Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 4Citation - Scopus: 6An Anticounterfeiting Technology Combining an Inp Nanoparticle Ink and a Versatile Optical Device for Authentication(Royal Society of Chemistry, 2021) Özçelik, Serdar; Taşcıoğlu, Didem; Özçelik, Serdar; 04.01. Department of Chemistry; 01. Izmir Institute of Technology; 04. Faculty of ScienceCounterfeiting is a growing issue and causes economic losses. Fluorescent inks containing In(Zn)P/ZnS/DDT colloidal nanoparticles are formulated and combined with a convenient optical device for authentication. The particle size and fluorescent colors of the colloidal nanoparticles were tuned by adjusting the reaction temperature. The particle stability and brightness were improved by the addition of dodecanethiol, coating the particle surface with an organic shell. Security patterns were printed on various substrates by applying the screen-printing technique. The patterns were invisible under daylight but observable under UV-light illumination, displaying five different emission colors. By adjusting the concentration of the nanoparticles in the ink, the security patterns were made almost not observable under UV-light illumination but clearly identified by a commercial fiber optics-based spectrometer and a handheld optical device, called a Quantag sensor that was developed in-house. Furthermore, the spectral signatures of barely noticeable patterns are unambiguously validated by the Quantag sensor. Accordingly, low cost and easily applicable anticounterfeiting technology powered by custom-formulated fluorescent inks and a handheld optical instrument are developed to authenticate valuable documents and products.Article Citation - WoS: 12Citation - Scopus: 14Laser Assisted Synthesis of Anisotropic Metal Nanocrystals and Strong Light-Matter Coupling in Decahedral Bimetallic Nanocrystals(Royal Society of Chemistry, 2021) Balcı, Fadime Mert; Balcı, Sinan; Polat, Nahit; Güvenç, Çetin Meriç; Karadeniz, Uğur; Tertemiz, Necip Ayhan; Balcı, Sinan; 04.04. Department of Photonics; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyThe advances in colloid chemistry and nanofabrication allowed us to synthesize noble monometallic and bimetallic nanocrystals with tunable optical properties in the visible and near infrared region of the electromagnetic spectrum. In the strong coupling regime, surface plasmon polaritons (SPPs) of metal nanoparticles interact with excitons of quantum dots or organic dyes and plasmon-exciton hybrid states called plexcitons are formed. Until now, various shaped metal nanoparticles such as nanorods, core-shell nanoparticles, hollow nanoparticles, nanoprisms, nanodisks, nanorings, and nanobipyramids have been synthesized to generate plasmon-exciton mixed states. However, in order to boost plasmon-exciton interaction at nanoscale dimensions and expand the application of plexcitonic nanocrystals in a variety of fields such as solar cells, light emitting diodes, and nanolasers, new plexcitonic nanocrystals with outstanding optical and chemical properties remain a key goal and challenge. Here we report laser-assisted synthesis of decahedral shaped noble metal nanocrystals, tuning optical properties of the decahedral shaped nanocrystals by galvanic replacement reactions, colloidal synthesis of bimetallic decahedral shaped plexcitonic nanocrystals, and strong plasmon-plasmon interaction in bimetallic decahedral shaped noble metal nanocrystals near a metal film. We photochemically synthesize decahedral Ag nanoparticles from spherical silver nanoparticles by using a 488 nm laser. The laser assisted synthesis of silver nanoparticles yields decahedral (bicolored) and prism (monocolored) shaped silver nanocrystals. The decahedral shaped nanoparticles were selectively separated from prism shaped nanoparticles by centrifugation. The optical properties of decahedral nanocrystals were tuned by the galvanic replacement reaction between gold ions and silver atoms. Excitons of J-aggregate dyes and SPPs of decahedral bimetallic nanoparticles strongly couple and hence decahedral shaped plexcitonic nanoparticles are prepared. In addition, localized SPPs of decahedral shaped bimetallic nanocrystals interact strongly with the propagating SPPs of a flat silver film and hence new hybrid plasmonic modes (plasmonic nanocavities) are generated. The experimental results are further fully corroborated by theoretical calculations including decahedral shaped plexcitonic nanoparticles and decahedral nanoparticles coupled to flat metal films.Article Citation - WoS: 55Citation - Scopus: 60Development of Molecularly Imprinted Polymers (mips) as a Solid Phase Extraction (spe) Sorbent for the Determination of Ibuprofen in Water(Royal Society of Chemistry, 2017) Ölçer, Yekta Arya; Demirkurt, Merve; Eroğlu, Ahmet Emin; Eroğlu, Ahmet Emin; Demir, Mustafa Muammer; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyIbuprofen is a well-known endocrine disrupter. In this study, highly selective molecularly imprinted polymers (MIPs) with different morphologies were synthesized via precipitation and bulk polymerization of methacrylic acid (MAA) and trimethylolpropane trimethacrylate (TRIM) in the presence of ibuprofen as a template. Non-imprinted polymers (NIPs) were also synthesized via the same procedure in the absence of ibuprofen. Spherical and monolithic MIPs were obtained using different experimental conditions, and the spherical MIP was shown to have better sorption towards ibuprofen. The optimum sample pH, sorbent amount, sample volume, and sorption time were determined to be 8.0, 25.0 mg, 10.0 mL, and 30.0 min, respectively. A methanol water mixture (MeOH:H2O, 80:20, pH 3.0) was employed as an eluent with >97% (±0.8, n = 3) desorption. The MIP demonstrated high selectivity towards ibuprofen in the presence of naproxen and ketoprofen. The validity of the proposed method was checked via spike recovery tests using drinking and tap water samples. The method worked efficiently for both water types, resulting in the recoveries of 97.2% (±0.3, n = 3) and 97.7% (±0.2, n = 3).Article Citation - WoS: 33Citation - Scopus: 36Epr Studies of Intermolecular Interactions and Competitive Binding of Drugs in a Drug-Bsa Binding Model(Royal Society of Chemistry, 2016) Akdoğan, Yaşar; Emrullahoğlu, Mustafa; Akdoğan, Yaşar; Üçüncü, Muhammed; Çakan Akdoğan, Gülçin; Emrullahoğlu, Mustafa; 03.09. Department of Materials Science and Engineering; 04.04. Department of Photonics; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyUnderstanding intermolecular interactions between drugs and proteins is very important in drug delivery studies. Here, we studied different binding interactions between salicylic acid and bovine serum albumin (BSA) using electron paramagnetic resonance (EPR) spectroscopy. Salicylic acid was labeled with a stable radical (spin label) in order to monitor its mobilized (free) or immobilized (bound to BSA) states. In addition to spin labeled salicylic acid (SL-salicylic acid), its derivatives including SL-benzoic acid, SL-phenol, SL-benzene, SL-cyclohexane and SL-hexane were synthesized to reveal the effects of various drug binding interactions. EPR results of these SL-molecules showed that hydrophobic interaction is the main driving force. Whereas each of the two functional groups (-COOH and -OH) on the benzene ring has a minute but detectable effect on the drug-protein complex formation. In order to investigate the effect of electrostatic interaction on drug binding, cationic BSA (cBSA) was synthesized, altering the negative net charge of BSA to positive. The salicylic acid loading capacity of cBSA is significantly higher compared to that of BSA, indicating the importance of electrostatic interaction in drug binding. Moreover, the competitive binding properties of salicylic acid, ibuprofen and aspirin to BSA were studied. The combined EPR results of SL-salicylic acid/ibuprofen and SL-ibuprofen/salicylic acid showed that ibuprofen is able to replace up to ∼83% of bound SL-salicylic acid, and salicylic acid can replace only ∼14% of the bound SL-ibuprofen. This indicates that ∼97% of all salicylic acid and ibuprofen binding sites are shared. On the other hand, aspirin replaces only ∼23% of bound SL-salicylic acid, and salicylic acid replaces ∼50% of bound SL-aspirin, indicating that ∼73% of all salicylic acid and aspirin binding sites are shared. These results show that EPR spectroscopy in combination with the spin labeling technique is a very powerful method to investigate drug binding dynamics in detail.Article Citation - WoS: 24Citation - Scopus: 27Physiological Concentrations of Albumin Favor Drug Binding(Royal Society of Chemistry, 2015) Tatlıdil, Diğdem; Üçüncü, Muhammed; Akdoğan, Yaşar; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 01. Izmir Institute of TechnologyThe ability to track drug binding and release makes electron paramagnetic resonance (EPR) spectroscopy well suited for drug delivery studies. Using the continuous wave (cw) EPR technique to extract information about the dynamics of the spin labeled drugs we can simultaneously determine the bound and unbound drugs. Here, spin labeled salicylic acid (SLSA) binding to and release from bovine serum albumin (BSA) is investigated, as a model for drug-transport protein interaction. We studied SLSA-BSA binding in a wide concentration range and found that the stoichiometry of the drug-protein increases significantly when the physiological range of BSA concentration is reached. Our EPR results explicitly reveal that up to ∼7 SLSA can bind to one albumin at the physiological concentration, whereas at lower BSA concentrations (<0.125 mM) the SLSA-BSA stoichiometry is maximum 2. Moreover, we studied drug release and showed that the ratio of bound to unbound SLSA concentrations remains relatively stable during dialysis. This indicates that the binding equilibrium of SLSA is not altered through the process of dialysis. This study demonstrates that cw EPR spectroscopy in combination with spin labeled drugs is an effective technique for binding and release studies and stoichiometric analysis of drug-protein interactions.Article Citation - WoS: 109Citation - Scopus: 124Chitosan Fiber-Supported Zero-Valent Iron Nanoparticles as a Novel Sorbent for Sequestration of Inorganic Arsenic(Royal Society of Chemistry, 2013) Horzum Polat, Nesrin; Demir, Mustafa Muammer; Shahwan, Talal; Demir, Mustafa Muammer; 03.09. Department of Materials Science and Engineering; 04.01. Department of Chemistry; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyThis study proposes a new sorbent for the removal of inorganic arsenic from aqueous solutions. Monodispersed nano zero-valent iron (nZVI) particles were nucleated at the surface of electrospun chitosan fibers (average fiber diameter of 195 ± 50 nm) by liquid phase reduction of FeCl3 using NaBH4. The material was characterized using SEM, TGA, XPS, XRD, and FTIR. The diameter of iron nanoparticles was found to vary between 75-100 nm. A set of batch experiments were carried out to elucidate the efficiency of the composite sorbent toward fixation of arsenite and arsenate ions. The ion concentrations in the supernatant solutions were determined using inductively coupled plasma-mass spectrometry (ICP-MS). The results revealed that the chitosan fiber supported nZVI particles is an excellent sorbent material for inorganic arsenic uptake at concentrations ranging from 0.01 to 5.00 mg L -1 over a wide range of pH values. Based on XPS analysis, As(iii) was found to undergo oxidation to As(v) upon sorption, while As(v) retained its oxidation state. By virtue of the successful combination of the electrospun fibers' mechanical integrity and the large reactivity of dispersed nZVI particles, the applicability of the resulting sorbent material in arsenic sorption holds broad promise.Article Citation - WoS: 16Citation - Scopus: 17Electrospun Amino-Functionalized Pdms as a Novel Spme Sorbent for the Speciation of Inorganic and Organometallic Arsenic Species†(Royal Society of Chemistry, 2013) Boyacı, Ezel; Horzum, Nesrin; Çağır, Ali; Demir, Mustafa Muammer; Eroğlu, Ahmet Emin; Demir, Mustafa Muammer; Eroğlu, Ahmet Emin; 04.01. Department of Chemistry; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologySol–gel based amine-functionalized SPME fibers (PDMS-weak anion exchanger) were prepared and used for direct mode extraction of dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and arsenate (As(V)) from aqueous solutions followed by HPLC-ICPMS determination. Two different methods of coating were employed: (i) electrospinning and (ii) dip coating. Electrospinning was used for the first time for preparation of sol–gel based SPME fibers and was found to be superior in terms of extracted amount of arsenicals, coating homogeneity, accessibility of amine groups on the surface, and preparation time for a single fiber. Various parameters such as solution pH, extraction time, agitation speed, extraction temperature, and ionic strength were studied. Optimum extraction conditions were determined as pH of 5.0, extraction time of 30 min, agitation speed of 700 rpm, and extraction temperature of 20 C. Extraction ability of the novel coating decreased by the addition of NaCl as a consequence of the competition between anionic arsenic species and chloride ions for active sites of the weak anion exchanger. This novel sol–gel coating prepared by electrospinning was found to be promising for SPME applications. Vibrational spectroscopy revealed the alignment of PDMS chains by elongational force under electrospinning process. The chain alignment accordingly orients the pendant amino functional groups perpendicular to the fiber surface, which may develop the free active functional groups available to the medium and lead to the enhancement of the extraction performance. Moreover, the proposed coating strategy through electrospinning might be able to break new ground for various applications in analytical chemistry as well as other disciplines.