Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 169Citation - Scopus: 177Thin Film Microextraction: Towards Faster and More Sensitive Microextraction(Elsevier Ltd., 2019) Ölçer, Yekta Arya; Tascon, Marcos; Eroğlu, Ahmet Emin; Boyacı, EzelThin film microextraction (TFME) is an analytical tool that has been proven to be suitable for integrated sampling and sample preparation of a wide variety of routine and on-site applications. Compared to the traditional microextraction techniques, the most important advantage of TFME is its enhanced sensitivity due to the relatively larger extractive phase spread over a larger surface area. The technique, in this way, facilitates fast extraction kinetics and high extractive capacity. Moreover, TFME offers high versatility for device development over classical SPME technologies due to the plethora of available extractive phases, coating methods and geometry options. The goal of this review is to provide a comprehensive summary of the contemporary advances in this exciting field covering novel extractive phases, technological and methodological developments, and relevant cutting-edge applications. Finally, a critical discussion of the future trends on TFME is also presented. (C) 2019 Elsevier B.V. All rights reserved.Article Citation - WoS: 29Citation - Scopus: 29Investigating Silicon Wafer Based Substrates for Dried-Droplet Analysis by Laser-Induced Breakdown Spectroscopy(Elsevier Ltd., 2019) Aras, Nadir; Yalçın, ŞerifeThis work communicates a critical assessment on the analytical capability of the three silicon wafer-based substrates; crystalline silicon (c-Si), oxide-coated silicon (SiO2-Si), and nitride-coated silicon (Si3N4-Si), for dried-droplet analysis by laser-induced breakdown spectroscopy. The methodology consists of loading, drying and analyzing steps. First, nanoliter volume of droplets are manually loaded onto the substrate and dried at room temperature. Then, the dry residue is subjected to high peak power (1.15 GW/cm(2)) laser pulses focused outside the minimum focal point condition and luminescent plasma is spectroscopically analyzed. Results revealed that nitride-coated substrate exhibits strong enhancements in signal intensity for most emission lines of the analyte species investigated: Cd, Cr, Cu, Mn, and Pb. Surface reflectivity and surface morphology were comparatively investigated to explore enhanced analytical performance of nitride-coated substrates. Experimental conditions were optimized and growth curves for all the elements are found linear with minimum regression constant of 0.96. LOD's of 62 pg Cd, 1.5 pg Cr, 0.5 pg Cu, 2 pg Mn and 11 pg Pb, in absolute amounts, were obtained. The accuracy and precision of the methodology were tested on certified reference water sample (CRM-TMDW), and ICP-multi-element standard sample (ICP-MES). The surface enhancement effect observed on Si3N4 coated substrates has improved the analytical capability of laser-induced breakdown spectroscopy for liquid analysis.Article Citation - WoS: 6Citation - Scopus: 6Palladium-Catalyzed Coupling of 2-En Carbonates With Terminal Alkynes(Elsevier Ltd., 2018) Taç, Doğan; Artok, LeventThe first palladium-catalysed coupling of the carbonates of (E)-configured conjugated enynols with terminal alkynes is described. This method allows the synthesis of vinyl-allenynes with good yields. It has been determined that the method is not suitable for the (Z)-configured substrates.Article Citation - WoS: 16Citation - Scopus: 19Nmr Studies on Natural and Synthetic Amavadin(Elsevier Ltd., 2000) Armstrong, Elaine M.; Collison, David; Ertok, Nigar; Garner, Catherine D.The stereochemistry of isolated natural product Amavadin, which contains a 1:2 complex of V(IV) with N-hydroxyimino-2,2′-dipropionic acid (HIDPAH3), and some synthetic complexes have been investigated. Amavadin was isolated from Amanita muscaria and oxidized with [NH4]2[Ce(NO3)6]. H2[Δ-V(S,S-HIDPA)2].3H2O, H2[Δ,Λ-V(S,S-HIDPA)2].3H2O and their equivalent oxidized species have been synthesized and characterized spectroscopically. A combination of COSY, NOE, 1H, 13C-NMR and CD spectroscopy have been used to prove that the isolated natural product Amavadin consists of an almost equal mixture of the Δ- and Λ-isomers of [V(S,S-HIDPA)2]2-. The stereochemistry of isolated natural product Amavadin, which contains a 1:2 complex of V(IV) with N-hydroxyimino-2,2'-dipropionic acid (HIDPAH3), and some synthetic complexes have been investigated. Amavadin was isolated from Amanita muscaria and oxidized with [NH4]2[Ce(NO3)6]. H2[Δ-V(S,S-HIDPA)2].3H2O, H2[Δ,Λ-V(S,S-HIDPA)2].3H2O and their equivalent oxidized species have been synthesized and characterized spectroscopically. A combination of COSY, NOE, 1H, 13C-NMR and CD spectroscopy have been used to prove that the isolated natural product Amavadin consists of an almost equal mixture of the Δ- and Λ-isomers of [V(S,S-HIDPA)2]2-.Book Part Citation - WoS: 7Citation - Scopus: 14Olive Oil Adulteration With Sunflower and Corn Oil Using Molecular Fluorescence Spectroscopy(Elsevier Ltd., 2010) Öztürk, Betül; Arıkan, Aysun; Özdemir, DurmuşAdulteration of olive oil with cheaper substitutes such as sunflower and corn oil is a major concern for the public. Rapid analysis methods are required for a quick and easy screening of possible adulteration attempts. Fluorescence spectroscopy coupled with a genetic algorithm-based multivariate calibration method allows the determination of olive oil adulteration with sunflower and corn oil. Because the standard error of prediction values are all below 1.30% (w/w) for the ternary set, fluorescence spectroscopy can be used as a fast screening method for possible olive oil adulteration with cheaper vegetable oils. In addition, the genetic algorithm used in the genetic inverse least squares (GILS) method is able to select and extract the most relevant information to build successful calibration models that have high predictive ability for the independent test samples.Article Citation - WoS: 44Citation - Scopus: 53Smart Phone Assisted Detection and Quantification of Cyanide in Drinking Water by Paper Based Sensing Platform(Elsevier Ltd., 2017) İncel, Anıl; Akın, Osman; Çağır, Ali; Yıldız, Ümit Hakan; Demir, Mustafa MuammerAn organometallic dye, europium tetrakis dibenzoylmethide triethylammonium (EuD4TEA) and gold nanoparticles (Au NPs) impregnated paper based sensor platform have been utilized for development of fluorescence turn-on cyanide assay in aqueous media. The ordinary filter paper with 6 μ m pore size were employed as solid support that facilitates impregnation of EuD4TEA and gold nanoparticles and provides durability. Detection mechanism relying on two processes (i) dissolution of gold nanoparticles causing fluorescence recovery and (ii) ligand exchange of triethyl amine with CN group stimulating cyanide specific fluorescence enhancement. The paper platform exhibit naked eye distinguishable color transition upon CN− addition from 10−2 to 10−12 M. To standardize the methodology a homemade image processing algorithm has been developed that enabling calibration of color change and quantify CN− concentration. The described algorithm is applicable to Android smart phones and facilitate transforming these devices into a quantitative cyanide detector. The overall methodology provides instrument free cyanide detection and therefore rapid control of water quality and safety at off-field conditions.Article Citation - WoS: 16Citation - Scopus: 19Designing of Spherical Chitosan Nano-Shells With Micellar Cores for Solvation and Safeguarded Delivery of Strongly Lipophilic Drugs(Elsevier Ltd., 2017) Cihan, Esra; Polat, Mehmet; Polat, HürriyetChitosan is a very effective biopolymer for drug delivery purposes due to its biocompatibility, positive charge and exceptionally pH sensitive degradability behavior in an aqueous medium. Nevertheless, its inability for dissolving lipophilic drug active material and the difficulties in controlling the size and shape of the synthesized particles in nanometer range are critical drawbacks in its effective use. In this study, a synthesis procedure which addresses both issues simultaneously is presented. The procedure is based on initial dissolution of lipophilic drug molecules within the hydrophobic cores of the micelles of a bio-compatible block-copolymer by ionic gelation and subsequent formation of a chitosan shell by polymerization around the micellar structures. Well-formed, hollow and perfectly spherical chitosan particles (nano-shells) in the 30–300 nm size range could be successfully manufactured. Characterization by STEM, TEM, AFM, FTIR and DLS, DLS-LDV techniques showed clearly that the drug was successfully incorporated into the chitosan structure. It was demonstrated that the particles enveloped the micelle(s) of a Pluronic copolymer (P-123) whose hydrophobic cores contained a strongly hydrophobic drug Probucol. The chitosan nano-shells are expected to act as an agent protecting the integrity of the drug-loaded micelles in the body fluid while providing a pH sensitive release medium. The drug uptake by the chitosan particles was very high. A very sharp increase in the amount of the drug released with a slight change in the acidity of the medium was an indication of the potential of the manufactured chitosan nano-shells as pH sensitive, target specific delivery vehicles for drug release.Article Citation - WoS: 10Citation - Scopus: 12Tuning Pendant Groups of Polythiophene on Carbon Nanotubes for Vapour Classification(Elsevier Ltd., 2017) Tu, Meng-Che; Svm, Hari Krishna; Thilini, Alahakoon; Wallace, Lim Tse Loong; Moochhala, Shabbir; Yıldız, Ümit Hakan; Palaniappan, Al.; Liedberg, BoPoly(3-alkoxythiophene) (PT) with varying ratios of triethylamine and 1-methyl imidazole pendant groups and horizontally aligned single walled carbon nanotubes (SWCNT) are utilized in this study for volatile organic compounds (VOCs) classification. PTs with five different ratios of pendant groups are incorporated with SWCNT and are evaluated as chemiresistor arrays for analysis of VOCs such as ethanol, acetone, toluene, chloroform, isoprene and ethylene. Varying PT pendant groups yielded differential SWCNT current responses attributed to their chemical affinities for the VOCs tested. Principal component analysis (PCA) for vapour classification illustrated that the vapour responses are separable, thus, highlighting vapour discrimination ability of SWCNT with controlled ratios of PT pendant groups. The proposed methodology is a facile VOC classification approach for two main reasons; (i) PT could easily modified with various pendants groups containing appropriate chemical moieties for preferential interaction with various VOCs and (ii) increasing the number PTs with appropriate pendant group modifications would provide additional inputs to PCA thereby enabling capturing and assaying of a wide range of VOCs.Article Citation - WoS: 8Citation - Scopus: 8Synthesis and Topoisomerase I Inhibitory Properties of Klavuzon Derivatives(Elsevier Ltd., 2017) Akçok, İsmail; Mete, Derya; Şen, Ayhan; Kasaplar, Pınar; Korkmaz, Kemal S.; Çağır, AliKlavuzon is a naphthalen-1-yl substituted α,β-unsaturated δ-lactone derivative, and is one of the anti-proliferative members of this class of compounds. Asymmetric and racemic syntheses of novel α,β-unsaturated δ-lactone derivatives are important to investigate their potential for the treatment of cancer. In this study, asymmetric and racemic syntheses of heteroatom-substituted klavuzon derivatives are reported. The syntheses were completed by a well-known three-step procedure. Anti-proliferative activity of seven novel racemic klavuzon derivatives were reported against MCF-7, PC3, HCT116 p53+/+ and HCT116 p53−/− cancer cell lines. Topoisomerase I inhibitory properties of 5,6-dihydro-2H-pyran-2-one derivatives were also studied. © 2017 Elsevier Inc.Article Citation - WoS: 2Citation - Scopus: 2Observation of the Side Chain O-Methylation of Glutamic Acid or Aspartic Acid Containing Model Peptides by Electrospray Ionization-Mass Spectrometry(Elsevier Ltd., 2017) Atik, Ahmet Emin; Güray, Melda Zeynep; Yalçın, TalatO-methylation of the side chains of glutamic acid (E) and aspartic acid (D) residues is generally observed modification when an acidified methanol/water (MeOH/dH2O) mixture is used as a solvent system during sample preparation for proteomic research. This chemical modification may result misidentification with endogenous protein methylation; therefore, a special care should be taken during sample handling prior to mass spectrometric analysis. In the current study, we systematically examined the extent of E/D methylation and C-terminus carboxyl group of synthetic model peptides in terms of different incubation temperatures, storage times, and added acid types as well as its percentages. To monitor these effects, C-terminus amidated and free acid forms of synthetic model peptides comprised of E or D residue(s) have been analyzed by electrospray ionization-mass spectrometry (ESI-MS). Additionally, LC–MS/MS experiments were performed to confirm the formation of methylated peptide product. The results showed that the rate of methylation was increased as the temperature increases along with prolong incubation times. Moreover, the extent of methylation was remarkably high when formic acid (FA) used as a protonation agent instead of acetic acid (AA). In addition, it was found that the degree of methylation was significantly decreased by lowering acid percentages in ESI solution. More than one acidic residue containing model peptides have been also used to explore the extent of multiple methylation reaction. Lastly, the ethanol (EtOH) and isopropanol (iPrOH) have been substituted separately with MeOH in sample preparation step to investigate the extent of esterification reaction under the same experimental conditions. However, in the positive perspective of view, this method can be used as a simple, rapid and cheap method for methylation of acidic residues under normal laboratory conditions.