Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 6Citation - Scopus: 8Enhanced Spontaneous Emission Rate in a Low-Q Hybrid Photonic-Plasmonic Nanoresonator(American Chemical Society, 2019) Gökbulut, Belkıs; İnanç, Arda; Topçu, Gökhan; Ünlütürk, Seçil Sevim; Özçelik, Serdar; Demir, Mustafa Muammer; İnci, Mehmet NaciIn this paper, CdTe quantum dots (QDs)-doped single electrospun polymer nanofibers are partially coated with gold nanoparticles to form distinct hybrid photonic-plasmonic nanoresonators to investigate the critical role of the cavity-confined hybrid mode on the modification of the spontaneous emission dynamics of the fluorescent emitters in low-Q photonic cavities. A total enhancement factor of 11.2 is measured via a time-resolved experimental technique, which shows that there is an increase of about three times in the spontaneous emission rate for the QDs-doped gold nanoparticle-decorated nanofibers as they are compared with those uncoated ones. The physical mechanism affecting the spontaneous emission rate of the encapsulated QDs in such a hybrid photonic-plasmonic nanoresonator is explained to be due to regeneration of the mode field in the nanofiber cavity upon the interaction of the dipoles with the surface plasmons of distinctive gold nanoparticles that surround the outer surface of the nanofiber.Article Citation - WoS: 30Citation - Scopus: 30Glycidyl-Methacry Late-Based Electrospun Mats and Catalytic Silver Nanoparticles(John Wiley and Sons Inc., 2008) Demir, Mustafa Muammer; Uğur, Gökçe; Gülgün, Mehmet A.; Menceloğlu, Yusuf Z.P(AN-GMA) and PGMA fibers coated with monodisperse silver nanoparticles have been prepared by a combination of electrospinning and electroless plating. The morphology of the electrospun fibers remains unchanged after surface hydrazination. Oxidation of hydrazine in an ammoniacal solution of AgNO 3 reduces and deposits silver atoms along the fiber surface, which then coalesce to Ag particles. The size of the silver nanoparticles is varied between 20-60 nm. Since the density of the active sites for silver reduction is lower in P(AN-GMA), a smaller particle size could be obtained. The catalytic activity of the silver nanoparticles has been confirmed.Article Citation - WoS: 15Aggregation of Fillers Blended Into Random Elastomeric Networks: Theory and Comparison With Experiments(John Wiley and Sons Inc., 2006) Demir, Mustafa Muammer; Menceloğlu, Yusuf Ziya; Erman, BurakA theoretical model describing aggregation of filler particles in amorphous elastomers is proposed. The model is based on a counting technique originally used in genome analysis to characterize the size and distribution of overlapping segments randomly placed on a DNA molecule. In the present model, the particles are first assumed to aggregate randomly upon mixing into the elastomer and then-sizes are calculated. The sizes and distributions of aggregates are also studied in the presence of attractive interparticle forces. Results of the proposed model are compared with experimental data on silica-filled end-linked poly(dimethyl-siloxane) networks. Comparison of the theory and experiment shows that the random aggregation assumption where no attractive forces exist between the particles is not valid and a significant attraction between the silica particles is needed in the theory to justify the experimental data obtained using atomic force microscopy. For filler content below 1.45 vol.-%, the model agrees, qualitatively, with experiment and shows the increase in cluster size with increasing amount of filler. It also explains the increase in the dispersion of aggregate sizes with increasing amount of filler.Article Citation - WoS: 12Probing Nanoscale Domains of J-Aggregates Deposited on a Mica Surface(American Chemical Society, 2004) Demir, Mustafa Muammer; Özçelik, Serdar; Birkan, BurakJ-aggregates of 1,1′,3,3′-tetraethyl-5,5′,6,6′- tetrachlorobenzimidazolocarbocyanine (TTBC) were deposited on a mica surface and probed by atomic force microscopy operated at tapping mode in air. Optical spectra showed that J-aggregates were formed in aqueous solutions. Atomic force microscopy images revealed that J-aggregates deposited on mica surfaces mainly present single domains with a mean height of 2.00 ± 0.25 nm and an average diameter of 100 ± 20 nm. Quantitative analysis of the morphology of images indicated that the single domain of J-aggregates exhibits very uniform height and diameter distributions with polydispersity indices of 1.02 and 1.04, respectively. Based on the results, we propose a two-dimensional nanostructure in which TTBC J-aggregates could be arranged in a monolayer.Article Citation - WoS: 20Citation - Scopus: 23Rhodamine-Immobilised Electrospun Chitosan Nanofibrous Material as a Fluorescence Turn-On Hg2+ Sensor(John Wiley and Sons Inc., 2016) Horzum, Nesrin; Mete, Derya; Karakuş, Erman; Üçüncü, Muhammed; Emrullahoğlu, Mustafa; Demir, Mustafa MuammerA turn-on fluorescence sensing system for mercuric (Hg2+) ions relying on a modified rhodamine B–chitosan fluorophore moiety was developed. This novel sensing approach relies on the simultaneous electrospinning of chitosan and rhodamine B hydrazide with phenylisothiocyanate functionality in hexafluoroisopropanol solution at 3.4 kV cm−1. The electrospun mats exhibited not only considerably enhanced fluorescence intensity in the presence of mercury ions, a result attributed to the ring opening of the spirolactam unit of the rhodamine-based fluorophore, but also a remarkably high sensitivity and selectivity toward Hg2+. In effect, the strategy has the potential to open new avenues in the design and development of other high-performance nanofibrous sensing materials for detecting target metal species of environmental interest.Article Citation - WoS: 49Citation - Scopus: 51Voc Sensors Based on a Metal Oxide Nanofibrous Membrane/Qcm System Prepared by Electrospinning(Royal Society of Chemistry, 2014) Horzum Polat, Nesrin; Taşçıoğlu, Didem; Özbek, Cebrail; Okur, Salih; Demir, Mustafa MuammerWe report a simple synthetic route to fabricate crystalline ZnO and CeO2/ZnO nanofibrous mats and their sensing characteristics against volatile organic compounds (VOCs) such as benzene, propanol, ethanol, and dichloromethane. Precursor fibers were fabricated by electrospinning of poly(vinyl alcohol) and metal salt(s) at 2.5 kV cm-1 in aqueous solution. The fibers were directly deposited on the crystal surface of a quartz crystal microbalance (QCM). The crystal, which was coated by nanostructured PVA/metal precursor(s) fibers, was subjected to calcination in air at 500 °C for 5 h. The formation of an oxide based nanofiber mat was revealed by scanning electron microscopy and X-ray diffraction. Upon exposure of the nanofiber mats to the VOCs, the compounds adsorbed onto the surface of oxidic fibers. The physisorption of the compounds was confirmed by FTIR and QCM. Both systems showed sensitivity to the VOCs and they hold a broad promise particularly for sensing applications of volatile alcoholic compounds. The introduction of CeO2 into the ZnO structure reduced the sensitivity of ZnO most probably due to the decrement of oxygen vacancies.Article Citation - WoS: 6Citation - Scopus: 6Hierarchial Coassembly of a Cyanine Dye in Poly(vinyl Alcohol) Fibrous Films by Electrospinning(American Chemical Society, 2013) Demir, Mustafa Muammer; Horzum, Nesrin; Özen, Bengisu; Özçelik, SerdarWe report molecular aggregate formation of TTBC (1,1′,3,3′- tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine) in submicrometer-sized PVA (poly(vinyl alcohol)) fibers by electrospinning. The formation of the molecular aggregate is examined by solution and instrumental parameters of electrospinning. The precursor solution of PVA/TTBC, in the range of 0.016-0.065 wt % is subjected to electrospinning under an electrical field ranging from 0.95 to 1.81 kV cm-1. Both randomly deposited and uniaxially aligned fibers are achieved by using two parallel-positioned metal strips as counter electrode. Photoluminescence and polarized Fourier transform infrared spectroscopies are employed to determine spectral properties of the fibers. H-aggregates are formed within the electrospun fibers, regardless of their alignment, and H- and J-type aggregates coexist in the alternative spin-coated and the cast films. A strongly polarized photoluminescence emission is observed in the direction of uniaxially aligned fibers as a result of the orientation of the H-aggregates along the fiber axis. We demonstrate that electrospinning is a process capable of forming and orienting TTBC aggregates during the structural development of the polymer/dye nanofibers. These fibrous films may potentially find applications in optics and electronics.Article Citation - WoS: 36Citation - Scopus: 38Investigation on Glassy Skin Formation of Porous Polystyrene Fibers Electrospun From Dmf(BME-PT, 2010) Demir, Mustafa MuammerMicrometer and submicrometer diameter of polystyrene (PS) fibers were electrospun from various dimethyl formamide (DMF) solutions at different weight fractions under 35% relative humidity. Increasing polymer fraction in the solution results in a gradual morphological transition from beads-with-incipient to bead-free fibers and also increases the diameter. The formation of uniform glassy skin presumably due to radial capillary flow within the liquid jet was confirmed by scanning electron microscope. The thickness of the skin varies with the weight fraction of PS; therefore, it was normalized with respect to average fiber diameter (AFD). The skin gets thinner as the weight fraction of PS increases. In addition, the fibers exhibit highly porous internal structure and smooth surface along with slight porosity. The development of porosity is attributed to liquid-liquid phase separation of water molecules in atmospheric moisture and DMF.Article Citation - WoS: 2Citation - Scopus: 2Composites of Reactive Silica Nanoparticles and Poly(glycidyl Methacrylate) With Linear and Crosslinked Chains by in Situ Bulk Polymerization(Taylor and Francis Ltd., 2010) Demir, Mustafa Muammer; Altın, Burcu; Özçelik, SerdarComposites of poly(glycidyl methacrylate) (PGMA) and L-lysine-coated silica nanoparticles with varying contents were prepared by in situ bulk polymerization using benzoyl peroxide (BPO) as free radical initiator. Silica nanoparticles covered by L-lysine molecules were synthesized using emulsion method. Dynamic light scattering measurements confirmed that the particles are highly monodisperse with the diameter of 10 nm and free of aggregates in the monomer (glycidyl methacrylate, GMA). Upon polymerization of the homogeneous particle/monomer dispersion, aggregates of individual silica nanoparticles are observed by tapping mode atomic force microscope (AFM). Amine and/or carboxylic acid sites on particle surface covalently react with the oxirane groups of the polymer backbone. The aggregation was substantially suppressed by using a difunctional comonomer divinyl benzene (DVB) in polymerization. A three-dimensional polymer network, P(GMA-DVB), forms throughout the system. This structure leads to significant progress in particle dispersion, therefore in physical properties of the resulting composite. We demonstrated that the composites prepared by crosslinked chains are thermally more stable and mechanically stiffer than those prepared by linear ones.Article Citation - WoS: 15Citation - Scopus: 15Controlling Spontaneous Emission of Cdse Nanoparticles Dispersed in Electrospun Fibers of Polycarbonate Urethane(American Chemical Society, 2009) Demir, Mustafa Muammer; Soysal, Duygu; Ünlü, Caner; Kuş, Mahmut; Özçelik, SerdarLuminescent fibrous composite films consisting of submicrometer diameter fibers were prepared by electrospinning of segmented polycarbonate urethane (PCU) in dimethyl formamide and tri-n-octylphosphine oxide (TOPO)-capped CdSe nanocrystals (5 nm in diameter) in toluene. Using a pair of conductive electrodes separated with an air gap, we successfully produced randomly deposited and uniaxially aligned electrospun fibers. The surface structure of the electrospun fibers was studied using atomic force microscopy (AFM) and was compared to the corresponding film prepared by casting. In cast film, tapping mode AFM imaging suggests that hard urethane segments organize into rodlike morphology dispersed in soft polycarbonate. When PCU/ CdSe dispersions were subjected to electrospinning, copolymer domains were forced to arrange into lamella along the fiber axis due to elongational flow and high stretching. Molecular orientation in the domains of the composite fibers was confirmed by polarized infrared spectroscopy. We demonstrated that formation of the oriented domains by electrospinning develops a hierarchical structure, which consequently modifies spectral properties because new multiple sharp lines appeared in the photoluminescence (PL) spectra of the fibers. In contrast to randomly deposited fibers, the PL intensity of uniaxially aligned fibers was found to be angle dependent. We propose that the elongated internal structure within the fibers controls the spontaneous emission of CdSe nanoparticles dispersed throughout the electrospun mat. A discussion on the nature of the controlled spontaneous emission is provided.