Chemistry / Kimya
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Article Citation - WoS: 61Citation - Scopus: 69Assessment of the Molecular Weight Distribution of Tannin Fractions Through Maldi-Tof Ms Analysis of Protein-Tannin Complexes(American Chemical Society, 2007) Mané, C.; Yalçın, Talat; Yalçın, Talat; Cheynier, V.; Cole, R. B.; Fulcrand, H.; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyAn innovative mass spectrometry method was developed for determining mass distributions of tannin fractions that cannot be approached through direct MALDI-TOF analysis. It was applied to three procyanidin fractions with average degrees of polymerizations = 3, 9, and 28, respectively, and one gallotannin fraction (Tara tannin). The proposed approach consists of MALDI-TOF analysis of the soluble complexes formed between these tannin fractions and bovine serum albumin (BSA). Complexes were detected as an unresolved "hump" following the BSA signal, and spectra were mathematically processed to determine the parameters relative to the protein-tannin complexes, which are the number-average molecular weight (Mn), the weight-average molecular weight (Mw), and the polydispersity index (PI) for each tannin fraction. Regarding condensed tannins, results are consistent with those of the standard method (thiolysis followed by HPLC separation) for all tested fractions. The method was successfully applied to a hydrolyzable tannin fraction but no standard method is available for comparison.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: 23Citation - Scopus: 28Direct Liquefaction of High-Sulfur Coals: Effect of the Catalyst, the Solvent, and the Mineral Matter(American Chemical Society, 2002) Gözmen, Belgin; Artok, Levent; Erbatur, Gaye; Erbatur, Oktay; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyTwo low-rank coals with high sulfur contents (Gediz subbituminous coal: 7.6 wt % S:dry basis. Çayirhan lignite: 5.7 wt% S:dry basis.) were subjected to hydroliquefaction. Liquefaction conditions included dry or solvent mediated runs under pressurized hydrogen without added catalyst or with the impregnated catalyst precursor ammonium heptamolybdate (AHM). Gediz coal having higher sulfur content gave 90% conversion in the absence of catalyst and solvent. Maximum conversion (98%) and maximum oil + gas yield (70%) from this coal were obtained by impregnating AHM onto coal and carrying out liquefaction in H 2/tetralin system at 450 °C for 30 min. Under the same conditions, Çayirhan lignite gave 85% conversion and 70.5% oil + gas yield. The superior hydrodesulfurization effect of impregnated AHM on the oil fraction when used in the absence of solvent (less than 0.1% S in lignite's oil and less than 1% S in subbituminous coal's oil following one-stage hydrogenation) is a promising finding of this work. AHM was found to be much more effective in liquefaction of Çayirhan lignite and this has been ascribed to the well-dispersion of AHM throughout this lignite's structure via a cation-exchange mechanism through oxygen functionalities. Strong evidence for the catalytic effect of clay minerals in coal structure on char-forming reactions during liquefaction was observed by making use of liquefaction reactions of demineralized coal samples. It was also observed that tetralin had a retarding effect on the condensation and subsequent cross-linking reactions.Article Citation - WoS: 13Citation - Scopus: 16Thermochromism in Oligothiophenes: the Role of the Internal Rotation(American Chemical Society, 2002) Elmacı, Nuran; Elmacı Irmak, Nuran; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyThe relation between thermochromism in polythiophenes and the internal rotation is studied by density-functional theory (DFT). For head-to-tail methyl-substituted thiophenes, rotational potential maps of dimer and trimer are calculated. With time-dependent-DFT methodology the absorption spectra of these oligomers in UV-vis region are calculated as functions of the torsional angles. Theoretical temperature-dependent UV-vis spectra are generated from the distribution of torsional angles. The results show that the internal rotation alone is not sufficient to explain the mechanism of thermochromism.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.Article Citation - WoS: 28Citation - Scopus: 29Formation of Pseudoisocyanine J-Aggregates in Poly(vinyl Alcohol) Fibers by Electrospinning(American Chemical Society, 2009) Demir, Mustafa Muammer; Özen, Bengisu; 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 TechnologySubmicrometer diameter, light emitting fibers of poly(vinyl alcohol) (PVA) doped with pseudoisocyanine (1,1′-diethyl-2,2′-cyanine bromide, PIC) dye were prepared by electrospinning. A horizontal setup was employed with a stationary collector consisting of two parallel-positioned metal strips separated by a void gap. Formation of uniaxially aligned and randomly deposited fibers in electrospun films was confirmed by microscopy. Photoluminescence (PL) spectroscopy is used to evaluate spectral properties of both types of fibers doped with PIC. While PIC molecules were individually dispersed in PVA solution, they assemble into J-aggregates upon electrospinning when the weight fraction of PIC molecules is above 2.5 wt %. The formation of J-aggregates was observed in both randomly deposited and uniaxially aligned electrospun fibers. Moreover, the fibers aligned uniaxially showed a high degree of polarized emission (PL |/PL⊥)10), arising from the orientation of J-aggregates along the fiber axis. On the other hand, isotropic emission of J-aggregates was observed from the fibers deposited randomly. As a conclusion, electrospinning was found to be an efficient and a practical method to form highly oriented J-aggregates dispersed into polymer fibers. To the best of our knowledge, it is the first time formation of J-aggregates (a bottom-up approach) and electrospinning (a topdown approach) is successfully combined.Article Citation - WoS: 119Citation - Scopus: 151Batch Removal of Aqueous Cu2+ Ions Using Nanoparticles of Zero-Valent Iron: a Study of the Capacity and Mechanism of Uptake(American Chemical Society, 2008) Karabelli, Duygu; Üzüm, Çağrı; Eroğlu, Ahmet Emin; Eroğlu, Ahmet Emin; Scott, Tom B.; Shahwan, Talal; Lieberwirth, Ingo; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyIn this study, nZVI prepared by borohydride reduction was applied for the removal of Cu2+ ions under a variety of experimental conditions. The uptake experiments investigated the effects of initial concentration, contact time, pH, and repetitive loading on the extent of retardation of Cu2+ ions. Within the applied conditions, the sorbent demonstrated fast uptake kinetics and outstanding fixation abilities up to an initial Cu2+ concentration of 200.0 mg/L. Partitioning of Cu2+ ions between liquid and solid phases demonstrated an isotherm of L-type. Within the studied conditions, the capacity of uptake was found to be 250 mg of Cu2+ per g of nZVI. According to X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) results, Cu2+ ions were sorbed primarily via a redox mechanism that resulted in the formation of Cu2O and Cu0. The contact of iron nanoparticles with aqueous media caused extensive formation of iron oxide. However, the material did not completely lose its removal capacity and was repeatedly applied at low concentrations for further uptake trials.