Browsing by Subject "Polymers"

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Open Access
Antibacterial electrospun poly(lactic acid) (PLA) nanofibrous webs incorporating triclosan/cyclodextrin inclusion complexes
(2013) Kayaci F.; Umu O.C.O.; Tekinay, T.; Uyar, T.
Solid triclosan/cyclodextrin inclusion complexes (TR/CD-IC) were obtained and then incorporated in poly(lactic acid) (PLA) nanofibers via electrospinning. α-CD, β-CD, and γ-CD were tested for the formation of TR/CD-IC by a coprecipitation method; however, the findings indicated that α-CD could not form an inclusion complex with TR, whereas β-CD and γ-CD successfully formed TR/CD-IC crystals, and the molar ratio of TR to CD was found to be 1:1. The structural and thermal characteristics of TR/CD-IC were investigated by 1H NMR, FTIR, XRD, DSC, and TGA studies. Then, the encapsulation of TR/β-CD-IC and TR/γ-CD-IC in PLA nanofibers was achieved. Electrospun PLA and PLA/TR nanofibers obtained for comparison were uniform, whereas the aggregates of TR/CD-IC crystals were present and distributed within the PLA fiber matrix as confirmed by SEM and XRD analyses. The antibacterial activity of these nanofibrous webs was investigated. The results indicated that PLA nanofibers incorporating TR/CD-IC showed better antibacterial activity against Staphylococcus aureus and Escherichia coli bacteria compared to PLA nanofibers containing only TR without CD-IC. Electrospun nanofibrous webs incorporating TR/CD-IC may be applicable in active food packaging due to their very high surface area and nanoporous structure as well as efficient antibacterial property. © 2013 American Chemical Society.
Open Access
Area-selective atomic layer deposition using an inductively coupled plasma polymerized fluorocarbon layer: A case study for metal oxides
(American Chemical Society, 2016) Haider, A.; Deminskyi, P.; Khan, T. M.; Eren, H.; Bıyıklı, Necmi
Area-selective atomic layer deposition (AS-ALD) has attracted immense attention in recent years for self-aligned accurate pattern placement with subnanometer thickness control. Here, we demonstrate a methodology to achieve AS-ALD by using inductively couple plasma (ICP) grown fluorocarbon polymer film as hydrophobic blocking layer for selective deposition. Our approach has been tested for metal-oxide materials including ZnO, Al2O3, and HfO2. Contact angle, X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometer, and scanning electron microscopy (SEM) measurements were performed to investigate the blocking ability of plasma polymerized fluorocarbon layers against ALD-grown metal-oxide films. A considerable growth inhibition for ZnO has been observed on fluorocarbon coated Si(100) surfaces, while the same polymerized surface caused a relatively slow nucleation for HfO2 films. No growth selectivity was obtained for Al2O3 films, displaying almost the same nucleation behavior on Si and fluorocarbon surfaces. Thin film patterning has been demonstrated using this strategy by growing ZnO on lithographically patterned fluorocarbon/Si samples. High resolution SEM images and XPS line scan confirmed the successful patterning of ZnO up to a film thickness of ∼15 nm. © 2016 American Chemical Society.
Open Access
Bacteria-immobilized electrospun fibrous polymeric webs for hexavalent chromium remediation in water
(Springer Berlin Heidelberg, 2016) Sarioglu, O.F.; Celebioglu A.; Tekinay, T.; Uyar, Tamer
The development of hexavalent chromium remediating fibrous biocomposite mats through the immobilization of a hexavalent chromium reducing bacterial strain, Morganella morganiiSTB5, on the surfaces of electrospun polystyrene and polysulfone webs is described. The bacteria-immobilized biocomposite webs have shown removal yields of 93.60 and 93.79 % for 10 mg/L, 99.47 and 90.78 % for 15 mg/L and 70.41 and 68.27 % for 25 mg/L of initial hexavalent chromium within 72 h, respectively, and could be reused for at least five cycles. Storage test results indicate that the biocomposite mats can be stored without losing their bioremoval capacities. Scanning electron microscopy images of the biocomposite webs demonstrate that biofilms of M. morganii STB5 adhere strongly to the fibrous polymeric surfaces and are retained after repeated cycles of use. Overall, the results suggest that reusable bacteria-immobilized fibrous biocomposite webs might be applicable for continuous hexavalent chromium remediation in water systems.
Open Access
CdSe/ZnS core-shell nanocrystal based scintillators for enhanced detection in UV
(IEEE, 2006) Demir, Hilmi Volkan; Soğancı, İbrahim Murat; Mutlugün, Evren
In this work, we present a novel scintillator that incorporates CdSe/ZnS core-shell nanocrystals to utilize both their high quantum fluorescence efficiency in the visible and high optical absorption in the UV for the purpose of facilitating UV imaging on a Si platform. Here we demonstrate enhancement in UV detection up to 800% with respect to the host polymer in the UV.
Open Access
Chemical funneling of colloidal gold nanoparticles on printed arrays of end-grafted polymers for plasmonic applications
(American Chemical Society, 2020-06) Pekdemir, S.; Torun, İ.; Şakir, M.; Ruzi, M.; Rogers, J. A.; Önses, M. Serdar
Spatially defined assembly of colloidal metallic nanoparticles is necessary for fabrication of plasmonic devices. In this study, we demonstrate high-resolution additive jet printing of end-functional polymers to serve as templates for directed self-assembly of nanoparticles into architectures with substantial plasmonic activity. The intriguing aspect of this work is the ability to form patterns of end-grafted poly(ethylene glycol) through printing on a hydrophobic layer that consists of fluoroalkylsilanes. The simultaneous dewetting of the underlying hydrophobic layer together with grafting of the printed polymer during thermal annealing enables fabrication of spatially defined binding sites for assembly of nanoparticles. The employment of electrohydrodynamic jet printing and aqueous inks together with reduction of the feature size during thermal annealing are critically important in achieving high chemical contrast patterns as small as ∼250 nm. Gold nanospheres of varying diameters selectively bind and assemble into nanostructures with reduced interparticle distances on the hydrophilic patterns of poly(ethylene glycol) surrounded with a hydrophobic background. The resulting plasmonic arrays exhibit intense and pattern-specific signals in surface-enhanced Raman scattering (SERS) spectroscopy. The localized seed-mediated growth of metallic nanostructures over the patterned gold nanospheres presents further routes for expanding the composition of the plasmonic arrays. A representative application in SERS-based surface encoding is demonstrated through large-area patterning of plasmonic structures and multiplex deposition of taggant molecules, all enabled by printing.
Open Access
Complex dynamics of sheared active particle suspensions
(2024-08) Bayram, Ayten Gülce
Active systems, whether natural or artificial, have a unique ability to extract energy from their surroundings, driving themselves out of equilibrium. This capability gives rise to a variety of non-equilibrium phenomena such as swarming and clustering, creating potential uses for new materials and technologies. Among these active systems, we are particularly interested in the complex dynamics and the rheological behaviors of active colloidal suspensions and chiral active polymer chains when they are exposed to shear flow. In this sense, active Brownian dynamics (ABP), one of the most common computational methods, is used to study the complex dynamics of these active systems. In addition, the Multiparticle Collision Dynamics (MPCD) method is chosen to simulate in a computationally efficient way how the solvent dynamics, especially the resulting hydrodynamic effects, around these active systems behave. Phase transitions and collective dynamics of active colloidal suspensions are fascinating topics in soft matter physics, particularly for out-of-equilibrium systems, which can lead to rich rheological behaviours in the presence of steady shear flow. The role of self-propulsion in the rheological response of a dense colloidal suspension is investigated by using particle-resolved Brownian dynamics simulations. First, the combined effect of activity and shear in the solid on the disordering transition of the suspension is analyzed. While both self-propulsion and shear destroy order and melt the system if critical values are exceeded, self-propulsion largely lowers the stress barrier needed to be overcome during the transition. We further explore the rheological response of the active sheared system once a steady state is reached. While passive suspensions show a solid-like behaviour, turning on particle motility fluidises the system. At low self-propulsion, the active suspension behaves in a steady state as a shear-thinning fluid. Increasing the self-propulsion changes the behaviour of the liquid from shear-thinning to shear-thickening. We attribute this to clustering in the sheared suspensions induced by motility. This new phenomenon of motility-induced shear thickening (MIST) can be used to tailor the rheological response of colloidal suspensions. Expanding the active Brownian dynamics simulation for particles of more complex shapes such as active polymers, we explore the complex formation of an active flexible polymer chain in linear shear flow in two spatial dimensions. The chiral head monomer is active and circling, while all other monomers are passive following both the motion of the head polymer and the shear flow. By the combination of activity, chirality and shear rate, a wealth of different states are found including the formation of a linear/complex folding and a spiralling state with both head-in and head-out morphologies. As the vorticity of the applied shear competes with the circling sense of the head, the chirality of the whole complex can be tuned by activity. Our results are relevant to characterize the response of living and artificial chiral active polymer chains to complex flow fields. These initial Brownian dynamics simulations of active polymer chains under shear flow did not account for hydrodynamic interactions (HI), which simplified the system to a dry environment influenced only by Gaussian-colored noises. Recognizing the potential impact of HI on the conformational and dynamical properties of these polymers, we advanced our study by incorporating shortly the hydrodynamic interactions using a hybrid Molecular Dynamics-Multiparticle Collision Dynamics (MD-MPCD) approach. In this way, we discuss the polymer dynamics and conformations for more realistic scenarios, observed in experiments. This hybrid approach is an improvement that captures the hydrodynamic effects of the solvent as well as thermal fluctuations. The swelling effect induced by HI is critical for these transitions, causing delayed conformational changes on the state diagram and preventing certain states already observed in the absence of HI. The results show that hydrodynamic interactions enhance linear folding and head-in spiraling states while suppressing complex folding and head-out spiraling. We could analyze simply the complex interplay between self-propulsion, shear, and hydrodynamics in active chiral polymer systems under shear flow, which will provide more realistic insights for future research and applications.
Open Access
Conjugated polymer nanoparticles
(2010) Tuncel, D.; Demir, Hilmi Volkan
Conjugated polymer nanoparticles are highly versatile nano-structured materials that can potentially find applications in various areas such as optoelectronics, photonics, bio-imaging, bio-sensing and nanomedicine. Their straightforward synthesis in desired sizes and properties, biocompatibility and non-toxicity make these materials highly attractive for the aforementioned applications. This feature article reviews the recent developments in the synthesis, characterization, properties and application of these exciting nanostructured materials.
Open Access
Conjugated polymer nanoparticles for cell labelling, imaging and drug delivery
(European Association for Chemical and Molecular Sciences, 2012-08) Tuncel, Dönüş; İbrahimova, Vusela; Gezici, Özlem
Nanoparticles based on conjugated polymers are emerging as a new class of luminescent nanoparticles. These nanoparticles have many potential applications including imaging agents, biosensors, and photonics owing to their high quantum yields, high molar absorptivity, photo stability and easy synthesis. The recent cell assay studies have also showed that these nanoparticles were not cytotoxic.4Moreover, conjugated polymer nanoparticles can be modified easily to deliver therapeutic agents such as cancer drugs, genetic materials (e.g. RNA, siRNA) and biomolecules to the desired targets. Here, we present the resent studies in our lab involving the synthesis and applications of nanoparticles using various conjugated polymers which emit blue, green, yellow and red. In order to obtain shape-persistent and stable nanoparticles, a novel method was developed in which the nanoparticles were prepared either via Cu-catalyzed or cucurbit[6]uril (CB6)-catalyzed click reactions between azide groups containing hydrophobic fluorene-based conjugated polymers and a hydrophilic diaminodialkyne containing cross-linker. Through the click reaction, not only does the cross-linking confer stability, but it also introduces functional groups, such as triazoles and amines, to the nanoparticles. TEM images of the nanoparticles also showed that they display very interesting morphologies. Incorporation of hydrophilic functional groups to the hydrophobic conjugated polymers resulted in a distinct phase separation, producing Janus-like or patchy particles.
Open Access
Construction of multi-layered white emitting organic nanoparticles by clicking polymers
(Royal Society of Chemistry, 2015) Keita, H.; Güzeltürk, B.; Pennakalathil, J.; Erdem, T.; Demir, Hilmi Volkan; Tuncel, D.
A series of blue, green and red emitting polymers that are appropriately functionalized with alkyne and azide functional groups have been prepared and clicked together to construct bi-layered and tri-layered white emitting core-shell type nanoparticles. Here the use of these organic hetero-nanoparticles as colour converters to realize a white light-emitting diode platform acquiring a colour quality comparable to the existing phosphor-based ones was also demonstrated. © The Royal Society of Chemistry.
Open Access
Core-shell quantum dot-embedded polymers for antistatic applications
(American Chemical Society, 2023-12-07) Ekim, Sunay Dilara; Aydın, Firdevs; Kaya, Görkem Eylül; Baytekin, H. Tarık; Asil, Demet; Baytekin, Bilge
Electrical charges develop on the surfaces of two insulator materials when they are in contact and separated. The retention of charges on insulator polymers causes material losses and hazards in industries using these polymers. Here, we show that a set of core-shell quantum dots embedded into a common polymer can destabilize the charges on the polymer. The locations of the charge carriers in the nanostructure, or the “type” of the dots, affect their discharging ability, which can also be manipulated or reverted remotely by light. The mechanism of antistatic action is presumed to contain interaction with polymer mechanospecies. The quantum dot embedding renders the polymers antistatic without changing their conductivity. Such antistatic additives, by which the polymers remain insulating, can be used to prevent static charges, e.g., in electronic coatings and in other antistatic applications.
Open Access
Development of an iterative learning controller for polymer based micro-stereolithography prototyping systems
(IEEE, 2016) Türeyen, Erkan Buğra; Karpat, Yiğit; Çakmakcı, Melih
Additive manufacturing has become increasingly popular for a wide range of applications in recent years. Micro-stereolithography (μSLA) is a popular method for obtaining polymer-based parts. Systems using the μSLA approach usually consist of a vertical positioning system, a light source and a container where the component is built gradually as the polymer is cured at the locations where the ultraviolet light is projected. It has been noted that the motion of the positioning system and the intensity of the light source is an important factor to achieve high level dimensional precision. In this paper a three dimensional error based learning scheme is presented to improve the time varying process parameters of the system so that the dimensional accuracy of the product is improved. A mathematical model of the curing process is used for developing the error based learning algorithm. The current process parameters as a function of time and the dimensional error obtained at each layer of the production are used for increasing the quality and precision of the same part in the next iteration. Our initial simulation results show significant improvements can be obtained in a few iterations if the correct learning parameters are used based on the target parts dimensional properties.
Open Access
Dispersion of multi-walled carbon nanotubes in an aqueous medium by water-dispersible conjugated polymer nanoparticles
(2010) Baykal, B.; Ibrahimova, V.; Er, G.; Bengü, E.; Tuncel, D.
Vertically aligned multi-walled carbon nanotubes (MWCNTs) synthesized by the alcohol catalytic CVD (ACCVD) technique are dispersed in water with the aid of water-dispersible conjugated polymer nanoparticles (CPNs). The interactions between CPNs and CNTs are studied with spectroscopy (UV-Vis, fluorescence and Raman) and electron microscopy techniques are used to confirm attachment of CPNs to the CNT sidewalls.
Open Access
Does the donor-acceptor concept work for designing synthetic metals? 1. theoretical investigation of poly(3-cyano-3′-hydroxybithiophene)
(American Chemical Society, 2002) Salzner, U.
Homo- and copolymers of hydroxythiophene and cyanothiophene have been investigated by employing density functional theory with the aim of determining the effect of donor-acceptor substitution on the electronic structure. The band gap of the copolymer is 0.11 eV smaller than that of polythiophene. Bandwidths of valence and conduction bands are reduced by 0.22 and 0.36 eV compared to polybithiophene. Conductivity after p- and n-doping could therefore be less than that of polythiophene. All properties of the copolymer are averages between those of the homopolymers. The charge separation between hydroxy- and cyano-substituted rings is 0.12 e in the neutral state and 0.13 e and the dication. The ionization potential and electron affinity of poly(hydroxythiophene) are 1.78 and 1.63 eV smaller than those of poly(cyanothiophene). According to the donor-acceptor concept, a decrease in band gap and an increase in bandwidths compared to the homopolymers should have resulted: We rationalize the absence of band broadening with reduced interaction between fragments with very different energies in agreement with perturbation theory.
Open Access
Effect of chalcogens on electronic and photophysical properties of vinylene-based diketopyrrolopyrrole copolymers
(American Chemical Society, 2015) Dhar, J.; Mukhopadhay, T.; Yaacobi-Gross, N.; Anthopoulos, T. D.; Salzner, U.; Swaraj, S.; Patil, S.
Three vinylene linked diketopyrrolopyrrole based donor−acceptor (D−A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV−vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm2 V−1 s −1.
Open Access
Effect of double growth factor release on cartilage tissue engineering
(2013) Ertan, A.B.; Yilgor P.; Bayyurt, B.; Çalikoǧlu, A.C.; Kaspar Ç.; Kök F.N.; Kose G.T.; Hasirci V.
The effects of double release of insulin-like growth factor I (IGF-I) and growth factor β1 (TGF-β1) from nanoparticles on the growth of bone marrow mesenchymal stem cells and their differentiation into cartilage cells were studied on PLGA scaffolds. The release was achieved by using nanoparticles of poly(lactic acid-co-glycolic acid) (PLGA) and poly(N-isopropylacrylamide) (PNIPAM) carrying IGF-I and TGF-β1, respectively. On tissue culture polystyrene (TCPS), TGF-β1 released from PNIPAM nanoparticles was found to have a significant effect on proliferation, while IGF-I encouraged differentiation, as shown by collagen type II deposition. The study was then conducted on macroporous (pore size 200-400μm) PLGA scaffolds. It was observed that the combination of IGF-I and TGF-β1 yielded better results in terms of collagen type II and aggrecan expression than GF-free and single GF-containing applications. It thus appears that gradual release of a combination of growth factors from nanoparticles could make a significant contribution to the quality of the engineered cartilage tissue. © 2011 John Wiley & Sons, Ltd.
Open Access
Electrospun crosslinked poly-cyclodextrin nanofibers: highly efficient molecular filtration thru host-guest inclusion complexation
(Nature Publishing Group, 2017) Celebioglu, A.; Yildiz, Z. I.; Uyar, T.
Water pollution is a serious concern for public health and environment in today's world; hence, there exists a strong demand to develop cost-effective, sustainable and eco-friendly membranes. Here, we produce a highly efficient molecular filter membrane based on bio-renewable material; cyclic oligosaccaharides known as cyclodextrins (CD). Crosslinked insoluble poly-CD nanofibers are produced by using electrospinning technique in the absence of any additional polymeric carrier. Poly-CD nanofibrous membrane exhibit significant affinity to a common class of organic pollutant (i.e. methylene blue (MB)). Remarkably, the electrospun poly-CD nanofibrous web can outdistance the commonly used filter material (i.e. activated carbon) in terms of removal capacity. The flexible and free-standing poly-CD nanofibrous membrane depicted outstanding filtration performance. We estimate of above 90% removal efficiency for highly concentrated solutions of MB pollutant (40 mg/L) under extremely high flux (3840 Lm-2h-1). Essentially, these poly-CD nanofibrous webs demonstrate quite rapid uptake of MB from liquid environment. Overall, bio-based flexible electrospun poly-CD nanofibrous membrane represents a highly efficient molecular filter for wastewater treatment.
Open Access
Electrospun polymeric nanofibrous composites containing TiO2 short nanofibers
(2011) Deniz, A. E.; Celebioglu A.; Kayaci, F.; Uyar, Tamer
In this study, polymeric nanofibrous composites containing anatase TiO 2 short nanofibers (TiO2-SNF) were successfully produced via electrospinning. The fabrication of the nanofibrous composite structure includes two steps. First, anatase TiO2 nanofibers were obtained by calcination of electrospun PVP/TiO2 nanofibers and then crushed into short nanofibers ranging from few microns in length. Second, these TiO 2-SNF were dispersed into polymer solutions and then electrospun into nanofibrous composites. We obtained nanofibers containing TiO2-SNF from different polymer types including PMMA, PAN, PET and PC. The SEM and TEM imaging indicated that some of the TiO2-SNF were fully covered by the polymeric matrix whereas some TiO2-SNF were partially covered and/or stick on the surface of the fibers. The photocatalytic activity of nanofibrous composites containing TiO2-SNF was evaluated by monitoring the photocatalytic decomposition of a model dye (rhodamine-6G) under UV irradiation. © 2011 Elsevier B.V. All rights reserved.
Open Access
Electrostatics of Polymer Translocation Events in Electrolyte Solutions
(American Institute of Physics Inc., 2016) Buyukdagli, S.; Ala-Nissila, T.
We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ∼10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.
Open Access
Energy based investigation of process parameters while drilling carbon fiber reinforced polymers
(Elsevier B.V., 2016) Karpat, Yiğit; Bahtiyar, O.
Carbon fiber reinforced polymers (CFRPs) are widely used in the aerospace industry due to their light weight, high strength, and low thermal conductivity. Drilling is a critical process that affects the quality of CFRP parts. This work studies the influence of process parameters on delamination and tool wear. Polycrystalline diamond helical drills are used in the experiments. It has been shown that drilling energy calculations can be used to set appropriate feed and speed parameters and for increasing drilling performance of CFRPs. The results also indicate the importance of thermal modeling of CFRP laminate for better understanding of the drilling process. © 2016 The Authors.
Open Access
Fabrication of flexible polymer–GaN core–shell nanofibers by the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition
(Royal Society of Chemistry, 2015) Ozgit Akgun, C.; Kayaci, F.; Vempati S.; Haider A.; Celebioglu A.; Goldenberg, E.; Kizir S.; Uyar, Tamer; Bıyıklı, Necmi
Here we demonstrate the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD) processes by fabricating flexible polymer-GaN organic-inorganic core-shell nanofibers at a processing temperature much lower than that needed for the preparation of conventional GaN ceramic nanofibers. Polymer-GaN organic-inorganic core-shell nanofibers fabricated by the HCPA-ALD of GaN on electrospun polymeric (nylon 6,6) nanofibers at 200 °C were characterized in detail using electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence measurements, and dynamic mechanical analysis. Although transmission electron microscopy studies indicated that the process parameters should be further optimized for obtaining ultimate uniformity and conformality on these high surface area 3D substrates, the HCPA-ALD process resulted in a ∼28 nm thick polycrystalline wurtzite GaN layer on polymeric nanofibers of an average fiber diameter of ∼70 nm. Having a flexible polymeric core and low processing temperature, these core-shell semiconducting nanofibers might have the potential to substitute brittle ceramic GaN nanofibers, which have already been shown to be high performance materials for various electronic and optoelectronic applications.