Browsing by Subject "Self Assembly"
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Item Open Access Bioactive porous peg-peptide composite hydrogels with tunable mechanical properties(2014) Göktaş, MelisMimicking the instructive cues of native extracellular matrix (ECM) is fundamental to understand and control the processes regulating cell function and cell fate. Extensive research on the structure and biological complexity of ECM has shown that three types of critical information from the ECM have influence on cellular behaviour: (1) biophysical properties (elasticity, stiffness), (2) biochemical properties (bioactive peptide epitopes of ECM molecules), and (3) nanoarchitecture (nanofibrillar structure, porosity) of ECM. Recent efforts have therefore focused on the construction of ECM mimetic materials to modulate tissue specific cell functions. Advances in biomaterial platforms include artificial ECM mimics of peptide conjugated synthetic polymer hydrogels presenting bioactive ligands produced with covalent chemistry. These materials have already found application in tissue engineering, however, these biomaterial platforms represent oversimplified mimics of cellular microenvironment and lack the complexity and multifunctional aspects of native ECM. In this work, we developed a novel polyethylene glycol (PEG)-peptide nanofiber composite hydrogel system with independently tunable biochemical, mechanical and physical cues that does not require any chemical modification of polymer backbone to create synthetic ECM analogues. This approach allows noninteracting modification of multifactorial niche properties (i.e. bioactive ligands, stiffness, porosity), since no covalent conjugation method was used to modify PEG monomers for the incorporation of bioactivity and porosity. Combining the self-assembled peptide nanofibers with crosslinked polymer network simply by facile mixing followed by photo-polymerization resulted in the formation of porous hydrogel systems. Resulting porous network can be functionalized with desired bioactive signalling epitopes by simply altering the amino acid sequence of peptide amphiphile molecules. In addition, the mechanical properties of the composite system can be precisely controlled by changing the PEG concentration. Ultimately, multifunctional PEG-peptide composite scaffolds reported in this work, can fill a critical gap in the available biomaterials as versatile synthetic mimics of ECM with independently tunable properties. Such a system could provide a useful tool allowing the investigation of how complex niche cues interplay to influence cellular behaviour and tissue formation both in 2D and 3D platforms.Item Open Access Material Binding Peptides for Nanotechnology(MDPI AG, 2011) Seker, U. O. S.; Demir, Hilmi VolkanRemarkable progress has been made to date in the discovery of material binding peptides and their utilization in nanotechnology, which has brought new challenges and opportunities. Nowadays phage display is a versatile tool, important for the selection of ligands for proteins and peptides. This combinatorial approach has also been adapted over the past decade to select material-specific peptides. Screening and selection of such phage displayed material binding peptides has attracted great interest, in particular because of their use in nanotechnology. Phage display selected peptides are either synthesized independently or expressed on phage coat protein. Selected phage particles are subsequently utilized in the synthesis of nanoparticles, in the assembly of nanostructures on inorganic surfaces, and oriented protein immobilization as fusion partners of proteins. In this paper, we present an overview on the research conducted on this area. In this review we not only focus on the selection process, but also on molecular binding characterization and utilization of peptides as molecular linkers, molecular assemblers and material synthesizers.Item Open Access New solvents for surfactant self-assembly : molten hydrated salts and concentrated aqueous electrolyte solutions(2013) Albayrak, CemalLyotropic liquid crystalline (LLC) mesophases are formed by at least two components: a surfactant and a solvent. Common solvents in the surfactant self-assembly include water, organic liquids, and ionic liquids. In this work, we show that molten hydrated salts of the type [M(H2O)m](X)n (where, M is a transiton metal cation and X is a suitable anion such as NO3 - , Cl- , and ClO4 - ), which have melting points close to room temperature (RT), can organize surfactant molecules into LLC mesophases. As an example, we have focused on the [Zn(H2O)6](NO3)2-C12EO10 system (where, C12EO10 is decaethylene monododecyl ether; H3C-(CH2)11-(OCH2CH2)10-OH). A binary phase diagram was constructed between -190oC and 110oC using differential scanning calorimetry (DSC), polarized optical microscopy (POM), X-ray diffractometry (XRD), fourier transform infrared spectroscopy (FT-IR), and raman spectroscopy. The phase diagram closely resembles the phase diagram of H2O-CmEOn systems, exhibiting typical phases such as spherical cubic, hexagonal, and bicontinuous cubic. It is also observed that the phase transitions are dictated by the critical packing parameter (CPP) as the solvent concentration is changed. The mesophases are unusually stable at low temperatures, where a LLC to mesostructured solid transformation has been observed with a glass transiton at - 52oC. The mesostructured solid phase is also stable at -190oC. The confinement of the salt species in the LLC domains prevents the crystallization of the salt at low temperatures. In the second part, from the analogy between [M(H2O)m](X)n type salts and concentrated electrolyte solutions of alkali metal salts, the mixtures of concentrated aqueous solutions of some Li+ salts (LiCl, LiBr, LiI, LiNO3 and LiClO4) with C12EO10 surfactant, were investigated. The mixtures exhibited LLC mesophases in a broad range of compositions. A ternary phase diagram was constructed for the LiNO3-H2O-C12EO10 system at room temperature using XRD and POM tecniques. In the LLC mesophases formed with the Li+ salts, the water remains as hydrated under ambient conditions and open atmosphere. In addition, the effect of anions on the phase behaviour follows a Hofmeister series except for the ClO4 - ion. Ionic conductivty of the LiX-H2O-C12EO10 (where X is Cland NO3 - ) mesophases has been determined in a broad range of the salt concentrations (5 to 7 salt/surfactant mole ratio) and temperature (-13 to 100oC). The LiCl-H2OC12EO10 LLC samples have also been used as a gel-electrolyte to run a polymer electrochromic device. The mesophase shows excellent performance in this device. The investigations were further extended to include some of the Ca2+ salts, namely CaCl2 and Ca(NO3)2. The concentrated aqueous solutions of both salts with C12EO10 and water exhibited LLC mesophases similar to the molten hydrated salts and concentrated solutions of Li+ salts. In the CaCl2.xH2O-C12EO10 system, an LLC to mesocrystalline phase transformation was observed, for the first time, where the salt, water and surfactant species freezes to a mesocrystalline phase at RT. Lastly, many other salt.xH2O-surfactant LLC mesophases were investigated using the following salts: NaCl, NaBr, NaI, CH3COONa, NaSCN, NaClO4, NaNO3, KNO3, KCl, KSCN, KI, MgCl2, Mg(NO3)2 and NaOH. In addition, the LLC mesophases of concentrated H3PO4 acid and C12EO10 were also investigated. Among these compounds, H3PO4 systems exhibited air stable LLC mesophases at RT and 25% relative humdity (RH). The MgCl2 system was found to exhibit air stable LLC mesophases for a couple of hours. The NaI, KSCN and NaClO4 systems were found to be stable at low salt concentrations with little or no mesostructured order. Other salt systems were unstable and leached out salt crystals rapidly. The NaOH system is unstable because of a reaction with CO2 in the air. In summary, we have found a correlation between the deliquescent relative humidity value of the salt and its LLC mesophase formation ability under ambient conditions.