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Publication Metadata only CS4GE9 center dot en: a novel compound with [GE-9](4-) clusters - synthesis, crystal structure and vibrational spectra(Wiley-V C H Verlag Gmbh, 2007) Carrillo-Cabrera, Wilder; Kırcalı, Aslıhan; Faessler, Thomas F.; Hoffmann, Stephan D.; Department of Chemistry; Department of Chemistry; Aydemir, Umut; Somer, Mehmet Suat; Faculty Member; Faculty Member; Department of Chemistry; College of Sciences; College of Sciences; 58403; 178882Red-orange prismatic crystals of CS4Ge9.en (en = ethyl-enediamine) were obtained via metathesis reaction of an en solution of K4Ge9 with a large excess of CsI. The compound is very sensitive to air and moisture. CS4Ge9.en is not isotypic to Rb4Ge9.en and crystallizes in a new structure type (monoclinic, space group P2(1)/c (No. 14); a = 16.757(3), h = 16.462(3), c = 15.657(2) angstrom, beta = 90.37(1)degrees; Z = 8; Pearson code mP200). The crystal structure comprises two types (A and B) of discrete [Ge-9](4-)units arranged in the motif of a distorted hexagonal close-packing (h.c.p.). In this h.c.p. framework, each tetrahedral hole is filled by one Cs atom and each larger octahedral hole is tilled by a group of one en and two Cs atoms. The topology of the two crystallographically distinct [Ge-9](4-) clusters corresponds to distorted, monocapped tetragonal antiprisms with bond lengths varying in the range 2.551-2.848 angstrom (type A cluster) or in the range 2.538-2.975 angstrom (less regular type B cluster). According to the DTA and TG measurements, CS4Ge9.en decomposes at 378 K under liberation of gaseous ethylenediamine yielding CS4Ge9. The Raman spectra of the title compound were interpreted based on the idealized C-4v symmetry of an isolated [Geg](4-) cluster. The characteristic breathing mode was localized at 222 cm(-1). The results are analyzed and discussed in context with those of the previously reported compounds CS4Ge9, K4Ge9 and Rb4Ge9.en.Publication Metadata only Cytotoxic platinum(II) complexes derived from saccharinate and phosphine ligands: synthesis, structures, DNA cleavage, and oxidative stress-induced apoptosis(Springer, 2020) İçsel, Ceyda; Yılmaz, Veysel T.; Aygün, Muhittin; Ulukaya, Engin; Animal Laboratory; Cevatemre, Buse; Researcher; Animal Laboratory; N/A; N/AA series of the structurally related platinum(II) saccharinate (sac) complexes with alkylphenylphosphines, namely cis-[Pt(sac)(2)(PPh2Me)(2)]center dot DMSO (1), cis-[Pt(sac)(2)(PPhMe2)(2)] (2), cis-[Pt(sac)(2)(PPh2Et)(2)] (3), and cis-[Pt(sac)(2)(PPhEt2)(2)]center dot 2DMSO (4), were synthesized and fully characterized; their structures were determined by X-ray crystallography. All the complexes were investigated for their anticancer potentials on three human cancer cells including A549 (lung), MCF-7 (breast), and HCT116 (colon) in addition to a noncancerous human bronchial epithelial cells (BEAS-2B). Specifically, 1 and 3 showed significant cytotoxic effects against MCF-7 and HCT116 cell lines in comparison to cisplatin, and were considered as the most potent ones in the series. The cytotoxic complexes were found to cleave DNA efficiently. In addition, the binding interactions of the complexes with DNA were confirmed by enzyme inhibition and molecular docking studies. Complexes 1 and 3 were capable of inducing apoptosis and arrested the cell cycle at the DNA synthesis (S) phase in MCF-7 cells. Furthermore, 1 and 3 caused the excessive generation of reactive oxygen species (ROS), leading to mitochondrial dysfunction and double-strand DNA breaks.Publication Metadata only Determination of thyroglobulin levels by radioimmunoassay method in anti thyroglobulin positive differentiated thyroid patients: one center clinical experience(Pergamon-Elsevier Science Ltd, 2020) Uçar, Burcu; Şen, Melis; Acar, Tayfun; N/A; Demirkol, Mehmet Onur; Faculty Member; School of Medicine; 196946It is very crucial to determine Tg accurately and precisely in thyroid cancer cases. Although there are many studies on the detection of Tg in thyroid cases in the literature, there are no sufficient clinical studies examining many cases with different features by using RIA methodology. Here, a radiometric and chromatographic method has been studied for the first time to eliminate the interference from anti-Tg positive patients. In this paper, radioimmunoassay (RIA) and immunoradiometric (IRMA) techniques were used for the analysis of 302 sera collected from patients for Tg and TgAb quantification. By the RIA technique, a reliable result was obtained by calculating the real Tg value quantitatively in 41 patients showing TgAb positivity out of 208 patients. Our findings show that the RIA assay is the most suitable approach for detection of changeable (low or undetectable) Tg value and metastases detected by post-therapeutic imaging in early-stage DTC cases showing preoperative and postoperative TgAb positivity. The new immunoradiometric method allows the real (%) Tg value to be reached in a part of TgAb-positive DTC. Even if TgAb positive in the metastatic and nonmetastatic DTC patient group. This allows the accurate clinical follow-up of patients.Publication Metadata only Electronic band structure and low-temperature transport properties of the type-I clathrate BA8NIXGE46-X-Y(Royal Soc Chemistry, 2015) Candolfi, C.; Ormeci, A.; Baitinger, M.; Burkhardt, U.; Oeschler, N.; Steglich, F.; Grin, Yu.; Department of Chemistry; Aydemir, Umut; Faculty Member; Department of Chemistry; College of Sciences; 58403We present the evolution of the low-temperature thermodynamic, galvanomagnetic and thermoelectric properties of the type-I clathrate Ba8NixGe46-x-y square(y) with the Ni concentration studied on polycrystalline samples with 0.0 <= x <= 6.0 by means of specific heat, Hall effect, electrical resistivity, thermopower and thermal conductivity measurements in the 2-350 K temperature range and supported by first-principles calculations. The experimental results evidence a 2a x 2a x 2a supercell described in the space group Ia (3) over bard for x <= 1.0 and a primitive unit cell a x a x a (space group Pm (3) over barn) above this Ni content. This concentration also marks the limit between a regime where both electrons and holes contribute to the electrical conduction (x <= 1.0) and a conventional, single-carrier regime (x > 1.0). This evolution is traced by the variations in the thermopower and Hall effect with x. In agreement with band structure calculations, increasing the Ni content drives the system from a nearly-compensated semimetallic state (x = 0.0) towards a narrow-band-gap semiconducting state (x = 4.0). A crossover from an n-type to a p-type conduction occurs when crossing the x = 4.0 concentration i.e. for x = 4.1. The solid solution Ba8NixGe46-x-y square(y) therefore provides an excellent experimental platform to probe the evolution of the peculiar properties of the parent type-I clathrate Ba8Ge43 square(3) upon Ge/Ni substitution and filling up of the vacancies, which might be universal among the ternary systems at low substitution levels.Publication Metadata only Enhanced water stability and high CO2 storage capacity of a Lewis basic sites-containing zirconium metal-organic framework(2021) Demir, Selçuk; Bilgin, Nuray; Çepni, Hamide Merve; Furukawa, Hiroyasu; Yılmaz, Fatih; N/A; Department of Chemical and Biological Engineering; Altıntaş, Çiğdem; Keskin, Seda; Researcher; Faculty Member; Department of Chemical and Biological Engineering; Graduate School of Sciences and Engineering; College of Engineering; N/A; 40548Metal–organic frameworks (MOFs) are an emerging class of materials employed for custom-designed purposes by judicious selection of linkers and metal ions. Among the MOFs composed of carboxylate linkers, Zr-based MOFs have attracted great attention due to their high thermal and chemical stabilities, which are important for practical applications, including capturing CO2 from a point source. UiO-67(bipy) containing 2,2′-bipyridine-5,5′-dicarboxylate is particularly useful among the Zr-MOF family due to the Lewis basic sites of the linker; however, the hydrolytic stability of UiO-67(bipy) does not seem to be as high as those of UiO-66 and UiO-67. To improve the hydrolytic stability without sacrificing the adsorption enthalpy of CO2 for selective CO2 capture, in this study, we added hydrophobic methyl groups to the backbone of the bipyridine linker. The synthesized 6,6′-dimethyl-2,2′-bipyridine-5,5′-dicarboxylic acid (H2Me2bipy) was used to prepare a Zr-based MOF [MOF-553, Zr6O4(OH)4(Me2Bipy)6]. In addition, the water stability and CO2 adsorption capacity of MOF-553 were compared to those of UiO-67(bipy). We revealed that MOF-553 is more robust and has a higher CO2 adsorption capacity than UiO-67(bipy), indicating that the methylation of the linker improves the water stability of the framework, which is advantageous for point-source CO2 capture.Publication Metadata only Isotropic zero thermal expansion and local vibrational dynamics in (SC,FE)F-3(American Chemical Society (ACS), 2017) Qin, Feiyu; Chen, Jun; Sanson, Andrea; Wang, Lu; Pan, Zhao; Xu, Jiale; Sun, Chengjun; Ren, Yang; Deng, Jinxia; Yu, Ranbo; Hu, Lei; Snyder, G. Jeffrey; Xing, Xianran; Department of Chemistry; Aydemir, Umut; Faculty Member; Department of Chemistry; College of Sciences; 58403Scandium fluoride (ScF3) exhibits a pronounced negative thermal expansion (NTE), which can be suppressed and ultimately transformed into an isotropic zero thermal expansion (ZTE) by partially substituting Sc with Fe in (Sc0.8Fe0.2)F-3 (Fe20). The latter displays a rather small coefficient of thermal expansion of -0.17 X 10(-6)/K from 300 to 700 K. Synchrotron X-ray and neutron pair distribution functions confirm that the Sc/ Fe-F bond has positive thermal expansion (PTE). Local vibrational dynamics based on extended X-ray absorption fine structure indicates a decreased anisotropy of relative vibration in the Sc/Fe-F bond. Combined analysis proposes a delicate balance between the counteracting effects of the chemical bond PTE and NTE from transverse vibration. The present study extends the scope of isotropic ZTE compounds and, more significantly, provides a complete local vibrational dynamics to shed light on the ZTE mechanism in chemically tailored NTE compounds.Publication Metadata only New ternary iron(III) aminobisphenolate hydroxyquinoline complexes as potential therapeutic agents(The Royal Society, 2019) Matos, Cristina P.; Yildizhan, Yasemin; Adiguzel, Zelal; Pavan, Fernando R.; Campos, Debora L.; Pessoa, Joao Costa; Ferreira, Liliana P.; Tomaz, Ana Isabel; Correia, Isabel; Ayhan, Ceyda Açılan; Faculty Member; School of Medicine; 219658In the quest for therapeutic iron-based metallodrugs, two new mixed-ligand iron(iii) complexes bearing the tripodal aminobisphenolate ligand N,N-bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine (H2L) and hydroxyquinoline co-ligands, 8-hydroxyquinoline (8HQ) or 5-chloro-8-hydroxyquinoline (Cl8HQ), are synthesized, fully characterized and formulated as [Fe(L)(8HQ)] (1) and [Fe(L)(Cl8HQ)] (2), respectively. These high-spin Fe(iii) complexes are stable in aqueous solution in the presence of equimolar amounts of Bovine Serum Albumin (BSA), which indicates a likely binding interaction with the protein. In fact, binding constant log values at pH 7.4 for HSA of 5.08 and 6.35 were obtained for 1 and 2, respectively. Compounds 1 and 2 are cytotoxic against both human triple-negative breast adenocarcinoma (MDA-MB-231) and human cervical carcinoma (HeLa) cancer cells, and the activity is significantly improved by inclusion of the co-ligands 8HQ and Cl8HQ to the precursor complex Fe(L). Moreover, 1 and 2 are more active than 8HQ and Cl8HQ, particularly at lower incubation times tested, 24 and 48 h. Cells treated with the complexes display typical features of apoptosis as assessed by cellular morphology, DNA condensation and TUNEL analysis. COMET assays show that both drug candidates induce genomic damage in both cell lines. The complexes exhibit DNA cleavage activity and DNA damage that may be related to their ability to generate ROS. Overall, data supports that 1 and 2 are both active anticancer drug candidates within the low micromolar range. This is particularly interesting in the case of the breast MDA-MB-231 line, a model for triple-negative breast cancer that is an aggressive form of breast cancer, highly invasive and with limited treatment options and very poor prognosis. Furthermore, both complexes exhibited good anti-Mycobacterium tuberculosis activity, suggesting that 1 and 2 might have a wide spectrum of biological activity and justify further research.Publication Metadata only Nickel−palladium alloy nanoparticles supported on reduced graphene oxide decorated with metallic aluminum nanoparticles (Al-rGO/NiPd): a multifunctional catalyst for the transfer hydrogenation of nitroarenes and olefins using water as a hydrogen source(Royal Soc Chemistry, 2021) Dagalan, Ziya; Behboudikhiavi, Sepideh; Turgut, Muhammet; Sevim, Melike; Kasapoglu, Ahmet Emre; Nisanci, Bilal; Department of Chemistry; Metin, Önder; Faculty Member; Department of Chemistry; College of Sciences; 46962We report herein an innovative design and synthesis of a novel multifunctional nanocatalyst for the transfer hydrogenation (TH) of nitroarenes and olefins using water as a hydrogen source and solvent. The presented nanocatalyst is composed of NiPd alloy nanoparticles (NPs) supported on reduced graphene oxide (rGO) decorated with metallic Al NPs (Al-rGO/NiPd). In the catalyst, metallic Al NPs serve as the sacrificing agent for hydrogen generation via the Al-H2O reaction, NiPd NPs act as the catalyst for the transfer of the generated hydrogen to the unsaturated compounds, and rGO functions as both a support material and stabilizer for the NPs. Among all tested catalysts, Al-rGO/Ni40Pd60 nanocatalysts are found to be the most efficient and selective catalysts in the presented TH of nitroarenes (14 examples) and olefins (14 examples) with yields reaching up to 99% under the optimized reaction conditions. Additionally, Al-rGO/Ni40Pd60 nanocatalysts are recyclable catalysts in the TH reactions by catalyzing ten consecutive runs in the TH of nitrobenzene without a significant drop in their initial catalytic activity, which is the first example in this regard. Last but not least, the current transfer hydrogenation protocol provides selectivity for the reduction of only the -NO2 group of nitroarenes bearing iodo or bromo substituents on the same aromatic ring. This study is the first example of a TH protocol that employs an Al-modified nanomaterial serving as both a hydrogen generator and reusable catalyst in water without using any additional hydrogen source.Publication Metadata only Structures and anticancer activity of chlorido platinum(II) saccharinate complexes with mono- and dialkylphenylphosphines(Elsevier Science Inc, 2019) İçsel, Ceyda; Yılmaz, Veysel T.; Aygün, Muhittin; Ulukaya, Engin; Animal Laboratory; Cevatemre, Buse; Researcher; Animal Laboratory; N/A; N/Acis-[PtCl(sac)(PPh2Me)(2)] (1), cis-[PtCl(sac)(PPhMe2)(2)] (2), trans-[PtCl(sac)(PPh2Et)(2)] (3) and trans- [PtCl(sac) (PPhEt2)(2)] (4) complexes (sac = saccharinate) were synthesized and characterized by elemental analysis and spectroscopic methods. The structures of 2-4 were determined by X-ray single-crystal diffraction. The interaction of the complexes with DNA was studied various biochemical, biophysical and molecular docking methods. Only the cis-configured complexes (1 and 2) showed nuclease activity and their binding affinity towards DNA was considerably higher than those of their trans-congeners (3 and 4). The chlorido ligand in the cis-configured complexes underwent aquation, making them more reactive towards DNA. Furthermore, 1 and 2 exhibited anticancer potency on breast (MCF-7) and colon (HCT116) cancer cells similar to cisplatin, whereas 3 and 4 were biologicallly inactive. Mechanistic studies on MCF-7 cells showed that higher nuclear uptake, cell cycle arrest at the S phase, dramatically increased DNA double-strand breaks, apoptosis induction, elevated levels of reactive oxygen species (ROS) and high mitochondrial membrane depolarization greatly contribute to the anticancer potency of 1 and 2.Publication Metadata only Switch of thermal expansions triggered by itinerant electrons in isostructural metal trifluorides(American Chemical Society (ACS), 2022) Qin, Feiyu; Wang, Xiaoying; Hu, Lei; Jia, Ning; Gao, Zhibin; Chen, Jun; Ding, Xiangdong; Sun, Jun; Department of Chemistry; Aydemir, Umut; Faculty Member; Department of Chemistry; College of Sciences; 58403Manageable thermal expansion (MTE) of metal trifluorides can be achieved by introducing local structure distortion (LSD) in the negative thermal expansion ScF3. However, an open issue is why isostructural TiF3, free of LSD, exhibits positive thermal expansion. Herein, a combined analysis of synchrotron X-ray diffraction, X-ray pair distribution function, and rigorous first-principles calculations was performed to reveal the important role of itinerant electrons in mediating soft phonons and lattice dynamics. Metallic TiF3 demonstrates itinerant electrons and a suppressed Gru''neisen parameter gamma -20, while insulating ScF3 absence of itinerant electrons has a considerable gamma -120. With increasing electron doping concentrations in ScF3, soft phonons become hardened and the gamma is repressed significantly, identical to TiF3. The presented results update the thermal expansion transition mechanism in framework structure analogues and provide a practical approach to obtaining MTE without inducing sizable structure distortion.