Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 2Citation - Scopus: 2Transition-Metal Direct C-H Arylation of Thiophene in Aqueous Media Via Potassium Peroxymonosulfate(John Wiley and Sons Inc., 2019) Özenler, Sezer; Kaya, Hakan; Elmacı, Nuran; Yıldız, Ümit HakanThis study covers the use of potassium peroxymonosulfate (PPS) which, is a mild and inexpensive catalyst, for direct coupling of C-H/C-H for water soluble thiophene. The 3-(4-methyl-3 '- thienyloxy)propyltriethylammonium bromide (M1) has been selected as model monomer that reacted PPS in 2.0, 0.20 and 0.020 monomer to PPS ratio. The reaction has been monitored via NMR spectroscopy revealing the monomer consumption and formation of dimers to tetramers as well as completion of reaction within 15 minutes. Resultant product is easily collected without tedious work up steps. The computational calculation has optimized the regularity of the coupling as head to tail, tail to tail, head to tail (HT-TT-HT) for tetramer. The regularity of tetramer which is further satisfied via NMR analysis showing emergence of new peaks at 3.56 and 4.48. The shifts in the UV maximum of reactive species have been monitored by absorbance spectroscopy showing time dependent red shift corresponds to growing from monomer to tetramers. The reaction has self-stopped due to low solubility of moderate condensates (higher than trimer), however further experiments have performed in water-organic mixtures showed great promises to obtain higher condensates.Article Citation - WoS: 6Citation - Scopus: 8Enhanced Spontaneous Emission Rate in a Low-Q Hybrid Photonic-Plasmonic Nanoresonator(American Chemical Society, 2019) Gökbulut, Belkıs; İnanç, Arda; Topçu, Gökhan; Ünlütürk, Seçil Sevim; Özçelik, Serdar; Demir, Mustafa Muammer; İnci, Mehmet NaciIn this paper, CdTe quantum dots (QDs)-doped single electrospun polymer nanofibers are partially coated with gold nanoparticles to form distinct hybrid photonic-plasmonic nanoresonators to investigate the critical role of the cavity-confined hybrid mode on the modification of the spontaneous emission dynamics of the fluorescent emitters in low-Q photonic cavities. A total enhancement factor of 11.2 is measured via a time-resolved experimental technique, which shows that there is an increase of about three times in the spontaneous emission rate for the QDs-doped gold nanoparticle-decorated nanofibers as they are compared with those uncoated ones. The physical mechanism affecting the spontaneous emission rate of the encapsulated QDs in such a hybrid photonic-plasmonic nanoresonator is explained to be due to regeneration of the mode field in the nanofiber cavity upon the interaction of the dipoles with the surface plasmons of distinctive gold nanoparticles that surround the outer surface of the nanofiber.Article Citation - WoS: 15Citation - Scopus: 17Improved Activity of Alpha-L From Geobacillus Vulcani Gs90 by Directed Evolution: Investigation on Thermal and Alkaline Stability(John Wiley and Sons Inc., 2019) Sürmeli, Yusuf; İlgü, Hüseyin; Şanlı Mohamed, Gülşahalpha-L-Arabinofuranosidase (Abf) is a potential enzyme because of its synergistic effect with other hemicellulases in agro-industrial field. In this study, directed evolution was applied to Abf from Geobacillus vulcani GS90 (GvAbf) using one round error-prone PCR and constructed a library of 73 enzyme variants of GvAbf. The activity screening of the enzyme variants was performed on soluble protein extracts using p-nitrophenyl alpha-L-arabinofuranoside as substrate. Two high activity displaying variants (GvAbf L307S and GvAbf Q90H/L307S) were selected, purified, partially characterized, and structurally analyzed. The specific activities of both variants were almost 2.5-fold more than that of GvAbf. Both GvAbf variants also exhibited higher thermal stability but lower alkaline stability in reference to GvAbf. The structural analysis of GvAbf model indicated that two mutation sites Q90H and L307S in both GvAbf variants are located in TIM barrel domain, responsible for catalytic action in many Glycoside Hydrolase Families including GH51. The structure of GvAbf model displayed that the position of L307S mutation is closer to the catalytic residues of GvAbf compared with Q90H mutation and also L307S mutation is conserved in both variants of GvAbf. Therefore, it was hypothesized that L307S amino acid substitution may play a critical role in catalytic activity of GvAbf. (C) 2018 International Union of Biochemistry and Molecular Biology, Inc.Article Citation - WoS: 6Citation - Scopus: 7Development of a Water-Soluble 3-Formylbodipy Dye for Fluorogenic Sensing and Cell Imaging of Sulfur Dioxide Derivatives(Elsevier Ltd., 2019) Işık, Murat; Şimşek Turan, İlke; Dartar, SuayA new water-soluble, highly fluorogenic 3-formylBODIPY dye that enables the sensing of SO2 derivatives in aqueous buffers and cancer cells is reported. The quaternary ammonium group appended through the mesa-position of the BODIPY dye ensures water solubility. The probe exhibits high specificity for cytosolic (bi)sulfites and fluoresces brightly in human lung adenocarcinoma cells (A549). (C) 2019 Elsevier Ltd. All rights reserved.Article Citation - WoS: 35Citation - Scopus: 36Colloidal Nanodisk Shaped Plexcitonic Nanoparticles With Large Rabi Splitting Energies(American Chemical Society, 2019) Mert Balcı, Fadime; Sarısözen, Sema; Polat, Nahit; Balcı, SinanWhen plasmons supported by metal nanoparticles interact strongly with molecular excitons or excitons of semiconducting quantum dots, plexcitons are formed in the strong coupling regime. The hybrid plexcitonic nanoparticles with a wide range of sizes and shapes have been synthesized by using wet chemistry methods or have been fabricated on solid substrates by using lithographic techniques. In order to deeply understand plasmon-exciton interaction at the nanoscale dimension and boost the performance of nanophotonic devices made of plexcitonic nanoparticles, new types of plexcitonic nanoparticles with tunable optical properties and outstanding stability at room temperature are urgently needed. Herein, we for the first time report pure colloidal nanodisk shaped plexcitonic nanoparticles with very large Rabi splitting energies, i.e., more than 350 meV. We synthesize silver nanoprisms by using seed mediated synthesis and then convert nanoprisms to nanodisks at a high temperature. Localized plasmon resonance of the silver nanodisk in the visible spectrum can be effectively tuned by heating. Subsequently, self-assembly of J-aggregate dyes on plasmonic nanodisks produces plexcitonic nanoparticles. We envision that colloidal nanodisk shaped plexcitonic nanoparticles with very large Rabi splitting energies and outstanding stability at room temperature will enlarge the application of plexcitonic nanoparticles in a variety of fields such as polariton laser, biosensor, plasmon molecular nanodevices, and energy flow at nanoscale dimensions.Article Citation - WoS: 2Citation - Scopus: 3Determination of Arsenic by Hydride Generation—laser-Induced Breakdown Spectroscopy: Characterization of Interelement Interferences(Taylor and Francis Ltd., 2018) Bölek, Deniz; Ünal Yeşiller, Semira; Yalçın, ŞerifeIn this study, interelement interferences were evaluated for the determination of arsenic in aqueous samples through laser-induced breakdown spectroscopy (LIBS) hyphenated with a hydride generation sample introduction system. Optimum instrumental and chemical parameters were selected and variation in LIBS signal intensity was recorded for As solution in the presence of comparable concentrations of interfering elements. No significant change in the signal intensity of As(I) 228.8 nm line was observed in the presence of alkali/alkali earth metals; however, the presence of hydride-forming elements has shown a noticeable decrease in the line emission strength of arsenic. The least variation in arsenic signal was observed in the presence of Ge, the most volatile of all. However, the signal has decreased to a greater extent in the presence of Sn, Sb, and Pb. The presence of interfering elements on electron temperature and electron number density of arsenic plasma has also been studied. Plasma temperatures calculated using both As and Ar emission lines in the Boltzmann equation were similar, being around 5000 K. The McWhirter criterion for stationary and homogenous plasmas was utilized for the establishment of the local thermodynamic equilibrium under the plasma conditions studied. Applicability of the technique for multielemental analysis of water samples was tested through spiking experiments. Arsenic signal showed 26% decrease in the multielemental mixture solution. LIBS is among a few atomic spectroscopic techniques that facilitate rapid and simultaneous multielemental analysis without extensive sample preparation steps. However, the analytical performance of the technique still requires more serious efforts to compete with other conventional techniques for routine analysis of environmental samples.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: 42Citation - Scopus: 47Ph Responsive Glycopolymer Nanoparticles for Targeted Delivery of Anti-Cancer Drugs(Royal Society of Chemistry, 2018) Yılmaz, Gökhan; Güler, Emine; Geyik, Caner; Demir, Bilal; Özkan, Melek; Odacı Demirkol, Dilek; Özçelik, Serdar; Timur, Suna; Becer, C. RemziOver the past decade, there has been a great deal of interest in the integration of nanotechnology and carbohydrates. The advances in glyconanotechnology have allowed the creation of different bioactive glyconanostructures for different types of medical applications, especially for drug delivery and release systems. Therefore, the use of more efficient biocompatible nanocarriers with high loading capacity, low overall toxicity and receptor-mediated endocytosis specificity is still in focus for the enhancement of the therapeutic effect. Conjugation of sugar derivatives onto gold nanoparticles presents unique properties that include a wide array of assembling models and size-related electronic, magnetic and optical properties. Here, pH-responsive drug-conjugated glycopolymer-coated gold nanoparticles were prepared by functionalization of gold nanoparticles with thiol-terminated glycopolymers and then subsequent conjugation of doxorubicin (DOX). Among the four different glycopolymers, their drug release, physicochemical characterization (spectroscopy, particle size and surface charge) and in vitro bioapplications with four different cell lines were compared. As a result, pH-sensitive drug delivery via sugar-coated AuNPs was performed thanks to hydrazone linkages between glycopolymers and DOX. Comparative viability tests also demonstrated the efficiency of glycopolymer-DOX conjugates by fluorescence cell imaging. The obtained results reveal that AuNP homoglycopolymer DOX conjugates (P4D) have significant potential, especially in human neuroblastoma cells in comparison to cervical cancer cells and lung cancer cells.Article Citation - WoS: 1Citation - Scopus: 1Comparative Proteomic Analysis of Bacillus Thuringiensis Wild-Type and Two Mutant Strains Disturbed in Polyphosphate Homeostasis(TUBITAK, 2018) Yeşilırmak, Filiz; Doruk, Tuğrul; Yılmaz, Şerif; Tunca Gedik, SedefPolyphosphate polymer (polyP) plays a very important role in every living cell. Synthesis of this linear polymer of phosphate (Pi) residues is catalyzed by the polyphosphate kinase (PPK) enzyme. It was shown that high levels of intracellular polyphosphate stimulated endotoxin production by Bacillus thuringiensis subsp. israelensis (Bti). In this study, proteomic analysis of the wild-type and two mutant strains, overexpressing the ppk gene (Bti pHTppk) and without the ppk gene (Bti ∆ppk), were used to clarify the relation between polyP and endotoxin production. Intracellular proteins were separated by two-dimensional gel electrophoresis; 41 spots of interest (proteins differentially expressed) were obtained and 35 of them were identified by mass spectrometry. Analysis of the protein profiles showed that there is a general decrease in the expression levels of proteins related with energy metabolism, amino acid metabolism, and purine biosynthesis in both Bti pHTppk and Bti ∆ppk. Gluconeogenesis and fatty acid metabolism were also slowed down in both strains, whereas expression of stress response proteins increased compared to the wild-type. These results suggested that changes in polyP concentration cause a general stress condition inside the cell, which in turn stimulates secondary metabolite synthesisArticle Citation - WoS: 13Citation - Scopus: 14Rhodium(i)-Catalyzed Carbonylative Arylation of Alkynes With Arylboronic Acids Using Formaldehyde as a Carbonyl Source(Georg Thieme Verlag, 2014) Wang, Chuang; Morimoto, Tsumoru; Kanashiro, Hiroyuki; Tanimoto, Hiroki; Nishiyama, Yasuhiro; Kakiuchi, Kiyomi; Artok, LeventThe rhodium(I)-catalyzed reaction of alkynes with arylboronic acids in the presence of formaldehyde resulted in a carbon monoxide gas-free carbonylative arylation to yield α,β-enones. The simultaneous loading of phosphine-ligated and phosphine-free rhodium(I) complexes is required for efficient catalysis, which catalyze the abstraction of a carbonyl moiety from formaldehyde (decarbonylation) and its subsequent introduction into the substrate (carbonylation), respectively.