Chemical Engineering / Kimya Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/14
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Article Citation - WoS: 8Citation - Scopus: 7Cvd-Deposited Oxygen-Selective Fluorinated Siloxane Copolymers as Gas Diffusion Layers(American Chemical Society, 2022) Cihanoğlu, Gizem; Ebil, ÖzgençCopolymer thin films of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (V4D4), 2-(perfluorohexylethylacrylate) (PFHEA), and 2-(perfluoroalkylethylmethacrylate) (PFEMA) were synthesized via initiated chemical vapor deposition (iCVD) as potential candidates for gas diffusion layers (GDLs) in gas diffusion electrodes (GDEs) for aqueous metal–air batteries. Thin-film GDLs exhibited an average water vapor transmission rate of 7.5 g m–2 day–1 and enhanced oxygen diffusion with oxygen permeabilities as high as 3.53 × 10–15 mol m m–2 s–1 Pa–1 (10.5 Barrer). The electrochemical performance of GDEs fabricated using commercial catalysts, current collectors, and synthesized GDLs was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements. The fabricated GDEs exhibited higher oxygen reduction current densities (228.2 mA cm–2) compared to commercial GDEs (132.7 mA cm–2). Copolymer GLDs exhibited an order of magnitude higher oxygen diffusion (39.5 × 10–8 cm2 s–1) in GDEs compared to commercial counterparts (1.84 × 10–8 cm2 s–1). Due to the high oxygen solubility of V4D4 and excellent hydrophobic behavior of PFHEA and PFEMA, their copolymers can effectively promote the diffusion of oxygen and restrict moisture intake, making them ideal materials for GDLs. Combining well-balanced properties of siloxane and fluorinated polymer chemistries, the iCVD process is an excellent low-cost method for the fabrication of GDLs for metal–air battery applications.Article Citation - WoS: 17Citation - Scopus: 22Responsive pentablock copolymers for siRNA delivery(Royal Society of Chemistry, 2015) Uz, Metin; Mallapragada, Surya K.; Alsoy Altınkaya, SacideIn this study, temperature and pH responsive cationic and amphiphilic pentablock copolymers, which consist of the temperature responsive triblock Pluronic F127 sandwiched between pH responsive PDEAEM (poly(2-diethylaminoethyl methacrylate)) end blocks, were used for the first time in the development of polyplex and gold nanoparticle (AuNP) based multicomponent siRNA delivery systems (MCSs). Copolymers in both systems protected siRNA from external effects, provided cell entry and endosomal escape. The thermoreversible micellization of the hydrophobic PPO block facilitated the cellular entry while the PDEAEM blocks enhanced the endosomal escape through protonated tertiary amine groups by pH buffering. The synergistic advantages of the different blocks showed an enhanced effect in the MCSs due to attachment and surface configuration reasons. The siRNA transfection efficiency of MCSs against luciferase expressing SKOV3 cells was 15% higher than both the polyplexes alone and the commercial siRNA transfection agent Lipofectamine RNAiMax at the same applied dose, without any toxicity. The results indicated that the multicomponent systems based on the responsive cationic pentablock copolymers and gold nanoparticles have promising potential as an efficient siRNA delivery vector for future applications.Article Citation - WoS: 42Citation - Scopus: 43Well-Defined Cholesterol Polymers With Ph-Controlled Membrane Switching Activity(American Chemical Society, 2012) Sevimli, Sema; İnci, Fatih; Zareie, Hadi M.; Bulmuş, VolgaCholesterol has been used as an effective component of therapeutic delivery systems because of its ability to cross cellular membranes. Considering this, well-defined copolymers of methacrylic acid and cholesteryl methacrylate, poly(methacrylic acid-co-cholesteryl methacrylate) P(MAA-co-CMA), were generated as potential delivery system components for pH-controlled intracellular delivery of therapeutics. Statistical copolymers with varying cholesterol contents (2, 4, and 8 mol %) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Dynamic light scattering (DLS) analysis showed that the hydrodynamic diameters of the copolymers in aqueous solutions ranged from 5 ± 0.3 to 7 ± 0.4 nm for the copolymers having 2 and 4 mol % CMA and 8 ± 1.1 to 13 ± 1.9 nm for the copolymer having 8 mol % CMA with increasing pH (pH 4.5-7.4). Atomic force microscopy (AFM) analysis revealed that the copolymer having 8 mol % CMA formed supramolecular assemblies while the copolymers having 2 and 4 mol % CMA existed as unimers in aqueous solution. The pH-responsive behavior of the copolymers was investigated via UV-visible spectroscopy revealing phase transitions at pH 3.9 for 2 mol % CMA, pH 4.7 for 4 mol % CMA, and pH 5.4 for 8 mol % CMA. Lipid bilayers and liposomes as models for cellular membranes were generated to probe their interactions with the synthesized copolymers. The interactions were determined in a pH-dependent manner (at pH 5.0 and 7.4) using surface plasmon resonance (SPR) spectroscopy and liposome leakage assay. Both the SPR analyses and liposome leakage assays indicated that the copolymer containing 2 mol % CMA displayed the greatest polymer-lipid interactions at pH 5.0, presenting the highest binding ability to the lipid bilayer surfaces, and also demonstrating the highest membrane destabilization activity. CellTiter-Blue assay showed that the copolymers did not affect the cell viability up to 30 μM over a period of 72 h. © 2012 American Chemical Society.Article Citation - WoS: 6Citation - Scopus: 7Solubility and Diffusivity of Methylmethacrylate and Butylacrylate Monomers in a Mma-Ba Copolymer(John Wiley and Sons Inc., 2007) Yürekli, Yılmaz; Alsoy Altınkaya, Sacide; Zielinski, John M.Mutual diffusion coefficients and sorption isotherms of methyl methacrylate (MMA) and butyl acrylate (BA) monomers in methyl methacrylate-butyl acrylate copolymer (MMA-BA) have been measured by gravimetric sorption. MMA is found to have higher solubility and diffusion rates in the copolymer than BA. Sorption data for MMA were interpreted using classical Flory-Huggins thermodynamic theory with a constant interaction parameter (χ). A modified version of this theory has been applied to correlate the sorption data of BA, which exhibit a temperature and concentration-dependent χ parameter. For MMA, the isotherm data reveal enhanced polymer-solvent interactions with increasing temperature, while for BA the data indicate a drive toward phase separation with increasing temperature. Despite the difference in thermodynamic behavior, both monomers are found to exhibit Fickian diffusion and the diffusivity data are correlated reasonably well with the Vrentas-Duda free volume theory. Some deviation between the free-volume correlation and the experimental data is observed at the lowest temperature and BA concentration examined.Article Citation - WoS: 21Citation - Scopus: 26Solubility and Diffusivity of Solvents and Nonsolvents in Poly(methyl Methacrylate Co Butyl Methacrylate)(Elsevier Ltd., 2005) Eser, Hülya; Tıhmınlıoğlu, FundaLocate full-text(opens in a new window)|Full Text(opens in a new window)|View at Publisher| Export | Download | Add to List | More... Fluid Phase Equilibria Volume 237, Issue 1-2, 25 October 2005, Pages 68-76 Solubility and diffusivity of solvents and nonsolvents in poly(methyl methacrylate co butyl methacrylate) (Article) Eser, H., Tihminlioglu, F. Department of Chemical Engineering, Izmir Institute of Technology, Gulbahce Urla- Izmir 35430, Turkey View references (25) Abstract In this study, thermodynamic properties, namely retention volume, infinitely dilute weight fraction activity coefficient, Flory-Huggins interaction parameter, solubility parameter of the polymer, partition coefficient and diffusion coefficients of the various solvents in poly(methyl methacrylate co butyl methacrylate) (PMMA co BMA) at infinite dilution of the solvent have been determined by inverse gas chromatography (IGC). In this technique, a small amount of the solvent was injected into the capillary column and its retention time was measured and used to calculate several polymer-solvent interaction parameters which are mentioned above. The solvents used in this study were methanol, ethanol, propanol, butanol, methyl acetate, ethyl acetate, propyl acetate, dichloromethane, trichloromethane, acetone, methyl methacrylate, butyl methacrylate for PMMA co BMA. The thermodynamic results, obtained from the experiments, indicated that trichloromethane and dichloromethane were the most suitable solvents among all the solvents studied for PMMA co BMA. The partition (K) and diffusion coefficients (Dp) of various solvents at infinite dilution of the solvent were calculated by using the model developed by Pawlisch et al. [C.A. Pawlisch, A. Macris, R.L. Laurence, Solute diffusion in polymers.1. The use of capillary column inverse gas chromatography, Macromolecules 20 (1987) 1564-1578]. The optimum K and D p values that best fit the data were found and the model predicted experimental data very well. Vrentas-Duda free volume theory was used to correlate the diffusion data and to investigate the effect of solvent size on diffusion process. The theory has shown to correlate diffusion data above the glass transition temperature very well for the PMMA-co-BMA-solvent system.