok kopolimerlerin hazırlanması, karakterizasyonu ve uygulamaları
Abstract
Amaç: Bu çalışmada, polidopaminin (PDA) doğal doku yapışkan özelliği ile ısıya duyarlı bir polimer olan poli(N-izopropilakrilamid)’in (PNIPAM) blok kopolimerinin sentezi kontrollü/ “yaşayan” polimerizasyon yöntemlerinden tersinir katılma-ayrılma zincir-transfer (Reversible Addition–Fragmentation Chain Transfer, RAFT) polimerizasyonuyla geliştirilmiştir. Malzeme bilimi, biyoteknoloji ve çevre mühendisliği açısından umut vadeden biyouyumluluğu yüksek antimikrobiyal uygulamalarda yeni nesil çözüm sunma potansiyeline sahip bir blok kopolimer sisteminin eldesi amaçlanmıştır. Gereç ve Yöntem: Tez kapsamında önce aldehit grubuna sahip p-(2-metakriloksietil)benzaldehit) monomeri (MAEBA) ve polimerizasyonun gerçekleşmesi için kullanılan bütil 2-siyanopropan2-il-karbonotritiyoat (CBPA) RAFT ajanının sentezleri gerçekleştirilmiştir. Sonrasında ticari olarak temin edilen N-izopropilakrilamid monomeri kullanılarak azobisizobütironitril ve CBPA varlığında homopolimer (PNIPAM) sentezlenmiştir. Homopolimerin macro-RAFT ajanı olarak kullanılması ile de MAEBA monomeri varlığında ile aldehit fonksiyonuna sahip bloğun sentezi gerçekleştirilmiştir. Elde edilen blok kopolimere Shiff bazı kimyasından yararlanılarak bazik ortamda trietil amin varlığında dopamin konjugasyonu gerçekleştirilmiştir. Bulgular: Sentezlenen tüm ara bileşiklerin ve polimerlerin yapıları spektroskopik ve kromatografik yöntemlerle aydınlatılmıştır. Dopamin aşılanmış blok kopolimerin fizyolojik pH değeri olan pH 7,4’de 72 saat boyunca dopamin salım profili incelendi. 72 saat sonunda salınan toplam dopamin miktarı %53,30 ± 9,38 olarak bulunmuştur. Sonuç: Tez kapsamında sentezlenen dopamin aşılanmış blok kopolimer antimikrobiyal uygulamalar ve dopaminin yüzey tutunma özelliğinden faydalanarak implant ara yüzlerinde öncü kompozit malzemelerden biri olarak kullanılmak üzere umut vaadetmektedir.
Objective: This study employed reversible addition-fragmentation chain transfer (RAFT) polymerization, a controlled living polymerization method, to synthesize poly(Nisopropylacrylamide) (PNIPAM), a heat-sensitive polymer with natural tissue adhesive properties similar to those of polydopamine (PDA). The aim was to obtain a block copolymer system that has the potential to provide a new-generation solution in highly biocompatible antimicrobial applications, promising in terms of materials science, biotechnology, and environmental engineering. Materials and Methods: Within the scope of this thesis, the synthesis of p-(2-methacryloxyethyl)benzaldehyde monomer (MAEBA) with an aldehyde group and butyl 2-cyanopropan-2-yl-carbonotrichioate (CBPA) RAFT agent used for polymerization was carried out. Then, homopolymer (PNIPAM) was synthesized in the presence of azobisisobutyronitrile and CBPA using commercially available N-isopropylacrylamide monomer. By using homopolymer as a macro-RAFT agent, synthesis of a block having aldehyde function was carried out in the presence of MAEBA monomer. Dopamine conjugation was executed with triethylamine in a basic medium, employing the Schiff base chemistry of the synthesized block copolymer. Results: The structures of all synthesized intermediates and polymers were determined using spectroscopic and chromatographic techniques. The dopamine release profile of the dopaminegrafted block copolymer was investigated over a 72-hour period at a physiological pH of 7.4. The total amount of dopamine released after 72 hours was found to be 53.30 ± 9.38%. Conclusion: The dopamine-grafted block copolymer developed in this thesis demonstrates potential as a premier composite material for implant interfaces, leveraging the antimicrobial properties and surface adhesion capabilities of dopamine.
Objective: This study employed reversible addition-fragmentation chain transfer (RAFT) polymerization, a controlled living polymerization method, to synthesize poly(Nisopropylacrylamide) (PNIPAM), a heat-sensitive polymer with natural tissue adhesive properties similar to those of polydopamine (PDA). The aim was to obtain a block copolymer system that has the potential to provide a new-generation solution in highly biocompatible antimicrobial applications, promising in terms of materials science, biotechnology, and environmental engineering. Materials and Methods: Within the scope of this thesis, the synthesis of p-(2-methacryloxyethyl)benzaldehyde monomer (MAEBA) with an aldehyde group and butyl 2-cyanopropan-2-yl-carbonotrichioate (CBPA) RAFT agent used for polymerization was carried out. Then, homopolymer (PNIPAM) was synthesized in the presence of azobisisobutyronitrile and CBPA using commercially available N-isopropylacrylamide monomer. By using homopolymer as a macro-RAFT agent, synthesis of a block having aldehyde function was carried out in the presence of MAEBA monomer. Dopamine conjugation was executed with triethylamine in a basic medium, employing the Schiff base chemistry of the synthesized block copolymer. Results: The structures of all synthesized intermediates and polymers were determined using spectroscopic and chromatographic techniques. The dopamine release profile of the dopaminegrafted block copolymer was investigated over a 72-hour period at a physiological pH of 7.4. The total amount of dopamine released after 72 hours was found to be 53.30 ± 9.38%. Conclusion: The dopamine-grafted block copolymer developed in this thesis demonstrates potential as a premier composite material for implant interfaces, leveraging the antimicrobial properties and surface adhesion capabilities of dopamine.