Browsing by Subject "Polyelectrolytes"
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Item Open Access Cucurbit [7] uril-threaded fluorene-thiophene-based conjugated polyrotaxanes(Royal Society of Chemistry, 2016) Idris, M.; Bazzar, M.; Guzelturk, B.; Demir, Hilmi Volkan; Tuncel, D.Here we investigate the effect of cucurbit[7]uril (CB7) on the thermal and optical properties of fluorene-thiophene based conjugated polyelectrolytes. For this purpose, poly(9,9′-bis(6′′-(N,N,N-trimethylammonium)hexyl)fluorene-alt-co-thiophenelene) P1 and poly(9,9′-bis(6′′-(N,N,N-trimethylammonium)propyl)fluorene-alt-co-thiophenelene) P2 and their CB7-based polyrotaxane counterparts, P1CB7 and P2CB7, are synthesized by threading the part of the conjugated backbone of these polymers with CB7 during their synthesis. Threading efficiency in the P1CB7 containing hexyl pendant of as high as 50% is achieved, but in the case of P2, with the propyl pendant, only around 15% is achieved. We observed significant changes in the optical properties of both P1CB7 and P2CB7 with respect to their polymers P1 and P2. Fluorescent quantum yields of P1 and P2 which are 0.11 and 0.35 have increased to 0.46 and 0.55 for P1CB7 (>4 fold) and P2CB7, respectively. Moreover, polyrotaxanes compared to their polymers exhibit longer fluorescence lifetimes in the solution and the solid state thanks to the suppressed overall nonradiative recombination via encapsulation of the conjugated polymer backbone. Thermal analysis also indicates that polyrotaxanes have higher thermal stabilities than their polymer counterparts. In order to demonstrate the applicability of the synthesized materials, we also fabricated proof-of-concept light emitting diodes from P1 and its CB7-based polyrotaxane counterpart P1CB7. The CB7-integrating polymer showed lower turn-on voltages with high electroluminescence colour purity due to balanced charge injection in P1CB7 as compared to the P1 polymer.Item Open Access Light‐to‐heat photothermal dynamic properties of polypyrrole‐based coating for regenerative therapy and lab‐on‐a‐chip applications(Wiley-VCH Verlag, 2020-09) Ulasevich, S.; Ryzhkov, N. V.; Andreeva, D. V.; Özden, D. S.; Pişkin, Erhan; Skorb, E. V.Targeted delivery and release of biomolecules, e.g., bone morphogenetic protein (BMP‐2), are gaining high interest due to the application for tissue engineering, diagnostics, surface‐enhanced therapy and lab‐on‐a‐chip. Here, a new hybrid temperature‐responsive system consisting of polypyrrole (PPy) layer, mesoporous titania surface (TMS), and BMP‐2 is proposed. The PPy layer has the light‐to‐heat photothermal property. Dynamic behavior of the PPy layer in response to light can regulate release of BMP‐2. The PPy‐based coatings on TMS have shown to be efficient for storage of BMP‐2 and can be tuned to release BMP‐2 under irradiation. Moreover, the possibility of local delivery and generation of a gradual release of BMP‐2 for regulated cell growth is shown. Furthermore, the fabricated surfaces possess excellent biocompatibility and low cytotoxicity for MC3T3‐E1 cells. It is shown that the released BMP‐2 can effectively promote osteogenic differentiation of MC3T3‐E1 cells. Thus, the TMS/PPy–BMP‐2 is suggested to prolong targeted release of the BMP‐2 for more than 25 days which stimulates osteoblasts’ proliferation. The new stimuli‐responsive hybrid system is promising for targeted, localized, sustained drug release and application in bone tissue engineering.Item Open Access Like-charge polymer-membrane complexation mediated by multivalent cations: one-loop-dressed strong coupling theory(American Institute of Physics, 2019) Büyükdağlı, Şahin; Podgornik, R.We probe the electrostatic mechanism driving adsorption of polyelectrolytes onto like-charged membranes upon the addition of tri- and tetravalent counterions to a bathing monovalent salt solution. We develop a one-loop-dressed strong coupling theory that treats the monovalent salt at the electrostatic one-loop level and the multivalent counterions within a strong-coupling approach. It is shown that the adhesive force of the multivalent counterions mediating the like-charge adsorption arises from their strong condensation at the charged membrane. The resulting interfacial counterion excess locally maximizes the screening ability of the electrolyte and minimizes the electrostatic polymer grand potential. This translates into an attractive force that pulls the polymer to the similarly charged membrane. We show that the high counterion valency enables this adsorption transition even at weakly charged membranes. Additionally, strongly charged membranes give rise to monovalent counterion-induced correlations and intensify the interfacial multivalent counterion condensation, strengthening the complexation of the polymer with the like-charged membrane, as well as triggering the orientational transition of the molecule prior to its adsorption. Finally, our theory provides two additional key features as evidenced by previous adsorption experiments: first, the critical counterion concentration for polymer adsorption decreases with the rise of the counterion valency and, second, the addition of monovalent salt enhances the screening of the membrane charges and suppresses monovalent counterion correlations close to the surface. This weakens the interfacial multivalent counterion condensation and results in the desorption of the polymer from the substrate.Item Open Access Preparation and characterization of ultra-thin films containing Au and Ag nanoparticles using layer-by-layer deposition technique(Bilkent University, 2009) Cönger, Can PınarThe main objective of this thesis is to investigate the layer-by-layer deposited polyelectrolyte and polyelectrolyte/metal nanoparticle films by using X-ray Photoelectron (XPS) and Optical Spectroscopy (UV-Vis). Within this purpose, in the first part of the study, layer-by-layer deposited single and oppositely charged bilayered films are investigated by XPS. To extract additional information in the molecular level, the samples are analyzed while applying an external voltage bias. It is shown that applying external electrical stimuli to a single polyelectrolyte layer coated Si/SiO2 system responds to the change in the polarity by molecular rearrangements, evidenced by the changes only in the intensity of the corresponding –N + (1s) peak. In the second part of the study, metal nanoparticle (Au and/or Ag) incorporated polyelectrolyte films are investigated by optical spectroscopy. Within this frame, multilayer gold and silver nanaoparticle/polyelectrolyte films are prepared both separately and in bimetallic form. In order to get further understanding about the optical responses of single type of metal nanoparticle incorporated systems, several experimental approaches are followed. These approaches also enable us to control and manipulate the optical properties of these compact structures. The last part focuses on incorporation of metallic ions into layer-by-layer assembled polyelectrolyte matrices through ion-exchange method. It is shown that metal ions can be incorporated and subsequently reduced within this polymer matrix by UV or X-ray irradiation and can also form nanoparticles.Item Open Access Response of polyelectrolyte layers to the SiO2 substrate charging as probed by XPS(2009) Conger, C. P.; Süzer, ŞefikA single layer of the Cationic polyelectrolyte poly(allyamine) hydrochloride (PAH) deposited, using the layer-by-layer technique, on a silicon substrate containing 5 nm oxide layer is investigated by XPS while applying an external potential bias to the sample to control and manipulate the charge built-up on the oxide layer. Under application of a -10 V bias, the oxide layer is positively charged due to Photoemission process, evidenced by the measured Si2p binding energy of 104.4 eV. Application of a +10 V bias attracts the low energy neutralizing electrons, stemming from a hot filament, and leads to a negatively charged oxide layer, also evidenced by the measured Si2p binding energy of 102.9 eV. The single polyelectrolyte overlayer also responds to this polarity change of the oxide layer underneath by displaying a somewhat larger shifts both in the C1s and Nls peaks. In addition to the shifts in the positions, the N1s peaks undergo a significant intensity depletion, mostly on the positively charged -N+ component. We interpret this intensity depletion to be the result of reorientation of some of the dangling positively charged groups by moving toward the negatively charged oxide underlayer. To our knowledge this is the first time that a chemically specific response to an electrical stimuli is reported using XPS. A bilayer LbL film consisting of PAH and PSS, exhibits even a larger charging shift, but this time no intensity alteration is observed, most probably due to locking of the -N+ groups by the -SO3 + counterions of the second layer. © 2009 American Chemical Society.