WoS İndeksli Yayınlar Koleksiyonu / WoS Indexed Publications Collection
Permanent URI for this collectionhttps://hdl.handle.net/11147/7150
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Article Citation - WoS: 21Citation - Scopus: 21Palladium-Catalyzed Alkoxycarbonylation of Conjugated Enyne Oxiranes: a Diastereoselective Method for the Synthesis of 7-Hydroxy(American Chemical Society, 2015) Kuş, Melih; Artok, Levent; Aygün, MuhittinPalladium-catalyzed alkoxycarbonylative 1,5-substitution of conjugated enyne oxiranes provides a diastereoselective route to (E)-configured 7-hydroxy-2,3,5-trienoates. The reactions proceeded in a highly stereoselective manner, possibly through sequential formation of π-allylpalladium and σ-vinylallenyl palladium complexes. The major diastereomeric form of the product is determined by the configuration of the alkenyl moiety of the substrate.Article Citation - WoS: 38Citation - Scopus: 36Structural Studies of Geosmin Synthase, a Bifunctional Sesquiterpene Synthase With ?? Domain Architecture That Catalyzes a Unique Cyclization-Fragmentation Reaction Sequence(American Chemical Society, 2015) Harris, Golda G.; Lombardi, Patrick M.; Pemberton, Travis A.; Matsui, Tsutomu; Weiss, Thomas M.; Cole, Kathryn E.; Köksal, Mustafa; Murphy, Frank V.; Vedula, L. Sangeetha; Chou, Wayne K. W.; Cane, David E.; Christianson, David W.Geosmin synthase from Streptomyces coelicolor (ScGS) catalyzes an unusual, metal-dependent terpenoid cyclization and fragmentation reaction sequence. Two distinct active sites are required for catalysis: the N-terminal domain catalyzes the ionization and cyclization of farnesyl diphosphate to form germacradienol and inorganic pyrophosphate (PPi), and the C-terminal domain catalyzes the protonation, cyclization, and fragmentation of germacradienol to form geosmin and acetone through a retro-Prins reaction. A unique αα domain architecture is predicted for ScGS based on amino acid sequence: each domain contains the metal-binding motifs typical of a class I terpenoid cyclase, and each domain requires Mg2+ for catalysis. Here, we report the X-ray crystal structure of the unliganded N-terminal domain of ScGS and the structure of its complex with three Mg2+ ions and alendronate. These structures highlight conformational changes required for active site closure and catalysis. Although neither full-length ScGS nor constructs of the C-terminal domain could be crystallized, homology models of the C-terminal domain were constructed on the basis of 36% sequence identity with the N-terminal domain. Small-angle X-ray scattering experiments yield low-resolution molecular envelopes into which the N-terminal domain crystal structure and the C-terminal domain homology model were fit, suggesting possible αα domain architectures as frameworks for bifunctional catalysis. © 2015 American Chemical Society.Article Citation - WoS: 56Citation - Scopus: 57Dynamic Nuclear Polarization of Spherical Nanoparticles(Royal Society of Chemistry, 2013) Akbey, Ümit; Altın, Burcu; Linden, Arne; Özçelik, Serdar; Gradzielski, Michael; Oschkinat, HartmutSpherical silica nanoparticles of various particle sizes (∼10 to 100 nm), produced by a modified Stoeber method employing amino acids as catalysts, are investigated using Dynamic Nuclear Polarization (DNP) enhanced Nuclear Magnetic Resonance (NMR) spectroscopy. This study includes ultra-sensitive detection of surface-bound amino acids and their supramolecular organization in trace amounts, exploiting the increase in NMR sensitivity of up to three orders of magnitude via DNP. Moreover, the nature of the silicon nuclei on the surface and the bulk silicon nuclei in the core (sub-surface) is characterized at atomic resolution. Thereby, we obtain unique insights into the surface chemistry of these nanoparticles, which might result in improving their rational design as required for promising applications, e.g. as catalysts or imaging contrast agents. The non-covalent binding of amino acids to surfaces was determined which shows that the amino acids not just function as catalysts but become incorporated into the nanoparticles during the formation process. As a result only three distinct Q-types of silica signals were observed from surface and core regions. We observed dramatic changes of DNP enhancements as a function of particle size, and very small particles (which suit in vivo applications better) were hyperpolarized with the best efficiency. Nearly one order of magnitude larger DNP enhancement was observed for nanoparticles with 13 nm size compared to particles with 100 nm size. We determined an approximate DNP penetration-depth (∼4.2 or ∼5.7 nm) for the polarization transfer from electrons to the nuclei of the spherical nanoparticles. Faster DNP polarization buildup was observed for larger nanoparticles. Efficient hyperpolarization of such nanoparticles, as achieved in this work, can be utilized in applications such as magnetic resonance imaging (MRI).Article Citation - WoS: 273Citation - Scopus: 327Transesterification of Nannochloropsis Oculata Microalga's Lipid To Biodiesel on Al2o3 Supported Cao and Mgo Catalysts(Elsevier Ltd., 2009) Umdu, Emin Selahattin; Tuncer, Mert; Şeker, ErolIn this study, we present the activities of Al2O3 supported CaO and MgO catalysts in the transesterification of lipid of yellow green microalgae, Nannochloropsis oculata, as a function of methanol amount and the CaO and MgO loadings at 50 °C. We found that pure CaO and MgO were not active and CaO/Al2O3 catalyst among all the mixed oxide catalysts showed the highest activity. Not only the basic site density but also the basic strength is important to achieve the high biodiesel yield. Biodiesel yield over 80 wt.% CaO/Al2O3 catalyst increased to 97.5% from 23% when methanol/lipid molar ratio was 30.Article Citation - WoS: 64Citation - Scopus: 67Hierarchically Structured Metal Oxide/Silica Nanofibers by Colloid Electrospinning(American Chemical Society, 2012) Horzum Polat, Nesrin; Mun˜oz-Espí, Rafael; Glasser, Gunnar; Demir, Mustafa Muammer; Landfester, Katharina; Crespy, DanielWe 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.