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  • Article
    Citation - WoS: 8
    Citation - Scopus: 8
    Improvement of Optical Properties and Redox Stability of Poly(3,4-Ethylenedioxythiophene)
    (Elsevier Sci Ltd, 2018) Ertan, Salih; Cihaner, Atilla
    In order to improve the optical properties and redox stability of poly(3,4-ethylenedioxythiophene) (PEDOT) without changing its electrochemical and electrochromic behaviour, it was supported with alkyl-substituted polyhedral oligomeric silsesquioxane (POSS) cage. The corresponding copolymers were obtained electrochemically via potentiostatic or potentiodynamic methods and compared to the parent homopolymers. Electrochemical polymerization of EDOT and POSS containing EDOT called EDOT-POSS in various monomer feed ratios was performed in an electrolyte solution of 0.1 M TBAPF(6) dissolved in a mixture of dichloromethane and acetonitrile (1/3: v/v). Just as PEDOT, the copolymers represented the similar band gap (1.61 eV), redox and electrochromic behaviors. On the other hand, when compared to the parent PEDOT, the presence of POSS cages in the copolymer backbone improved the redox stability and optical properties of PEDOT such as higher percent transmittance change (65% at 621 nm), higher transparency at oxidized state, lower switching time (similar to 1.0 s) and higher coloration efficiency (463 cm(2)/C for 95% switching) as well as higher electrochemical stability (86% of its electroactivity retains after 1750 cycles under ambient conditions).
  • Article
    Citation - WoS: 11
    Citation - Scopus: 11
    Electrochemical and Optical Properties of Substituted Phthalimide Based Monomers and Electrochemical Polymerization of 3,4-Ethylenedioxythiophene Oligomeric Silsesquioxane (poss) Analogue
    (Elsevier Sci Ltd, 2019) Cakal, Deniz; Ertan, Salih; Cihaner, Atilla; Onal, Ahmet M.
    A new series of donor-acceptor-donor type trimeric monomers bearing substituted phthalimide units as acceptor units and thiophene and 3,4-ethylenedioxythiophene (EDOT) as donor units was synthesized and characterized. The strength of acceptor units and intramolecular charge transfer between donor and acceptor units were investigated by using electrochemical and optical methods. The main advantage of phthalimide unit over other acceptor units is the ease of its functionalizability. Thus, utilizing this property, a phthalimide derivative (E2P-POSS) bearing polyhedral oligomeric silsesquioxane (POSS) cage was introduced successfully with EDOT and polymerized electrochemically. The corresponding electroactive polymer, PE2P-POSS, has a band gap of 1.72 eV and is an electrochromic polymer: gray when neutralized and eggplant purple when oxidized.
  • Article
    Catalyst-Free Synthesis of Thiourea-Linked Dumbbell-Shaped POSS for Ultrasensitive Determination of Prilocaine in Human Blood With Computational Insights
    (Elsevier, 2026) Bilge, Selva; Bayraktar, Ece Nur; Erkmen, Cem; Balci, Burcu; Abofoul, Anas; Ozkut, Merve Icli; Cihaner, Atilla
    Although various electrochemical sensors have been reported for the determination of local anesthetic drugs, most existing platforms suffer from limited sensitivity, insufficient surface stability, or inadequate electron-transfer efficiency, particularly when applied to complex biological matrices. Moreover, the potential of hybrid polyhedral oligomeric silsesquioxane (POSS)-based nanostructures combined with metal oxide nano-particles for improving electroanalytical performance has not yet been thoroughly explored. In this study, a high-sensitivity electrochemical nanosensor was developed for the determination of prilocaine (PC), an amide-type local anesthetic, using a glassy carbon (GC) electrode modified with POSS-titanium dioxide (TiO2) nano-particles (Nps). The combination of modifications provided a unique electrode surface by combining the high stability of POSS with the strong adsorption properties of TiO2 Nps, thereby increasing both surface loading and adsorption capacity. To elucidate the structure of the modification combination, 1H and 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopic techniques, as well as Brunauer-Emmett-Teller (BET), X-Ray diffraction (XRD), Electrochemical impedance spectroscopy (EIS), and high-resolution transmission electron microscopy (HRTEM) analysis techniques were used, respectively. The analytical performance of the developed nanosensor was systematically optimized using differential pulse voltammetry (DPV), adsorptive stripping differential pulse voltammetry (AdSDPV), square wave voltammetry (SWV), and adsorptive stripping square wave voltammetry (AdSSWV) techniques. As a result of the optimization studies, the lowest limit of detection (LOD) was 3.66 x 10-8 M with the AdSSWV technique. DFT results corroborated the mechanism, indicating ring-centered electron donation (HOMO) and adsorption-favored N/O regions (MEP). Low LOD values were also recorded with other techniques, demonstrating the method's high sensitivity in analyte detection. In real sample analysis tests, PC recovery value in human blood samples was determined to be 98.69% using the AdSDPV technique. Despite the matrix effect, the nanosensor demonstrated high accuracy and reproducibility. The results indicate that the developed POSS-TiO2 Nps modified GC electrode sensor offers a high-performance, reliable, and good electrochemical detection platform suitable for use in biological and clinical applications.