Browsing by Subject "Fluorescence"
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Item Open Access Broadband optical transparency in plasmonic nanocomposite polymer films via exciton-plasmon energy transfer(OSA - The Optical Society, 2016) Dhama R.; Rashed, A. R.; Caligiuri V.; El Kabbash M.; Strangi, G.; De Luca A.Inherent absorptive losses affect the performance of all plasmonic devices, limiting their fascinating applications in the visible range. Here, we report on the enhanced optical transparency obtained as a result of the broadband mitigation of optical losses in nanocomposite polymeric films, embedding core-shell quantum dots (CdSe@ZnS QDs) and gold nanoparticles (Au-NPs). Exciton-plasmon coupling enables non-radiative energy transfer processes from QDs to metal NPs, resulting in gain induced transparency of the hybrid flexible systems. Experimental evidences, such as fluorescence quenching and modifications of fluorescence lifetimes confirm the presence of this strong coupling between plexcitonic elements. Measures performed by means of an ultra-fast broadband pump-probe setup demonstrate loss compensation of gold NPs dispersed in plastic network in presence of gain. Furthermore, we compare two films containing different concentrations of gold NPs and same amount of QDs, to investigate the role of acceptor concentration (Au-NPs) in order to promote an effective and efficient energy transfer mechanism. Gain induced transparency in bulk systems represents a promising path towards the realization of loss compensated plasmonic devices. © 2016 Optical Society of America.Item Open Access Chemical modulation of singlet oxygen generation rates in thermal endoperoxide decomposition & novel fluorescent sensors for hyperphosporylated tau proteins(2016-05) Kaya, CansuChemical control over singlet oxygen generation is an open to improvement because of the importance of this reactive species in biological systems. In the first project, we aimed to synthesize a silylated 1,4-dimethylnaphthalene endoperoxide derivative which is expected to release singlet oxygen on thermolysis at a relatively slow rate at room temperature. Upon the deprotection of the silyl units with fluorine ions, it is expected it to release singlet oxygen at a much higher rate, giving rise to a control over the release of the product. The absorption and the fluorescence measurement with a trap molecule which consumes the generated singlet oxygen reveals promising results for the future work for the control of singlet oxygen generation rates. In the second part of this thesis, we focused on the synthesis of a novel fluorescent sensor of a BODIPY derivative which is capable of sensing Zinc cations. The zinc complex is also expected to have a further usage for the sensing of hyperphosphorylated tau proteins, which are commonly produced in the brains of people with Alzheimer’s disease. With this, it has a potential usage in the field of early detection of Alzheimer’s disease.Item Open Access Çokyollu kanal parametre kestirimi için yeni bir dizilim sinyal işleme tekniği(IEEE, 2007-06) Güldoǧan, Mehmet Burak; Arıkan, OrhanBu bildiride, çarpraz belirsizlik işlevinin kullanıldığı yeni bir dizilim sinyal işleme tekniği önerilmektedir. Geliştirilen teknik bir algılayıcı dizilimine gelen sinyallerden herbirinin geliş yönünü (GY), zaman gecikmesini Doppler kaymasını ve genliğini dürümlü bir sekilde kestirir. Önerilen Çarpraz Belirsizlik İşlevi - Yön Bulma (ÇBI-YB) tekniği ile Çoklu Sinyal Sınıflandırması (MUSIC) algoritmasının performansları sentetik sinyaller kullanılarak kök Ortalama Karesel Hata (kOKH) cinsinden değişik işaret Gürültü Oranı (İGO) değerleri için karşılaştırılmıştır. Önerilen tekniğin başarımı kayıt edilmiş çokyollu yüksek-enlem iyonosfer verileri üzerinde irdelenmiştir. Elde edilen sonuçlar, düşük İGO değerlerinde dahi çokyollu sinyal kaynaklarını ayırmada önerilen ÇBİ-YB tekniğinin ciddi başarım artışı sağladığını göstermektedir.Item Open Access Çokyollu ortamda çapraz belirsizlik işlevi-yön bulma tekniğinin başarım analizi(IEEE, 2008-04) Güldoǧan, Mehmet Burak; Arıkan, OrhanBu bildiride, Çapraz Belirsizlik İşlevi-Yön Bulma (CAFDF) tekniğinin çokyollu ortamlardaki sinyallerin zaman gecikmesi, Doppler kayması, geliş yönü(GY) ve genlik kestirimindeki başarımı ile yiiksek çözünürlüklü algoritmalar olan Uzay-Almaşan Genelleşmiş Beklenti-Enbüyüitme (SAGE) ve Çoklu Sinyal Sınıflandırılması(MUSIC)'in sentetik sinyaller iizerindeki başarımları kıyaslanmıştır. Algoritmalann performansları, kök Ortalama Karesel Hata (kOKH) cinsinden degişik işaret Gürültü Oranı (iGO) değerlerinde Monte Carlo denemelerine dayalı olarak sunulmuştur. Sentetik kanallarda istatiksel kıyaslama amaçlı Cramer-Rao alt sınırları eklenmiştir. Simülasyon sonuçları göstermektedir ki, orta ve düşük iGO değerlerinde CAF-DF diğer iki algoritmaya göre üstünlük sağlamaktadır.Item Unknown Colloidal photoluminescent refractive index nanosensor using plasmonic effects(De Gruyter, 2018) Guzatov, D. V.; Gaponenko, S. V.; Demir, Hilmi VolkanFluorescence enhancement by metal nanostructures which is sensitive to refractive index n of an ambient medium is suggested as an operation principle of a novel refractive index sensor for liquids. Calculations are made for spherical and spheroidal Ag particles, and potential feasibility of sensitivity of the order of Δn=10-4 is demonstrated. Sensors of this type can be made fully colloidal with metal bodies deposited on a substrate or comprising a metal layer covering colloidal assembly of dielectric particles to serve as a test strip as well as placed on a fiber tip end to get local probing of refractive index in the tip-enhanced refractometry mode. Colloidal core-shell semiconductor nanocrystals may become the best candidates for this type of sensors whereas molecular probes may be affected by chemical properties of tested liquids.Item Unknown Comparison of the CAF-DF and sage algorithms in multipath channel parameter estimation(IEEE, 2008-07) Güldoğan, M. Burak; Arıkan, OrhanIn this paper, performance of the recently proposed Cross Ambiguity Function - Direction Finding (CAF-DF) technique is compared with the Space Alternating Generalized Expectation Maximization (SAGE) technique. The CAF-DF, iteratively estimates direction of arrival (DOA), time-delay, Doppler shift and amplitude corresponding to each impinging signal onto an antenna array by utilizing the cross ambiguity function. On synthetic signals, based on Monte Carlo trials, performances of the algoritms are tested in terms of root Mean Squared Error (rMSE) at different Signal-to-Noise Ratios (SNR). Cramer-Rao lower bound is included for statistical comparisons. Simulation results indicate the superior performance of the CAF-DF technique over SAGE technique for low and medium SNR values. © 2008 IEEE.Item Unknown Concentric ring structures as efficient SERS substrates(Institute of Electrical and Electronics Engineers, 2013) Cinel, N. A.; Cakmakyapan, S.; Ertas, G.; Özbay, EkmelPlasmonic nanopatterned structures that can work as highly efficient surface-enhanced Raman scattering (SERS) substrates are presented in this study. A 'coupled' concentric ring structure has been designed, fabricated, tuned, and compared to an 'etched' concentric ring structure and plain gold film via SERS experiments. The proposed design gives Raman signal intensity 630 times larger than plain gold film and 8 times larger than an 'etched' concentric ring structure. The surface plasmons were imaged with the fluorescence imaging technique and supporting numerical simulations were done.Item Unknown Controlled optical transition rates in nanodroplets(IEEE, 2000) Özçelik, SerdarThe time-resolved fluorescence measurements of 3,3′-diethyl-5,5′-dichloro-9-phenylthiacarbocyanine (DDPT) in bulk solvents and methanol-in-oil reverse micellar systems is presented which include nano-sized methanol droplets stabilized with anionic surfactant aerosol-OT (AOT) in n-heptane, at room temperature. Relative fluorescence intensities of DDPT increase with a factor of 16 in m/o reverse micelles in comparison to those in bulk methanol. The radiative and nonradiative rate constants decreases in methanol dispersions, indicating that internal motions of DDPT in the droplets is reduced due to strong electrostatic interactions between the positively charged DDPT and the negatively charged sulfonate head-groups of AOT.Item Unknown 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 Unknown Designing excited states: theory-guided access to efficient photosensitizers for photodynamic action(2011) Cakmak, Y.; Kolemen, S.; Duman, S.; Dede, Y.; Dolen, Y.; Kilic, B.; Kostereli, Z.; Yildirim, L. T.; Dogan, A. L.; Guc, D.; Akkaya, E. U.The in silico design of tetraradical S 1 states was validated experimentally through synthesis, followed by characterization including phosphorescence measurements, use of trap molecules, and cell culture studies, leading to a series of orthogonal dimers of Bodipy chromophores with remarkable singlet oxygen efficiencies (see picture). A new path for the rational development of efficient photosensitizers is thus revealed.Item 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.Item Open Access Fluorescent Si QD decoration onto a flexible polymeric electrospun nanofibrous mat for the colorimetric sensing of TNT(Royal Society of Chemistry, 2017) Arslan, O.; Aytac Z.; Uyar, TamerUV range light was used for the facile, effective and large-scale synthesis of visible light emitting, surface-protected silicon quantum dots (Si QDs) starting from an amine-functionalized alkoxy silane precursor. Within mild and easy hydrolysis/condensation environments, the use of an amine-functionalized precursor together with a reducing agent resulted in a bright visible green light that could be used for fluorescent analytical detection systems. Visible light emitting Si QDs were investigated and it was found that their emission character depends on the illumination time, hydrolysis/condensation conditions and pretreatments for the silane coupling agents. A Nylon 6,6 electrospun nanofibrous mat was selected as a substrate for decoration by the Si QDs in order to fabricate a flexible and free-standing polymeric nanofibrous mat posessing a visible light emitting character so that it could act as a visible colorimetric sensor. The visible light emitting Si QDs were decorated onto the Nylon 6,6 nanofibrous mats via covering the surfaces as a ‘nanodress’ by a simple impregnation/dip-coating and heat-curing methods. The analytical results revealed that the Si QDs decorated flexible polymeric nanofibrous mats could be utilized for colorimetric trinitrotoluene (TNT) detection in low concentrations.Item Open Access From virtual to physical: Integration of chemical logic gates(2011) Guliyev, R.; Ozturk, S.; Kostereli, Z.; Akkaya, E. U.Integration by parts: Advanced information processing at the molecular level requires integrated logic gates, which has to date been possible only virtually. Now, two independently working AND molecular logic gates are brought together by "click" chemistry to form integrated logic gates which respond exactly as predicted from such an integration scheme (see picture, EET=excitation energy transfer).Item Open Access Generalized theory of förster-type nonradiative energy transfer in nanostructures with mixed dimensionality(American Chemical Society, 2013-04-16) Hernandez-Martinez, P. L.; Govorov, A. O.; Demir, Hilmi VolkanForster-type nonradiative energy transfer (NRET) is widely used, especially utilizing nanostructures in different combinations and configurations. However, the existing well-accepted Forster theory is only for the case of a single particle serving as a donor together with another particle serving as an acceptor. There are also other special cases previously studied; however, there is no complete picture and unified understanding. Therefore, there is a strong need for a complete theory that models Forster-type NRET for the cases of mixed dimensionality including all combinations and configurations. We report a generalized theory for the Forster-type, NRET, which includes the derivation of the effective dielectric function due to the donor in different confinement geometries and the derivation of transfer rates distance dependencies due to the acceptor in different confinement geometries, resulting in a complete picture and understanding of the mixed dimensionality.Item Open Access Highly fluorescent pyrene-functional polystyrene copolymer nanofibers for enhanced sensing performance of TNT(American Chemical Society, 2015) Senthamizhan, A.; Celebioglu A.; Bayir, S.; Gorur, M.; Doganci, E.; Yilmaz, F.; Uyar, TamerA pyrene-functional polystyrene copolymer was prepared via 1,3-dipolar cycloaddition reaction (Sharpless-type click recation) between azide-functional styrene copolymer and 1-ethynylpyrene. Subsequently, nanofibers of pyrene-functional polystyrene copolymer were obtained by using electrospinning technique. The nanofibers thus obtained, found to preserve their parent fluorescence nature, confirmed the avoidance of aggregation during fiber formation. The trace detection of trinitrotoluene (TNT) in water with a detection limit of 5 nM was demonstrated, which is much lower than the maximum allowable limit set by the U.S. Environmental Protection Agency. Interestingly, the sensing performance was found to be selective toward TNT in water, even in the presence of higher concentrations of toxic metal pollutants such as Cd2+, Co2+, Cu2+, and Hg2+. The enhanced sensing performance was found to be due to the enlarged contact area and intrinsic nanoporous fiber morphology. Effortlessly, the visual colorimetric sensing performance can be seen by naked eye with a color change in a response time of few seconds. Furthermore, vapor-phase detection of TNT was studied, and the results are discussed herein. In terms of practical application, electrospun nanofibrous web of pyrene-functional polystyrene copolymer has various salient features including flexibility, reproducibility, and ease of use, and visual outputs increase their value and add to their advantage.Item Embargo Hybrid biosensing systems for the detection of biomolecules and disease biomarkers(2023-08) Aslan, YusufOptical metasurfaces are configurations of artificially structured surfaces designed to obtain unusual electromagnetic properties. The ability to manipulate a confined electromagnetic field enables metasurfaces to be utilized as optical point-of-care (POC) biosensors for the detection of low concentrations of biomarkers. Moreover, the integration of fluorescent molecules and plasmonic metasurfaces is utilized to enhance both plasmonic and fluorescent signals; however, the nanoscale distance and spectral overlap between the fluorescent emitter and plasmonic metasurface are crucial for the separation of the fluorescence-coupled plasmonic radiation and non-radiative induced plasmon surface entrapment. In this study, fluorescently labeled (FITC) proteins are integrated over a plasmonic metasurface via three different surface modifications for obtaining a hybrid biosensing system that boosts the device’s plasmonic sensitivity and lowers the detection limit. The metasurface is fabricated via physical vapor deposition of titanium (10 nm), silver (30 nm), and gold (15 nm), respectively over polycarbonate nanograting substrates of optical disks (DVDs). Additionally, the surface modifications are arranged via short-distance, medium-distance, and long-distance modifications for fluorescently labeled molecule binding. After the evaluations, the highest plasmonic wavelength shift over the FITC labeled protein binding is obtained from the medium-distance modification with ~4.4 times signal enhancement over the short-distance modification. The medium-distance modification is further combined with an immunoassay for the detection of Alzheimer’s disease. Consequently, this study paves the way for designing new arrangements on a metasurface to couple with fluorescence molecules while enhancing the analytical performance of the plasmonic biosensor.Item Open Access Increased quantum efficiency and reduced red-shift in polymer nanoparticle luminophors(IEEE, 2008-11) Huyal, İlkem Özge; Özel, Tuncay; Tuncel, Dönüş; Demir, Hilmi VolkanIn this paper, using a polyfluorene derivative, increased fluorescence quantum efficiency and reduced red-shift in the film form of polymer nanoparticle luminophors is achieved, when compared to directly spin coated polymer thin films.Item Open Access Inter-varietal structural variation in grapevine genomes(Wiley-Blackwell Publishing Ltd., 2016) Cardone, M. F.; D'Addabbo, P.; Alkan C.; Bergamini, C.; Catacchio, C. R.; Anaclerio, F.; Chiatante, G.; Marra, A.; Giannuzzi, G.; Perniola, R.; Ventura M.; Antonacci, D.Grapevine (Vitis vinifera L.) is one of the world's most important crop plants, which is of large economic value for fruit and wine production. There is much interest in identifying genomic variations and their functional effects on inter-varietal, phenotypic differences. Using an approach developed for the analysis of human and mammalian genomes, which combines high-throughput sequencing, array comparative genomic hybridization, fluorescent in�situ hybridization and quantitative PCR, we created an inter-varietal atlas of structural variations and single nucleotide variants (SNVs) for the grapevine genome analyzing four economically and genetically relevant table grapevine varieties. We found 4.8 million SNVs and detected 8% of the grapevine genome to be affected by genomic variations. We identified more than 700 copy number variation (CNV) regions and more than 2000 genes subjected to CNV as potential candidates for phenotypic differences between varietiesItem Open Access Investigation of binding properties of dicationic styrylimidazo[1,2-a]pyridinium dyes to human serum albumin by spectroscopic techniques(John Wiley and Sons Ltd, 2017) Özdemir, A.; Gökoğlu, E.; Yılmaz, Esra; Yalçın, E.; Gökoğlu, E.; Seferoğlu, Z.; Tekinay, T.The binding interaction between two dicationic styrylimidazo[1,2-a]pyridinium dyes and human serum albumin (HSA) was investigated at physiological conditions using fluorescence, UV–vis absorption, and circular dichroism (CD) spectroscopies. Analysis of the fluorescence titration data at different temperatures suggested that the fluorescence quenching mechanism of HSA by these dyes was static. The calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) indicated that hydrogen bonding and van der Waals forces played a major role in the formation of the dye–HSA complex. Binding distances (r) between dyes and HSA were calculated according to Förster's non-radiative energy transfer theory. Studies of conformational changes of HSA using CD measurements indicate that the α-helical content of the protein decreased upon binding of the dyes.Item Open Access Ion sensing, light harvesting, energy conversion & self-assembly in rationally designed molecular constructs(2013) Büyükçakır, OnurIn this thesis, we have constructed rationally designed functional supramolecular systems. In the first chapter, we reported two Bodipy based chemodosimeters to detect fluoride both in solution and in polymethylmethaacraylate (PMMA) matrix. In the second part, we synthesized tetrastyrl-Bodipy derivatives by condensing methyl substituents of 1,3,5,7-tetramethyl-Bodipy dyes with different aromatic aldehydes. The resulting dyes have sharp and intense emission maxima in the near-IR region and they are robust candidates for functional supramolecular systems because of their outstanding properties. In next chapter, we investigated light harvesting properties of these new generation near-IR emissive dyes. In designed light harvesters, a near-IR emissive tetrastyrl-Bodipy dye which was decorated with short wavelength Bodipy fluorophores function as antenna units. In the forth chapter, we reported a Cu(I)-diimine complex as a photosensitizer for dye-sensitized solar cells (DSSC). It was demonstrated that Cu(I) diimine complex with capability of ultrafast electron injection to TiO2 nanoparticles can be a very good candidate for replacing ruthenium based polypyridyl complexes with a much lower cost. This research potentially can generate significant impact for those working on solar energy conversion and DSSC. In the final chapter, we propose to utilize oscillations in pH to move the two components of pseudorotoxane in relation to each other and this is the first example of a pseudorotaxane in which the mobile component is shuttling autonomously.
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