Master Degree / Yüksek Lisans Tezleri
Permanent URI for this collectionhttps://hdl.handle.net/11147/3008
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Master Thesis Studying Dopa Adhesion on Polystyrene Under Water(Izmir Institute of Technology, 2021) Yıldız, Remziye; Akdoğan, Yaşar; Emrullahoğlu, MustafaMussels wet adhesive performance has been arousing curiosity for a long time. It is found that 3,4-dihydroxyphenylalanine (DOPA) is responsible for adhesive properties of mussels. Despite a large body of research characterizing the interactions DOPA with hydrophilic surfaces, relatively few works have addressed the mechanism of interactions with hydrophobic surfaces. The benzene ring of DOPA is the main attributor to the adhesion on hydrophobic polystyrene (PS) surface. However, here we showed that two hydroxyl groups of catechol have also effects on wet adhesion. We studied wet adhesive properties of DOPA, tyrosine and phenylalanine functionalized PEG polymers, PEG-(N-Boc-L-DOPA)4, PEG-(N-Boc-L-Tyrosine)4, PEG-(N-Boc-L-Phenylalanine)4, on spin labeled PS nanobeads (SL-PS) by electron paramagnetic resonance (EPR) spectroscopy. Surface coverage ratio of SL-PS upon additions of PEG-(N-Boc-L-DOPA)4, PEG-(N-Boc-L-Tyrosine)4 and PEG-(N-Boc-L-Phenylalanine)4 showed that SL-PS was covered with 70%, 50% and 0%, respectively. This showed that spontaneous wet adhesion on PS increases with the number of amino acids hydroxyl groups. This is also supported with the density functional theory (DFT) energy calculations and ab-initio molecular dynamics (AIMD) simulations. In water, interactions between water molecules and hydroxyl groups on the catechol induce catechol adhesion via π-π stacking between the catechol and double styrene rings which were already tilted out with water.Master Thesis Adhesion of Dopa Functionalized Gels To Spin Labeled Surfaces(Izmir Institute of Technology, 2017) Göksel, Yaman; Akdoğan, Yaşar; Emrullahoğlu, MustafaThis study investigates the force free adhesive properties of synthetic polymer in aqueous media using electron paramagnetic resonance (EPR) spectroscopy. Due to poor performance of commercial adhesives in wet environments, scientists are interested in different types of adhesives to overcome this difficulty. On this context, mussels attract attention because of their versatile properties to adhere different types of surfaces from rocks to ship hulls underwater. Adhesion occurs when mussel secretes mussel foot proteins (MFPs) in order to form threads and plaques. Seven types of MFPs are unique in plaque contains high amount of L-3,4-dihydroxyphenylalanine (DOPA) amino acid which is reputed to be responsible for adhesion. In this research, branched polyethylene glycol (PEG) based polymers functionalized with DOPA were synthesized and their force-free adhesive properties to hydrophobic polystyrene and hydrophilic silica nanobeads were investigated in solution. These nanobead surfaces were conjugated with spin label molecules to probe adhesion dynamics using EPR spectroscopy. In addition, gel forms of polymers obtained using NaIO4, FeCl3 and Cr2O7 were used as adhesive materials for EPR measurements. All of these adhesive materials showed adhesion to spin labeled polystyrene (SL-PS) surface. However, non-DOPA containing PEG showed no indication of adhesion thus, demonstrating the importance of DOPA in wet adhesion. In addition, EPR results showed that DOPA based PEG polymers were unable to adhere to spin labeled silica (SL-SiO2) surface. This behavior was attributed to hydration layers around silica nanobeads. These layers formed around hydrophilic SiO2 surface prevent interaction between nanobead surface and polymeric material.Master Thesis Obtaining Underwater Adhesive Materials and Characterization of Their Adhesive Properties To Different Surfaces by Esr Spectroscopy(Izmir Institute of Technology, 2016) Kırpat, İklima; Akdoğan, YaşarThis study describes the design, synthesis and spectral behavior of underwater adhesive materials which adhere to surfaces without any external force. The materials with wet adhesive properties have a wide application field from biomedical implantation and covering to antifouling materials. Mussel’s stickiness to rocks, ships, etc. inspite of strong waves in the sea inspires us to synthesize adhesives materials. Mussels attach to solid surfaces strongly using their threads and plaques. The complex fluid (mussel foot proteins, Mfps) secreted from mussels is solidified in the sea water and forms threads, each equipped with a distal adhesive plaque. Mfps have large amount of L-3,4-dihydroxyphenylalanine (DOPA) amino acid and this amino acid is responsible for adhesion of mussels to underwater surfaces. The presence of stable hydration layers around both the adhesive materials and surface results in strong hydration repulsive forces that undermine adhesion. So far, applied external forces were used to break through or disrupt the hydration layers which prevent adhesion. In this research branched PEG based polymers were modified with different amounts of DOPA in order to obtain underwater adhesive material. Their adhesive properties to spin labeled (SL) nanoparticles were tested without applying an external force by electron spin resonance (ESR) spectroscopy. As model surfaces we synthesized hydrophobic SL-polystyrene and hydrophilic SL-silica nanoparticles. ESR results showed that four arm DOPA modified PEG is able to adhere to SL-polystyrene but not to SL-silica. Moreover, adhesions of the polymers were tested by making hydrogels using iodate (IO3-) and iron (III) (Fe3+) ions. ESR results showed that hydrogels prepared from four arm DOPA modified PEG/IO3- mixture has better adhesive property to SL-polystyrene compare to hydrogels prepared from four arm DOPA modified PEG/Fe3+ mixture and adhesion of IO3- based gel form is better compared to molecule form.