Browsing by Author "Tuncel, D."

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Open Access
[5]Rotaxane and [5]pseudorotaxane based on cucurbit[6]uril and anchored to a meso-tetraphenyl porphyrin
(2006) Tuncel, D.; Cindir, N.; Koldemir, Ü.
Water soluble [5]rotaxane and [5]pseudorotaxane based on cucurbit[6]uril and anchored to a meso-tetraphenyl porphyrin have been synthesized and characterized by spectroscopic methods (1H-NMR, 13C-NMR and UV), and by elemental analysis, and mass spectrometry. The preliminary results of the pH-driven switching properties of [5]rotaxane investigated through 1H-NMR spectroscopy are reported. These results were compared with those obtained from a model porphyrin, which was prepared by the de-threading cucurbit[6]uril from [5]pseudorotaxane under basic conditions. © Springer 2006.
Open Access
Catalytic self-threading: a new route for the synthesis of polyrotaxanes
(American Chemical Society, 2004) Tuncel, D.; Steinke, J. H. G.
Main chain and branched polyrotaxanes have been synthesized in which polymerization and rotaxane formation occur simultaneously, due to the presence of the catalytically active self-threading macrocycle cucurbit[6]uril. Using monomers that contain stopper groups to prevent the catalytic macrocycle from noncatalytic threading, it was possible to prepare polyrotaxanes in high yields with molecular weights up to 39000. These polyrotaxanes are structurally perfect in the sense that exactly two macrocyles are threaded onto each structural repeat unit. Investigations into the polymerization mechanism have demonstrated that the catalyst cucurbit[6]uril is highly sensitive toward the structure of the monomers employed and a poorly designed monomer may result in complete inactivity. Features of the mechanism are discussed in some detail.
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
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
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.
Open Access
Cucurbituril-based supramolecular engineered nanostructured materials
(Royal Society of Chemistry, 2014-11-03) Gürbüz, S.; Idris, M.; Tuncel, D.
Cucurbituril (CB) is a unique macrocycle with a rigid symmetrical structure, which is composed of two identical hydrophilic portals decorated with partially negatively charged carbonyl groups and a hydrophobic cavity. A number of different nanostructured materials, including nanoparticles, nanocomposites, vesicles and rods, have been prepared by taking advantage of the varying cavity size of the CB homologues, their ability to accommodate more than one guest in their cavities, their rigid symmetrical structures, as well as the water solubility of CB7. These nanostructures could find a wide range of potential applications in the areas of self-healing materials, nanomedicine, plasmonics, and nanocatalysis. Here, we review the recent progresses in the synthesis, properties and application of CB-based supramolecular engineered nanostructures, which are either constructed through CB-assisted self-assembly or from post-functionalized-CB homologues.
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
Dual functionality of conjugated polymer nanoparticles as an anticancer drug carrier and a fluorescent probe for cell imaging
(Royal Society of Chemistry, 2014) Gezici, Ö.; Durmaz, I.; Güven, E. B.; Ünal, Ö.; Özgün, A.; Cetin Atalay, R.; Tuncel, D.
Multifunctional nanoparticles based on a green emitting, hydrophobic conjugated polymer, poly[(9,9-bis{propeny}fluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1,3}-thiodiazole)] (PPFBT), that acts both as a fluorescent reporter and a matrix to accommodate an anti-cancer compound, camptothecin (CPT), were prepared, characterized and their potential as a fluorescent probe for cell imaging and as a drug delivery vehicle were evaluated via in vitro cell assays. The cell viability of human hepatocellular carcinoma cell line (Huh7) was investigated in the absence and presence of CPT with sulforhodamine B (SRB) and real-time cell electronic sensing (RT-CES) cytotoxicity assays.
Open Access
The effect of cucurbit[n]uril on the solubility, morphology, and the photophysical properties of nonionic conjugated polymers in an aqueous medium
(2010) Tuncel, D.; Artar, M.; Hanay, S. B.
The effects of cucurbit[n]uril on the dissolution and the photophysical properties of nonionic conjugated polymers in water are described. For this purpose, a fluorine-based polymer, namely, poly[9,9-bis{6(N,N-dimethylamino) hexyl}fluorene-co-2,5-thienylene (PFT) was synthesized and characterized by spectroscopic techniques including 1D and 2D NMR, UV-vis, fluorescent spectroscopy, and matrix-assisted laser desorption mass spectrometry (MALDI-MS). For the first time, it was demonstrated that a nonionic conjugated polymer can be made soluble in water through an inclusion complex formation with CB8. The structure of the complex was elucidated by NMR experiments including 1H and selective 1D-NOESY. This complex emits green and is highly fluorescent with fluorescent quantum yield of 35%. In contrast, CB6 or water-soluble CB7 although they are chemically identical to CB8 do not have any effect on the dissolution and photophysical properties of PFT. By preparing a protonated version of PFT, the optical properties of PFT in methanol, protonated PFT and PFT@CB8 in water have been studied and compared. It was also observed that the morphology of the polymer PFT was affected by the presence of CB8. Thus CB8-assisted self-assembly of polymer chains leads to vesicles formation; these structures were characterized by DLS, AFM, SEM, and TEM fluorescent optical microscopy.
Open Access
Facile synthesis of cross-linked patchy fluorescent conjugated polymer nanoparticles by click reactions
(2011) İbrahimova, V.; Ekiz, S.; Gezici, Ö.; Tuncel, D.
Here, we report a novel method to synthesize multifunctional nanoparticles that can be used in biological studies, such as in cell imaging and as a carrier for biomolecules/drugs. The nanoparticles were prepared either via Cu-catalyzed or cucurbit[6]uril (CB6)-catalyzed click reactions between azide groups containing hydrophobic blue, green and yellow emitting 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. Moreover, CB6 not only acted as a catalyst to facilitate the copper-free click reaction, but it also allowed us to obtain nanoparticles containing rotaxanes in which the triazole units were encapsulated by CB6 units. 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
High-stability, high-efficiency organic monoliths made of oligomer nanoparticles wrapped in organic matrix
(American Chemical Society, 2016) Soran-Erdem Z.; Erdem, T.; Gungor K.; Pennakalathil, J.; Tuncel, D.; Demir, Hilmi Volkan
Oligomer nanoparticles (OL NPs) have been considered unsuitable for solid-state lighting due to their low quantum yields and low temperature stability of their emission. Here, we address these problems by forming highly emissive and stable OL NPs solids to make them applicable in lighting. For this purpose, we incorporated OL NPs into sucrose matrix and then prepared their all-organic monoliths. We show that wrapping the OL NPs in sucrose significantly increases their quantum yield up to 44%, while the efficiency of their dispersion and direct solid-film remain only at ∼6%. We further showed ∼3-fold improved temperature stability of OL NP emission within these monoliths. Our experiments revealed that a physical passivation mechanism is responsible from these improvements. As a proof-of-concept demonstration, we successfully employed these high-stability, high-efficiency monoliths as color converters on a blue LED chip. Considering the improved optical features, low cost, and simplicity of the presented methodology, we believe that this study holds great promise for a ubiquitous use of organic OL NPs in lighting and possibly in other photonic applications.
Open Access
Highly luminescent CB[7]-based conjugated polyrotaxanes embedded into crystalline matrices
(Wiley-VCH Verlag, 2017) Erdem, T.; Idris, M.; Demir, Hilmi Volkan; Tuncel, D.
π-Conjugated polymers suffer from low quantum yields (QYs) due to chain–chain interactions. Furthermore, their emission in solid films is significantly quenched due to aggregation leading further decrease in QY. These are the two main issues of these materials hampering their widespread use in optoelectronic devices. To address these issues, here the backbone of poly(9,9′-bis(6″-(N,N,N-trimethylammonium)hexyl)fluorene-alt-co-thiophenelene) is isolated by threading with cucurbit[7]uril (CB7). Subsequently, the conjugated polyrotaxanes are incorporated into organic crystalline matrices to obtain highly efficient color-converting solids suitable for solid-state lighting. Upon threading the polymer backbone with CB7s, although the QY of the resulting polyrotaxane in solution state increases, the quenching problem in their solid state is not completely tackled. To solve this problem, these conjugated polyrotaxanes are embedded into various crystalline matrices and their remarkably high QYs (>50%) in the solution are successfully maintained in the solid state. To demonstrate the suitability of these aforementioned materials for solid-state lighting, a proof-of-concept light-emitting diode is constructed by employing their powders as color converters.
Open Access
Molecular switch based on a cucurbit[6]uril containing bistable [3]rotaxane
(2007) Tuncel, D.; Özsar, Ö.; Tiftik, H. B.; Salih, B.
A bistable CB6-based [3]rotaxane with two recognition sites has been prepared very efficiently in a high yield synthesis through CB6 catalyzed 1,3-dipolar cycloaddition; this rotaxane behaves as a reversible molecular switch and exhibits conformational changes caused by the movement of rings under base, acid and heat stimuli from one location to the other. © The Royal Society of Chemistry.
Open Access
Morphology-dependent energy transfer of polyfluorene nanoparticles decorating InGaN/GaN quantum-well nanopillars
(American Chemical Society, 2013) Erdem, T.; Ibrahimova, V.; Jeon, D. W.; Lee, I. H.; Tuncel, D.; Demir, Hilmi Volkan
Conjugated polymer nanoparticles (CPNs), prepared in aqueous dispersion from poly[(9,9-bis{3- bromopropyl}fluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1,3}-thiodiazole)] (PFBT-Br), are incorporated into a nanopillar architecture of InGaN/GaN multiple quantum wells (MQWs) to demonstrate a new organic/inorganic class of nanostructured excitonic model system. This hybrid system enables intimate integration for strong exciton−exciton interactions through nonradiative energy transfer (NRET) between the integrated CPNs and MQW pillars. The NRET of these excitonic systems is systematically investigated at varied temperatures. In these hybrids, InGaN/GaN MQWs serve as the donor of the NRET pair, while immobilized PFBT-Br polymer serves as the acceptor. To understand morphology-dependent NRET, PFBT-Br CPNs coating InGaN/GaN MQWs are made to defold into polymer chains by in situ treatment with a good solvent (THF). The experimental results indicate that NRET is significantly stronger in the case of CPNs compared with their defolded polymer chains. At room temperature, while the NRET efficiency of open polymer chains−nanopillar system is only 10%, PFBT-Br CPNs exhibit a substantially higher NRET efficiency of 33% (preserving the total number of polymer molecules). The NRET efficiency of the nanoparticle systems is observed to be 25% at 250 K, 22% at 200 K, 19% at 150 K, and 15% at 100 K. On the other hand, the defolded polymer chains exhibit significantly lower NRET efficiencies of 17% at 250 K, 16% at 200 K, 11% at 150 K, and 5% at 100 K. This work may potentially open up new opportunities for the hybrid organic/inorganic systems where strong excitonic interactions are desired for light generation, light harvesting, and sensing applications.
Open Access
Nanoparticle labeling of bone marrow-derived rat mesenchymal stem cells: their use in differentiation and tracking
(Hindawi Publishing Corporation, 2015) Akhan, E.; Tuncel, D.; Akcali, K. C.
Mesenchymal stem cells (MSCs) are promising candidates for cellular therapies due to their ability to migrate to damaged tissue without inducing immune reaction. Many techniques have been developed to trace MSCs and their differentiation efficacy; however, all of these methods have limitations. Conjugated polymer based water-dispersible nanoparticles (CPN) represent a new class of probes because they offer high brightness, improved photostability, high fluorescent quantum yield, and noncytotoxicity comparing to conventional dyes and quantum dots. We aimed to use this tool for tracing MSCs’ fate in vitro and in vivo. MSC marker expression, survival, and differentiation capacity were assessed upon CPN treatment. Our results showed that after CPN labeling, MSC markers did not change and significant number of cells were found to be viable as revealed by MTT. Fluorescent signals were retained for 3 weeks after they were differentiated into osteocytes, adipocytes, and chondrocytes in vitro. We also showed that the labeled MSCs migrated to the site of injury and retained their labels in an in vivo liver regeneration model. The utilization of nanoparticle could be a promising tool for the tracking of MSCs in vivo and in vitro and therefore can be a useful tool to understand differentiation and homing mechanisms of MSCs.
Open Access
Non-covalent interactions between carbon nanotubes and conjugated polymers
(Royal Society of Chemistry, 2011) Tuncel, D.
Carbon nanotubes (CNTs) are interest to many different disciplines including chemistry, physics, biology, material science and engineering because of their unique properties and potential applications in various areas spanning from optoelectronics to biotechnology. However, one of the drawbacks associated with these materials is their insolubility which limits their wide accessibility for many applications. Various approaches have been adopted to circumvent this problem including modification of carbon nanotube surfaces by non-covalent and covalent attachments of solubilizing groups. Covalent approach modification may alter the intrinsic properties of carbon nanotubes and, in turn make them undesirable for many applications. On the other hand, a non-covalent approach helps to improve the solubility of CNTs while preserving their intrinsic properties. Among many noncovalent modifiers of CNTs, conjugated polymers are receiving increasing attention and highly appealing because of a number of reasons. To this end, the aim of this feature article is to review the recent results on the conjugated polymer-based non-covalent functionalization of CNTs with an emphasis on the effect of conjugated polymers in the dispersibility/solubility, optical, thermal and mechanical properties of carbon nanotubes as well as their usage in the purification and isolation of a specific single-walled nanotube from the mixture of the various tubes.
Open Access
Non-radiative resonance energy transfer in bi-polymer nanoparticles of fluorescent conjugated polymers
(Optical Society of American (OSA), 2010) Ozel I.O.; Ozel, T.; Demir, Hilmi Volkan; Tuncel, D.
This work demonstrates the comparative studies of non-radiative resonance energy transfer in bi-polymer nanoparticles based on fluorescent conjugated polymers. For this purpose, poly[(9,9-dihexylfluorene) (PF) as a donor (D) and poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) as an acceptor (A) have been utilized, from which four different bi-polymer nanoparticle systems are designed and synthesized. Both, steady-state fluorescence spectra and time-resolved fluorescence measurements indicate varying energy transfer efficiencies from the host polymer PF to the acceptor polymer MEH-PPV depending on the D-A distances and structural properties of the nanoparticles. The first approach involves the preparation of PF and MEH-PPV nanoparticles separately and mixing them at a certain ratio. In the second approach, first PF and MEH-PPV solutions are mixed prior to nanoparticle formation and then nanoparticles are prepared from the mixture. Third and fourth approaches involve the sequential nanoparticle preparation. In the former, nanoparticles are prepared to have PF as a core and MEH-PPV as a shell. The latter is the reverse of the third in which the core is MEH-PPV and the shell is PF. The highest energy transfer efficiency recorded to be 35% is obtained from the last system, in which a PF layer is sequentially formed on MEH-PPV NPs. © 2010 Optical Society of America.
Open Access
On the origin of high quality white light emission from a hybrid organic / inorganic light emitting diode using azide functionalized polyfluorene
(Royal Society of Chemistry, 2008) Huyal I.O.; Koldemir, U.; Ozel, T.; Demir, Hilmi Volkan; Tuncel, D.
High quality white light generation with high colour rendering index (CRI) was achieved by integrating a cross-linkable azide functionalized polyfluorene derivative, namely poly[(9,9-dihexylfluorene)-co-alt-(9,9-bis(6-azidohexyl) fluorene)] (PFA), as a down-converting fluorescent material on the inorganic n-UV InGaN/GaN LED platform. For comparison, two other polyfluorene based polymers, namely poly[(9,9-dihexylfluorene)-co-alt-(9,9-bis(6-bromohexyl) fluorene)] (PFB) and poly[9,9-dihexyl-9H-fluorene] (PF), were tested for white light generation. While PFA and PF both led to white light generation, PFB fell out of the white region on the chromaticity diagram. Compared to PFA, both of the control groups (PF and PFB) exhibited much lower CRI. To gain a better insight into the mechanisms playing a key role for the generation of such high quality white light in PFA, all of these polymers were further subjected to a series of experiments such as controlled exposure to heat at 220 °C for 2 h under Ar and in air. The polymers PFA and PFB, which include cross-linkable groups, produced broad emission spectra in the region of 430-650 nm upon annealing in the absence of oxygen under Ar atmosphere while almost no change was observed in the emission spectrum of PF without any cross-linkable groups. PFA undergoes cross-linking through the decomposition of azide leading to reactive nitrene species, whereas in PFB cross-linking probably occurs via debromination. This result clearly proved that the broadening can not be attributed only to photo or thermal oxidation, but it is also due to cross-linking. PFA was also exposed to n-UV light from the InGaN/GaN LED to investigate its photostability. In these experiments, the spectral changes in absorbance and emission properties and thermal transitions of these polymers were monitored by FT-IR, UV-Vis and fluorescent spectrometry, and differential scanning calorimetry (DSC). These experiments indicated that PFA provides high quality white light opportunely via cross-linking and remains stable once cross-linking is formed in a solid film.
Open Access
One-pot synthesis of hybrid conjugated oligomer-Ag nanoparticles
(American Chemical Society, 2017) Balkan, T.; Kizir S.; Tuncel, D.
Here we report one-pot, straightforward synthesis of hybrid conjugated oligomer-silver nanoparticles (AgNPs) by utilizing tertiary alkyl amine and fluorenebenzothiodiazole- containing conjugated oligomer that both acts as a reducing agent in the reduction of silver ions into metallic silver and as a matrix to accommodate the newly formed AgNPs. By tuning the reaction conditions, it is possible to control the sizes and the structural features of hybrid nanoparticles as either raspberry or core−shell type hybrid structures.
Open Access
Optical and electronic properties of fluorene-based copolymers and their sensory applications
(John Wiley & Sons, Inc., 2013) Ibrahimova, V.; Kocak, M. E.; Önal, A. M.; Tuncel, D.
A series of novel, fluorene-based conjugated copolymers, poly[(9,9-bis{propenyl}-9H-fluorene)-co-(9,9-dihexyl9H-fluorene)] (P1), poly[(9,9-bis{carboxymethylsulfonyl-propyl}- fluorenyl-2,7-diyl)-co-(9,9-dihexyl-9H-fluorene)] (P2) and poly[(9,9- dihexylfluorene)-co-alt-(9,9-bis-(6-azidohexyl)fluorene)] (P3), are synthesized by Suzuki coupling reactions and their electrochemical properties, in the form of films, are investigated using cyclic voltammetry. The results reveal that the polymer films exhibit electrochromic properties with a pseudo-reversible redox behavior; transparent in the neutral state and dark violet in the oxidized state. Among the three polymers, P2 possesses the shortest response time and the highest coloration efficiency value. These polymers emit blue light with a band gap value of around 2.9 eV and have high fluorescent quantum yields. Their metal ion sensory abilities are also investigated by titrating them with a number of different transition metal ions; all of these polymers exhibit a higher selectivity toward Fe3þ ions than the other ions tested with Stern–Volmer constants of 4.41 106 M1 , 3.28 107 M1 , 1.25 106 M1 , and 6.56 106 M1 for P1, P2, water soluble version of P2 (P2S) and P3, respectively.