Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 1Citation - Scopus: 1A Multi-Layered Graphene Based Gas Sensor Platform for Discrimination of Volatile Organic Compounds Via Differential Intercalation(Royal Society of Chemistry, 2023) Özkendir İnanç, Dilce; Ng, Zhi Kai; Başkurt, Mehmet; Keleş, Berfin; Vardar, Gökay; Şahin, Hasan; Tsang, Siu Hon; Palaniappan, Alagappan; Yıldız, Ümit Hakan; Teo, EhtSelective and sensitive detection of volatile organic compounds (VOCs) is of critical importance for environmental monitoring, disease diagnosis and industrial applications. Among VOCs, assay development for primary alcohols has captured significant research attention since their toxicity causes adverse effects on gastrointestinal and central nerve systems, resulting in irreversible blindness, and coma, and can be even fatal at high exposure levels. However, selective detection of primary alcohols is extremely challenging owing to the similarity in their molecular structure and characteristic groups. Herein, we have attempted to investigate the differential methanol (MeOH)-ethanol (EtOH) discriminative properties of single-layer, bi-layer, and multi-layer graphene morphologies. Chemiresistors fabricated using the three morphologies of graphene illustrate discriminative MeOH-EtOH responses, which is attributed to the phenomenon of differential intercalation of MeOH within layered graphene morphologies as compared to that of EtOH. This hypothesis is verified by density functional theory calculations, which revealed that the adsorption of EtOH molecules on the graphene surface is more energetically favorable as compared to that of MeOH molecules, thereby inhibiting their intercalation within the layered graphene morphologies. It is further evaluated that the degree of MeOH intercalation increases with increasing layers of graphene for obtaining differential MeOH-EtOH responses. Experimental results suggest possibilities to develop selective and sensitive MeOH assays fabricated using various graphene morphologies in a combinatorial sensor array format.Article Citation - WoS: 3Citation - Scopus: 3Continuous Production of Hyperbranched Polyhydrocarbons by Electrochemical Polymerization of Chlorinated Methanes(Royal Society of Chemistry, 2022) Seo, Jae Hong; Nam, Hyun Ju; Rajendiran, Rajmohan; Seong, Won Kyung; Jiang, Yi; Kim, Min Hyeok; Büyükçakır, OnurA continuous production of polyhydrocarbon (PHC) by electrochemical polymerization of chlorinated hydrocarbons is presented. Monomer loading and product transfer were controlled by changing flow direction in a home-built continuous flow system that facilitates preparation, work-up, and scale-up of electrochemical polymerization. The polymerization can be tuned by adjusting reaction time, cell configuration, molar ratio of input chemicals, and the solvent type. CH2Cl2, CHCl3, and CCl4 were used to synthesize PHC. The reduction of the monomers at the cathode was studied by cyclic voltammetry and chronoamperometry. We investigated the structure and composition of PHCs from FT-IR and NMR spectra along with elemental analysis. Sufficient amounts of product are generated by continuous production and characterization of the product PHCs by a wide variety of methods is possible. Particularly, structural analysis by various C-13 NMR techniques suggests a new pathway for the synthesis of hyperbranched PHCs by electrochemical polymerization.Article Citation - WoS: 5Citation - Scopus: 5Structural Analysis of Hyperbranched Polyhydrocarbon Synthesized by Electrochemical Polymerization(Royal Society of Chemistry, 2022) Jiang, Yi; Kim, Minhyeok; Nam, Hyunju; Kwak, Sang Kyu; Ruoff, Rodney S.; Lee, Sun Hwa; Seo, Jae Hong; Shin, Eunhye; Joo, Se Hun; Büyükçakır, OnurWe describe a structural analysis method for a hyperbranched polyhydrocarbon (PHC) produced by electrochemical polymerization. Nuclear magnetic resonance (NMR) techniques including 1H-NMR, quantitative 13C-NMR, DEPT 13C-NMR, and 1H-13C HSQC 2D NMR along with elemental analysis and FTIR were used to experimentally assess the likely structure of this complex polymer with random branching. The polymer structure was modeled based on the NMR results. Room temperature density, refractive index, melting temperature, and IR spectrum were good matches to the values, and spectrum, calculated using the simulated structure. Calculated Hildebrand solubility parameters for the simulated structure rationalize the room temperature solubility measured in a range of solvents. The experimental and modeling methods are likely to be applicable to any type of highly branched random branching polymer. To the best of our knowledge, this is the first comprehensive elucidation of the structure of an unknown and randomly hyperbranched polymer by combining experimental results and theoretical simulation, and the methods described should find broad use in the future.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: 2Citation - Scopus: 2Palladium-Catalysed Regio- and Stereoselective Arylative Substitution of Gamma,delta-Epoxy Esters and Amides by Sodium Tetraaryl Borates(Royal Society of Chemistry, 2020) Bilgi, Yasemin; Kuş, Melih; Artok, LeventPalladium-catalysed reactions of gamma,delta-epoxy-alpha,beta-unsaturated esters and amides with NaBAr(4)reagents proceeded regio- and stereoselectively, producing allylic homoallyl alcohols with aryl-substituents in the allylic position for a wide range of substrates. AsPh(3)was found to be a competent ligand for the arylation reaction, whereas phosphine ligand/Lewis acidic organoboron combinations favoured the substitution reaction by oxygen nucleophiles (e.g.H2O, ROH).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: 22Citation - Scopus: 22Fluorescein Propiolate: a Propiolate- Decorated Fluorescent Probe With Remarkable Selectivity Towards Cysteine(Royal Society of Chemistry, 2019) Karakuş, Erman; Sayar, Melike; Dartar, Suay; Kaya, Beraat Umur; Emrullahoğlu, MustafaA fluorescent probe decorated with an alkynyl ester unit (e.g. propiolate) displayed a selective turn-on type fluorescent response towards cysteine. Following a sequential addition-cyclisation pathway mediated by the addition of cysteine, the pre-fluorescent dye rapidly transformed into a new structure and induced a fluorescent response clearly observable with the naked eye.