Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 13Citation - Scopus: 14Synthesizing and Evaluating the Photodynamic Efficacy of Asymmetric Heteroleptic A(7)b Type Novel Lanthanide Bis-Phthalocyanine Complexes(Royal Society of Chemistry, 2021) Önal, Emel; Tüncel, Özge; Albakour, Mohamad; Gümüşgöz Çelik, Gizem; Gül Gürek, Ayşe; Özçelik, SerdarIn this study heteroleptic A(7)B type novel Lu(iii) and Eu(iii) lanthanide phthalocyanines (LnPc(Pox)[Pc '(AB(3)SH)]) with high extinction coefficients have been synthesized as candidate photosensitizers with reaction yields higher than 33%. The singlet oxygen quantum yields of LuPc(Pox)[Pc '(AB(3)SH)] and EuPc(Pox)[Pc '(AB(3)SH)], respectively, were measured 17% and 1.4% by the direct method in THF. The singlet oxygen quantum yield of LuPc(Pox)[Pc '(AB(3)SH)] in THF is the highest among lutetium(iii) bis-phthalocyanine complexes to date. The photodynamic efficacy of the heteroleptic lanthanide phthalocyanines was evaluated by measuring cell viabilities of A549 and BEAS-2B lung cells, selected to representing in vitro models for testing cancer and normal cells against potential drugs. The cell viabilities demonstrated concentration dependent behavior and were varied by the type of phthalocyanines complexes. Irradiation of the cells for 30 minutes with LED array at 660 nm producing flux of 0.036 J cm(-2) s(-1) increased cell death for LuPcPox-OAc, LuPc(Pox)[Pc '(AB(3)SH)] and ZnPc. The IC50 concentrations of LuPc(Pox)[Pc '(AB(3)SH)] and ZnPc were determined to be below 10 nM for both cell lines, agreeing very well with the singlet oxygen quantum yield measurements. These findings suggest that LuPc(Pox)[Pc '(AB(3)SH)] and particularly LuPcPox-OAc are promising drug candidates enabling lowered dose and shorter irradiation time for photodynamic therapy.Article Citation - WoS: 23Citation - Scopus: 23Bodipy-Vinyl Dibromides as Triplet Sensitisers for Photodynamic Therapy and Triplet-Triplet Annihilation Upconversion(Royal Society of Chemistry, 2021) Dartar, Suay; Üçüncü, Muhammed; Karakuş, Erman; Hou, Yuqi; Zhao, Jianzhang; Emrullahoğlu, MustafaWe devised a new generation of halogen-based triplet sensitisers comprising geminal dibromides at the vinyl backbone of a BODIPY fluorophore. Incorporating geminal dibromides into the pi-conjugation of BODIPY enhanced intersystem crossing due to the heavy atom effect, which in turn improved the extent of excited triplet states.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) Taşcıoğlu, Didem; Sevim Ünlütürk, Seçil; Özçelik, SerdarCounterfeiting 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) Mert Balcı, Fadime; Sarısözen, Sema; Polat, Nahit; Güvenç, Çetin Meriç; Karadeniz, Uğur; Tertemiz, Necip Ayhan; Balcı, SinanThe 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: 21Citation - Scopus: 22Redox-Responsive Release of Active Payloads From Depolymerized Nanoparticles(Royal Society of Chemistry, 2017) Lv, Li-Ping; Jiang, Shuai; İnan, Alper; Landfester, Katharina; Crespy, DanielThe difference in the reactivity of two monomers, aniline (ANI) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT), was employed to design nanoparticles with completely different nanostructures. The monomers were simultaneously polymerized by tandem oxidative polymerization occurring in the miniemulsion droplets. DMcT is also a corrosion inhibitor and its polymer can be depolymerized by reduction, which avoids the unwanted release of the payload DMcT when the capsules are not activated. The redox-responsive release profile of DMcT from the composite particles is controlled by the morphology of the particles and it was investigated for monolithic, multi-hollow, and yolk-shell structures. These PANI/PDMcT composite particles may find potential application in Li-S batteries or in the self-healing systems for corrosion protection.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: 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; Demir, Mustafa Muammer; Eroğlu, Ahmet EminIbuprofen 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: 16Citation - Scopus: 18Polyglycolide-Montmorillonite as a Novel Nanocomposite Platform for Biosensing Applications(Royal Society of Chemistry, 2017) Ünal, Betül; Yalçınkaya, Esra Evrim; Gümüştaş, Sıla; Sönmez, Burak; Özkan, Melek; Balcan, Mehmet; Odacı Demirkol, Dilek; Timur, SunaIn catalytic biosensors, the immobilization of biomolecules in a suitable matrix is one of the vital parameters for obtaining improved systems. Clays, which are intercalated with various organic compounds, have a great tendency to develop biosensors with high stability, sensitivity and reproducibility. Herein, a polymer/clay nanocomposite based on natural silicate montmorilonite (Mt) and a biodegradable polymer polyglycolide (PGA) was prepared and characterized by FT-IR, thermogravimetric analysis, differential thermogravimetric analysis and X-ray diffraction. Then, the resulting matrix was used as a fixation matrix for pyranose oxidase (POx), which was selected as a model enzyme. The bioactive layer was fabricated by immobilization of POx on glassy carbon electrodes by means of PGA-Mt and bovine serum albumin. The POx biosensor revealed a good linear range from 0.01 to 0.5 mM glucose with a LOD of 1.2 μM. After the optimization of the working and preparation conditions, characterization studies were performed for glucose detection. Finally, the PGA-Mt/POx biosensor was confirmed to have detected glucose in beverages without needing any sample pre-treatment.Article Citation - WoS: 41Citation - Scopus: 44Vapor Phase Solvatochromic Responses of Polydiacetylene Embedded Matrix Polymers(Royal Society of Chemistry, 2017) Tu, Meng-Che; Cheema, Jamal Ahmed; Yıldız, Ümit Hakan; Palaniappan, Alagappan; Liedberg, BoThe solvatochromic response of polydiacetylene (PDA) in the vapor phase is enabled upon incorporation with matrix polymers such as polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyacrylic acid (PAA), and poly-4-vinylpyridine (P4VP). The matrix polymers provide a soft/gel-like framework for accommodating photopolymerized PDA, while facilitating its conformational alternations upon interaction with preconcentrated volatile organic compounds (VOCs). The matrix polymers enabled the differentiation of VOCs owing to their varying morphology, chemical affinity and solubility in VOCs. The ratios between PDA and the matrix polymers are optimized according to the obtained solvatochromic responses evaluated in varying temperature, humidity and storage conditions. As a proof of concept, a finger-print array for differentiation of 7 VOCs is demonstrated using matrix polymer-embedded PDA. The obtained results indicate that the response time and sensitivity of the proposed methodology supersedes previous reports on solvatochromic VOC assays. Furthermore, the proposed methodology would enable differentiation of a wide range of VOCs upon incorporation of additional matrix polymers with varying sorption properties.Article Citation - WoS: 22Citation - Scopus: 23A Guanidinium Modified Rhodamine-Based Fluorescent Probe for in Vitro/Vivo Imaging of Gold Ions(Royal Society of Chemistry, 2015) Karakuş, Erman; Çakan Akdoğan, Gülçin; Emrullahoğlu, MustafaWe devised a rhodamine-based fluorescent probe functionalized with a guanidinium moiety, which both operates efficiently in pure aqueous media and displays a selective fluorescence response to Au3+ ions. We also demonstrated the successful fluorescence imaging of Au3+ within living cells and a vertebrate species, the zebrafish.