Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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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: 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.Article Citation - WoS: 13Citation - Scopus: 15Ancillary Effects of Surfactants on Filtration of Low Molecular Weight Contaminants Through Cellulose Nitrate Membrane Filters(Elsevier Ltd., 2016) Olcay, Aybike Nil; Polat, Mehmet; Polat, HürriyetRemoval of contaminants with low molecular weight (<800 Dalton) requires the use of advanced separation techniques such as ultrafiltration (UF) or micellar enhanced ultrafiltration (MEUF). However, surface active agents invariably co-exist in waste waters along with these contaminants or they may be added intentionally as part of the separation process as in the case of MEUF. Though it is quite likely that both the filter medium and the contaminants would interact with the surfactant molecules or their micelles, there is not sufficient emphasis in the literature on the concomitant aspects of such interactions.The ancillary effects created by anionic (sodium dodecyl sulfate, SDS), cationic (hexadecyltrimethyl ammonium bromide, CTAB) and non-ionic (ethoxylated octylphenol, TX-100) surfactants on the mechanism and efficiency of the filtration process were investigated in this study. Methylene blue (MB) and cellulose nitrate membrane (CNM) filters were employed as model retentate and the separation medium. A combination of surface tension, contact angle and charge measurements demonstrated that the addition of surfactants had a remarkable effect on the filtration outcome. The effect depended on both the type and concentration of the surfactant and was manifested mainly through the creation of MB-surfactant entities which acted differently than the MB alone; but more importantly, through the interactions of the surfactant molecules/micelles and the MB-surfactant pairs with the separation membrane.Article Citation - Scopus: 2Enthalpy-Driven Selective Loading of Cdse0.75s0.25 Nanoalloys in Triblock Copolymer Polystyrene-B(Elsevier Ltd., 2016) Aşkın, Görkem; Çeçen, Volkan; Ünlütürk, Seçil Sevim; Özçelik, Serdar; Demir, Mustafa MuammerCdSe0.75S0.25 nanoalloys were blended with asymmetric triblock copolymer of polystyrene-b-polyisoprene-b-polystyrene(PS-SIS) in tetrahydrofuran. The fraction of styrene block varies from 14 to 22% with respect to isoprene by mass. The morphology of the copolymer cast film experiences a phase change from cylinder to lamella. CdSe0.75S0.25 nanoalloys were prepared by two-phase method. The surface of the nanoalloys was capped by either oleic acid (OA) or n-tri-octylphosphonic acid (TOPO) in situ. The mean diameter of the alloyed particles is around 12 nm in both systems. The chemical nature of the nanoalloy surface was found to influence the dispersion of the particles over polymer volume. The size of the nanoalloy domains in PS is 50 nm, on average, consisting of approximately 0.7 wt% nanoalloys. However, the size of the nanoalloy domains is smaller when they are loaded into PS-SIS. The structure formation is predominantly determined by enthalpic compatibilization. Atomic force microscopy results suggest that the nanoalloys capped with TOPO sequester into PS-rich domains and enlarge the domain. On the other hand, the ones capped with OA prefer to locate in polyisoprene domains. The increase of particles over 1.0 wt% distorts the lamella structure.Article Citation - WoS: 17Citation - Scopus: 19Reactions of Acyl Phosphonates With Organoaluminum Reagents: a New Method for the Synthesis of Secondary and Tertiary ?-Hydroxy Phosphonates(Elsevier Ltd., 2011) Seven, Özlem; Polat Çakır, Sıdıka; Hossain, Mohammad Shakhawoat; Emrullahoğlu, Mustafa; Demir, Ayhan SıtkıThe reactions of organoaluminum reagents (trimethylaluminum, triethylaluminum, etc.) with aryl and alkyl acyl phosphonates, which lead to the formation of α-hydroxy phosphonates in moderate to good yields, are reported. This method provides easy access to secondary and tertiary α-hydroxy phosphonates depending on the reaction conditions. The reactions of triethylArticle Citation - WoS: 20Citation - Scopus: 20Genome-Wide Identification of Genes That Play a Role in Boron Stress Response in Yeast(Elsevier Ltd., 2011) Uluışık, İrem; Kaya, Alaattin; Ünlü, Ercan Selçuk; Avşar, Kadir; Karakaya, Hüseyin Çağlar; Yalçın, Talat; Koç, AhmetBoron is an essential micronutrient for plants and it is either necessary or beneficial for animals. Studies identified only few genes related to boron metabolism thus far and details of how boron is imported into cells and used in cell metabolism are largely unknown. In order to identify genes that play roles in boron metabolism, we screened the entire set of yeast haploid deletion mutants and identified 6 mutants that were resistant to toxic levels of boron, and 21 mutants that were highly sensitive to boron treatment. Furthermore, we performed a proteomic approach to identify additional proteins that are significantly up-regulated by boron treatment. Our results revealed many genes and pathways related to boron stress response and suggest a possible link between boron toxicity and translational control.Article Citation - WoS: 31Citation - Scopus: 35Electrochemical Investigation of Biomolecular Interactions Between Platinum Derivatives and Dna by Carbon Nanotubes Modified Sensors(Elsevier Ltd., 2010) Yapaşan, Ece; Çalışkan, Ayfer; Karadeniz, Hakan; Erdem, ArzumThe biomolecular interactions of platinum derivatives widely used as anticancer drugs: cis-diamminedichloroplatinum(II) and oxaliplatin with calf thymus double-stranded DNA were studied using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) in combination with single-walled carbon nanotubes modified graphite electrode (SWCNTs-GE) and unmodified graphite electrode (bare GE). The performance of these biomolecular interactions were explored at the electrode surface by monitoring the changes at guanine oxidation signal in terms of optimum interaction times by comparing the results of SWCNTs-GE with bare one. The features of these electrochemical sensors based on carbon nanotubes for monitoring of biomolecular interactions were discussed and compared with the earlier conventional ones. © 2009 Elsevier B.V. All rights reserved.Article Citation - WoS: 20Citation - Scopus: 24Preparation and Characterization of Sodium Dodecyl Sulfate Doped Polypyrrole Solid Phase Micro Extraction Fiber and Its Application To Endocrine Disruptor Pesticide Analysis(Elsevier Ltd., 2013) Korba, Korcan; Pelit, Levent; Okçu Pelit, Füsun; Özdokur, K. Volkan; Ertaş, Hasan; Eroğlu, Ahmet Emin; Ertaş, Fatma NilA robust in house solid-phase micro extraction (SPME) surface has been developed for the headspace (HS)-SPME determination of endocrine disruptor pesticides, namely, Chlorpyrifos, Penconazole, Procymidone, Bromopropylate and Lambda-Cyhalothrin in wine sample by using sodium dodecylsulfate doped polypyrrole SPME fiber. Pyrrole monomer was electrochemically polymerized on a stainless steel wire in laboratory conditions in virtue of diminishing the cost and enhancing the analyte retention on its surface to exert better selectivity and hence the developed polymerized surface could offer to analyst to exploit it as a fiber in headspace SPME analysis. The parameters, mainly, adsorption temperature and time, desorption temperature, stirring rate and salt amount were optimized to be as 70°C and 45min, 200°C, 600rpm and 10gL-1, respectively. Limit of detection was estimated in the range of 0.073-1.659ngmL-1 for the pesticides studied. The developed method was applied in to red wine sample with acceptable recovery values (92-107%) which were obtained for these selected pesticides.Article Citation - WoS: 2Citation - Scopus: 2Polarized Absorption Spectra of Highly Oriented Two-Dimensional Aggregates of Tetrachlorobenzimidazolocarbocyanine in Thin Films(Elsevier Ltd., 2008) Özçelik, Serdar; Gülen, DemetReaching a control on the mesoscopic morphology and internal molecular arrangement of cyanine aggregates is an important step for realization of devices with tailor-made optical properties. Despite a wealth of research, understanding of the relationship between molecular organization, excitonic states and dynamics of aggregates is still preliminary. To this end, we have employed polarized absorption spectroscopy to investigate the relationship between internal molecular organization and excitonic states of J-aggregates in 1,1′,3,3′tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (TTBC) thin films in poly-vinyl alcohol (PVA). Angular dependence of the UV-vis spectra has been measured at 11 different orientations between the electric field polarization and the macroscopic alignment axis. Aggregate spectral response consisted of an asymmetrically split Davydov pair of bands exhibiting opposite polarization: an H-band (505 nm, Lorentzian-like, polarized along the macroscopic film axis) and a J-band (594 nm, one-dimensional J-aggregate like band shape, polarized perpendicular to the macroscopic film axis). The polarized absorption observations were found to be consistent with a herringbone model for which the internal molecular arrangement, the excited state structure and dynamics have recently been detailed by us upon interpretation of isotropic absorption data in ionic aqueous solution.Article Citation - WoS: 4Citation - Scopus: 6Absorption Spectrum of Monomeric Pseudoisocyanine: a New Perspective and Its Implications for Formation and Spectral Response of J-Aggregates in Solution and in Thin Films(Elsevier Ltd., 2008) Gülen, Demet; Özçelik, SerdarWe argued against the current spectral assignment for absorption spectrum of monomeric PIC which is widely accepted since the pioneering works of Scheibe and Jelley [G. Scheibe, Angew. Chem. 49 (1936) 563; E.E. Jelly, Nature 138 (1936) 1009]. A new spectrum is presented along with its conceptual basis. The hypothesized spectrum attributes the previous 0-0 (≈525 nm) and 0-1 (≈490 nm) assignments, respectively, to intermediates acting as the precursor of J-aggregates and to the 0-0 transition of monomeric PIC and brings the spectrum in accord with the seemingly universal spectral fingerprint of cyanines. The hypothesis is used to analyze and interpret the temperature dependence of the UV-vis absorption of PIC aggregates in saline aqueous solution by incorporating the J-band simulations within frenkel exciton formalism. Its implications for aggregate formation kinetics are given on the basis of current spectroscopic evidence. The hypothesis readily answers several long-standing questions: Why compared to many other cyanines at least an order of magnitude higher dye concentration is needed to form J-aggregates of PIC? Why are there no precursors, since aggregation is expected to be a consecutive process? A large number of observations on steady-state and time-resolved spectral properties, and aggregation kinetics in solution/thin films are likely to find reasonable explanations within this hypothesis.
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