Chemistry / Kimya
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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; Özçelik, Serdar; İnanç, Arda; Demir, Mustafa Muammer; Topçu, Gökhan; Ünlütürk, Seçil Sevim; Özçelik, Serdar; Demir, Mustafa Muammer; İnci, Mehmet Naci; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyIn 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: 31Citation - Scopus: 36Integration of Triboluminescent Eud4tea Crystals To Transparent Polymers: Impact Sensor Application(American Chemical Society, 2017) İncel, Anıl; Eanes, Mehtap; Demir, Mustafa Muammer; Demir, Mustafa Muammer; Emirdağ Eanes, Mehtap; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyLanthanide-based organometallic materials are well-known candidate triboluminescent (TL) materials that can show bright emission when a mechanical force is applied. These materials are usually in the form of crystalline powders, and it is often useful to integrate these samples into a polymer matrix in order to achieve processability, enabling coating from a solution/molten state or fabrication as a complex-shaped matrix. In this work, micrometer-sized europium tetrakis (dibenzoylmethide) triethylammonium (EuD4TEA) crystals were synthesized and integrated with various transparent polymers (PMMA, PS, PVDF, and PU) using two approaches: (i) blending and (ii) surface impregnation. In the former method, the crystalline particles were molecularly dissolved; therefore, a TL response cannot be achieved. More than 10 wt % TL crystals in the composite is needed to obtain TL signals. However, TL signal was achieved at 2.5 wt % when a composite was prepared by the latter approach. TL intensity shows exponential decay with consecutive mechanical action. The TL emission of PU-based surface impregnated composite expires with long-lived emission, and maximum TL response with respect to applied force was measured between 2.45 and 42.0 N.Article Citation - WoS: 195Optical Properties of Composites of Pmma and Surface-Modified Zincite Nanoparticles(American Chemical Society, 2007) Demir, Mustafa Muammer; Demir, Mustafa Muammer; Akbey, Ümit; Bubeck, Christoph; Park, Insun; Lieberwirth, Ingo; Wegner, Gerhard; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 01. Izmir Institute of TechnologyLocate full-text(opens in a new window)|Full Text(opens in a new window)|View at Publisher| Export | Download | Add to List | More... Macromolecules Volume 40, Issue 4, 20 February 2007, Pages 1089-1100 Optical properties of composites of PMMA and surface-modified zincite nanoparticles (Article) Demir, M.M.a, Koynov, K.a, Akbey, Ü.a, Bubeck, C.a, Park, I.ab, Lieberwirth, I.a, Wegner, G.a a Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz, Germany b Seoul National University, School of Chemistry, Korea, South Korea View references (65) Abstract Composites that show visible light transmittance, UV absorption, and moderately high refractive index, based on poly(methyl methacrylate) (PMMA) and zinc oxide (zincite, ZnO) nanoparticles, were prepared in two steps. First, surface-modified ZnO nanoparticles with 22 nm average diameter were nucleated by controlled precipitation via acid-catalyzed esterification of zinc acetate dihydrate with pentan-1-ol. The surface of growing crystalline particles was modified with tert-butylphosphonic acid (tBuPO3H2) in situ by monolayer coverage. Particle size and graft density of -PO3H 2 on the particle surface were controlled by the amount of surfactant applied to the reaction solution. Second, the surface-modified particles were incorporated into PMMA by in-situ bulk polymerization. Free radical polymerization was carried out in the presence of these particles using AIBN as initiator. Volume fraction (0) of the particles was varied from 0.10 to 7.76% (0.5 to 30 wt %). Although the particles are homogeneously dispersed in monomer, segregation of the individual particles upon polymerization was observed. Optical constants of the films ca. 2.0 μm including absorption and scattering efficiencies, indices of refraction, and dispersion constants were determined. The absorption coefficient at 350 nm increases linearly with ZnO, obeying Beer's law at low particle contents. However, it levels off toward a value of about 5000 cm-1 and shows a negative deviation at high concentrations because of aggregation of the individual particles. Waveguide propagation loss coefficients of the composite films were examined by prism coupling. A steep increase of the loss coefficient was found with a slope of 52 dB cm-1 vol %-1 as the volume fraction of the particle increases. The refractive index of the composites depends linearly on volume fraction of ZnO and varies from 1.487 to 1.507 (φ = 7.76%) at 633 nm. The dispersion of refractive index was found to be consistent with Cauchy's formula.Article Citation - WoS: 2Dimensions of Polystyrene Particles Deposited on Mica From Dilute Cyclohexane Solution at Different Temperatures(American Chemical Society, 2002) Demir, Mustafa Muammer; Demir, Mustafa Muammer; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 01. Izmir Institute of TechnologyUsing atomic force microscopy, the height, diameter, and volume of polystyrene particles deposited on mica from dilute cyclohexane solution at different temperatures are determined. Dimensions exhibit a strong temperature dependence. The heights of the deposited particles are only a few atomic diameters, the major dimension being parallel to the mica surface. The number of single polystyrene molecules in a deposited particle cannot be determined directly by atomic force microscopy. However, the maximum number of molecules that may be present in a particle may be estimated. Below 35 °C, the particles possibly consist of single collapsed molecules. This number increases with temperature and becomes as large as about 30 molecules per particle at 80 °C. The volume occupied by a single chain in solvent is calculated as a function of temperature and compared with observed volumes of dry particles on mica. A linear relationship is observed between single chain volumes in solvent and corresponding particle volumes on mica. On the average, the volume of a single chain in solution is 10 times the volume of a dry particle at the corresponding temperature. Fluctuations of chain volumes that are dominant in solution are also present in the volumes of particles deposited and dried on mica.Article Citation - WoS: 12Probing Nanoscale Domains of J-Aggregates Deposited on a Mica Surface(American Chemical Society, 2004) Demir, Mustafa Muammer; Özçelik, Serdar; Özçelik, Serdar; Demir, Mustafa Muammer; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyJ-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: 64Citation - Scopus: 67Hierarchically Structured Metal Oxide/Silica Nanofibers by Colloid Electrospinning(American Chemical Society, 2012) Horzum Polat, Nesrin; Demir, Mustafa Muammer; Mun˜oz-Espí, Rafael; Glasser, Gunnar; Demir, Mustafa Muammer; Landfester, Katharina; Crespy, Daniel; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 01. Izmir Institute of TechnologyWe present herein a new concept for the preparation of nanofibrous metal oxides based on the simultaneous electrospinning of metal oxide precursors and silica nanoparticles. Precursor fibers are prepared by electrospinning silica nanoparticles (20 nm in diameter) dispersed in an aqueous solution of poly(acrylic acid) and metal salts. Upon calcination in air, the poly(acrylic acid) matrix is removed, the silica nanoparticles are cemented, and nanocrystalline metal oxide particles of 4-14 nm are nucleated at the surface of the silica nanoparticles. The obtained continuous silica fibers act as a structural framework for metal oxide nanoparticles and show improved mechanical integrity compared to the neat metal oxide fibers. The hierarchically nanostructured materials are promising for catalysis applications, as demonstrated by the successful degradation of a model dye in the presence of the fibers.Article Citation - WoS: 73Citation - Scopus: 73Toward Transparent Nanocomposites Based on Polystyrene Matrix and Pmma-Grafted Ceo 2 Nanoparticles(American Chemical Society, 2011) Parlak, Onur; Demir, Mustafa Muammer; Demir, Mustafa Muammer; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 01. Izmir Institute of TechnologyThe association of transparent polymer and nanosized pigment particles offers attractive optical materials for various potential and existing applications. However, the particles embedded into polymers scatter light due to refractive index (RI) mismatch and reduce transparency of the resulting composite material. In this study, optical composites based on polystyrene (PS) matrix and poly(methyl methacrylate) (PMMA)-grafted CeO 2 hybrid particles were prepared. CeO 2 nanoparticles with an average diameter of 18 ± 8 nm were precipitated by treating Ce(NO 3) ·6H 2O with urea in the presence of a polymerizable surfactant, 3-methacyloxypropyltrimethoxy silane. PMMA chains were grafted on the surface of the nanoparticles upon free radical in situ solution polymerization. While blending of unmodified CeO 2 particles with PS resulted in opaque films, the transparency of the composite films was remarkably enhanced when prepared by PMMA-grafted CeO 2 hybrid particles, particularly those having a PMMA thickness of 9 nm. The improvement in transparency is presumably due to the reduction in RI mismatch between CeO 2 particles and the PS matrix when using PMMA chains at the interface.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; Özçelik, Serdar; Özçelik, Serdar; Demir, Mustafa Muammer; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyWe 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: 5Citation - Scopus: 6Tailored Ceo2 Nanoparticles Surface in Free Radical Bulk Polymerization of Methyl Methacrylate(American Chemical Society, 2013) Tunusoğlu, Özge; Demir, Mustafa Muammer; Demir, Mustafa Muammer; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 01. Izmir Institute of TechnologyPolymerization of monomer/nanoparticle dispersion, namely in situ polymerization, has been frequently used for the fabrication of polymer nanocomposites. However, the interference of nanoparticle surface with polymerization in the course of composite formation has been tacitly neglected. In this work, surface-functionalized ceria nanoparticles were prepared using various capping agents: 3-(mercaptopropyl) trimethoxy silane, thioglycolic acid, 3-mercaptopropionic acid, and hexadecyltrimethyl ammonium bromide. Both in situ and ex situ approaches were applied for surface functionalization. The particles were dispersed into methyl methacrylate and free radical polymerization was carried out. The process of nanocomposite formation was examined in terms of conversion, molecular weight, and molecular weight distribution. The polymerization responded merely to the in situ functionalized particles. Regardless of the capping agents used, the particles function as a retarder and inhibitor. Their interaction with polymerization medium showed many complexities such that molecular weight was found to be strongly dependent on the capping agent employed.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; Özçelik, Serdar; Kuş, Mahmut; Özçelik, Serdar; Demir, Mustafa Muammer; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyLuminescent 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.