Yazar "Altinisik, Sinem" seçeneğine göre listele

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    Enhanced Photocatalytic Hydrogen Evolution by Star-Shaped Viologen-Sensitized TiO2 Nanoparticles
    (Amer Chemical Soc, 2023) Turgut, Kubra; Altinisik, Sinem; Yanalak, Gizem; Koyuncu, Sermet; Hatay Patir, Imren
    Viologens are well-suited for serving as electron-transfer mediators in redox systems due to their low reduction potential and ability to form stable radical cations. Because of this feature, viologens can play a key role in modifying semiconductors toward enhanced photocatalytic performance. Herein, a series of hybrid photocatalysts composed of TiO2 nanoparticles and star-shaped viologen derivatives with different alkyl chains [TPCBP-X_TiO2; X: ethyl (E), butyl (B), hexyl (H) and octyl (O)] were prepared for the photocatalytic hydrogen evolution from water under visible-light irradiation. The TPCBP-X molecules not only provide photosensitization of TiO2 nanoparticles in the visible-light region but also act as an efficient electron-transfer mediator for the transfer of photoinduced electrons to TiO2 and Pt. Among these photocatalysts, TPCBP-E_TiO2 exhibited a 1.013 mmol g(-1) h(-1) H-2 evolution rate with an apparent quantum yield (AQY) of 20.15% (470 nm), which dramatically improved hydrogen evolution activity among the other structures [TPCBP-X_TiO2 (X; B, H, O)] due to the more porous and uniform surface, resulting in its low barrier effect for electron transfer. In addition, in the presence of a Pt cocatalyst, TPCBP-E_TiO2 yielded a H-2 evolution rate of 17.7 mmol g(-1), which is about 2.2 times higher than that of pure TPCBP-E_TiO2 (8.1 mmol g(-1)) after 8 h of visible-light illumination.
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    New metallophthalocyanines including benzylphenoxy groups and investigation of their organic-field effect transistor (OFET) features
    (Elsevier Sci Ltd, 2022) Ozdemir, Mucahit; Altinisik, Sinem; Koksoy, Baybars; Canimkurbey, Betul; Koyuncu, Sermet; Durmus, Mahmut; Bulut, Mustafa
    In this study, metal and metal-free novel phthalocyanines containing peripheral and non-peripheral tetra 2-ben-zylphenoxy groups were synthesized. The compounds were characterized by UV-Vis, FT-IR, H-1 NMR, and MALDI-TOF mass spectrometry as well as elemental analysis. These new phthalocyanines exhibited excellent solubility in most organic solvents, and their redox behavior was investigated in different solvents such as dimethyl sulfoxide (DMSO) and dichloromethane (DCM). The redox behavior of the peripheral and non-peripheral phthalocyanine compounds 1a -c and 2a -c was determined by cyclic voltammetry and in situ spec-troelectrochemistry. According to organic field-effect transistors (OFETs) measurements, the peripheral and non-peripheral phthalocyanine-cobalt complexes which have higher mobility than others were utilized top-gate bottom-contact OFETs fabrication. The output characteristics of the device show that its mobility is approximately 5 x 10(-2) cm(2)/Vs with p-type accumulation.
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    PEG-functionalized carbazole-based polymers for UV-protected hydrophilic glass coatings
    (Elsevier Science Sa, 2023) Altinisik, Sinem; Kortun, Arzu; Nazli, Ahmet; Cengiz, Ugur; Koyuncu, Sermet
    The UV-absorbing and non-fogging glass coatings containing carbazole-based conjugated backbone with different lengths of hydrophilic PEG subunit (KP-PEG) were produced. The characterizations of the polymers were carried out by using different techniques such as FT-IR, 1H NMR, GPC, TGA and DSC. Transmittance and thin-film morphology analyses, which are essential for UV protection and wettability, were investigated by UV-Vis absorption, AFM and TEM techniques, respectively. Transparent thin films prepared by the polymer solutions in chloroform were obtained by spin coating method at a scan rate of 2000 rpm. The wettability performance and antifogging properties of these surfaces were investigated depending on the PEG length in the polymer subunit. The water contact angle of the surfaces was improved to the range between 60 degrees and 29 degrees depending on the amount of PEG group. KP-PEG750 is the best polymer thin film in terms of having the highest roughness, optimum UV absorption and the low contact angle value.
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    Photoinduced step-growth polymerizations of thiophene-carbazole based covalent organic polymer
    (Elsevier Sci Ltd, 2023) Celiker, Tugba; Altinisik, Sinem; Yagci, Yusuf; Koyuncu, Sermet
    A novel metal-free photochemical method for the synthesis of porous conjugated polymers was used to inves-tigate the effects of introducing thiophene co-monomer to the carbazole-based polymer, 4,4 '-bis(3,6-di(thiophen-2-yl)-9H-carbazol-9-yl)-1,1 '-biphenyl (CBP-Th), in terms of its structural, optical, electrochemical and morphological properties. Irradiation of a CBP-Th monomer solution led to the formation of a dark-colored polymer, PCBP-Th, and the role of thiophene on polymerization was investigated, involving electron transfer between CBP-Th and the iodonium ion in the exciplex produced by proton release and radical coupling reactions. The UV-Vis spectra broadened and redshifted due to the elongation of conjugation and solid-state pi-pi in-teractions by extra thiophene additive after the polymerization process. The addition of thiophene co-monomer also resulted in decreasing the onset potentials and thus slightly raised HOMO positions determined by the DPV technique. In theoretical calculations, it has been observed that the charge distribution of PCBP-Th at HOMO is over the entire conjugated structure and it has localization in thiophene-thiophene bridges at LUMO. Since the thiophene co-monomer changes the intermolecular distance, the thermal stability of PCBP-Th polymers de-creases and accordingly increases the amorphous characters. According to AFM, TEM and SEM images, intro-ducing the thiophene co-monomer led to the formation of larger clusters, resulting in a more pronounced surface texture on both the powders and thin films.
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    Reactive Extraction of Betaine from Sugarbeet Processing Byproducts
    (Amer Chemical Soc, 2023) Altinisik, Sinem; Zeidan, Hani; Yilmaz, M. Deniz; Marti, Mustafa E.
    Betaine from natural sources is still preferred over its synthetic analogue in secondary industries. It is currently obtained by expensive separation means, which is one of the main reasons for its high cost. In this study, reactive extraction of betaine from sugarbeet industry byproducts, that is, molasses and vinasse, was investigated. Dinonylnaphthalenedisulfonic acid (DNNDSA) was used as the extraction agent, and the initial concentration of betaine in the aqueous solutions of byproducts was adjusted to 0.1 M. Although maximum efficiencies were obtained at unadjusted pH values (pH 6, 5, and 6 for aqueous betaine, molasses, and vinasse solutions, respectively), the effect of aqueous pH on betaine extraction was negligible in the range of 2-12. The possible reaction mechanisms between betaine and DNNDSA under acidic, neutral, and basic conditions were discussed. Increasing the extractant concentration significantly increased (especially in the range of 0.1-0.4 M) the yields, and temperature positively (but slightly) affected betaine extraction. The highest extraction efficiencies (similar to 71.5, 71, and 67.5% in a single step for aqueous betaine, vinasse, and molasses solutions, respectively) were obtained with toluene as an organic phase solvent, and it was followed by dimethyl phthalate, 1-octanol, or methyl isobutyl ketone, indicating that the efficiency increased with decreasing polarity. Recoveries from pure betaine solutions were higher (especially at higher pH values and [DNNDSA] < 0.5 M) than those from vinasse and molasses solutions, indicating the adverse influence of byproduct constituents; however, the lower yields were not due to sucrose. Stripping was affected by the type of organic phase solvent, and a significant amount (66-91% in single step) of betaine in the organic phase was transferred to the second aqueous phase using NaOH as the stripping agent. Reactive extraction has a great potential for use in betaine recovery due to its high efficiency, simplicity, low energy demand, and cost.
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    Sequential and Simultaneous Photoinduced Radical and Step- Growth Polymerizations of Carbazole Functional Styrene
    (Amer Chemical Soc, 2022) Celiker, Tugba; Altinisik, Sinem; Vaitusionak, Aliaksei; Kostjuk, Sergei V.; Koyuncu, Sermet; Yagci, Yusuf
    Photoinduced radical and step-growth polymerizations of carbazole functional styrene (vinyl phenyl carbazole, VPC) by sequential and one-pot strategies have been investigated. The obtained polymers were characterized by FTIR, H-1-NMR, GPC, UV-Vis, PL, CV, and BET analyses. The theoretical charge distribution and HOMO-LUMO calculation by DFT were well-matched with those obtained from optical and electrochemical measurements. In the sequential approach, visible light-induced free-radical photopolymerization of VPC by using bisacyl phosphineoxide results in the formation of linear polymers with side-chain carbazole moieties. The resulting polymers exhibit a smooth surface as a consequence of decreasing crystallinity. As evidenced by TEM analysis, the subsequent photoiniated step-growth polymerization of the carbazole groups by using diphenyliodonium hexafluorophosphate (DPI) yields hyperbranched and cross-linked polymers with the microspheres on the surface. In the one-pot approach, concomitant photoinitiated free-radical and step-growth polymerizations by using DPI results in the formation of cross-linked polymers with dispersed distribution. The total nitrogen uptake of VPC-based polymers by using Brunauer-Emmett-Teller (BET) surface area was found to be between about 150 and 190 m(2)/g at 77 K.
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    Tetra-Carbazole based electroactive donor-acceptor dyes: Effect of the phenyl bridging unit on the electrochromic performance
    (Elsevier Sci Ltd, 2022) Doyranli, Ceylan; Altinisik, Sinem; Ozdemir, Mucahit; Koyuncu, Sermet
    In this study, a new Donor-Acceptor-Donor (D-A-D) electroactive molecules (HCQM1 and HCQM2) containing 9H-carbazole and 9-phenyl-9H-carbazole as donor along with quinoxaline (HQ) as acceptor were synthesized and then coated on Indium Tin Oxide/Glass (ITO/Glass) surface by the electrochemical oxidation process. The HOMO-LUMO band gap values obtained by electrochemical oxidation and reduction onsets were calculated as 2.64 and 2.68 eV, respectively. On the other hand, UV-Vis absorption measurements showed that the charge transfer band of HCQM1 was detected at 500 nm with 50 nm red shift upon compared with the HCQM2. According to AFM results, it is seen that the roughness of the poly(HCQM2) film is higher than the poly(HCQM1) film. Finally, the polymer film of HCQM2 showed multi-electrochromic color change (yellow, green, and dark blue) upon the oxidation process. When the electrochromic performance of the HCQM1 and HCQM2 polymer films was compared, it was discovered that the HCQM2 with phenylene spacer unit has better stability and a higher percentage transmittance change (& UDelta;T%) between neutral and oxidized states.
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    Tuning the Electrochromic Properties of Fluorinated Benzochalcogenodiazole Based Donor-Acceptor Polymers
    (Wiley-V C H Verlag Gmbh, 2020) Colak, Betul; Altinisik, Sinem; Koyuncu, Fatma Baycan; Canimkurbey, Betul; Koyuncu, Sermet
    In this study, a series of benzochalcogenodiazole based donor acceptor monomers namely 4,7-bis(4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (TST), 5,6-difluoro-4,7-bis(4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (TST2) and 4,7-bis(4-hexyl-2-thienyl)-2,1,3-benzoselenadiazole (TSeT) were synthesized by Stille reaction and then directly polymerized on to Indium Tin Oxide coated glass (ITO/Glass) surface by electrochemical polymerization process. According to UV-Vis measurements, a 20 nm blue shift was detected at low energy band after fluorination of TST (TST2). Besides, a 40 nm red shift was observed by changing S to Se on the benzochalcogenodiazole moiety (TSeT). Thus, the optical band gaps were varied as 2.32, 2.45 and 2.16 eV for TST, TST2 and TSeT, respectively. According to AFM results, rougher surface was observed in the PTSeT thin film than that of PTST and PTST2. Thin films of electrodeposited polymers onto ITO/glass surface displayed ambipolar multi-electrochromic behavior both anodic and cathodic region. The ambipolar charge distribution was also observed in the theoretical DFT calculations. When the electrochromic performance of the polymer films was compared to each other, it was seen that the PTST2 has a better stability and higher the percentage transmittance change (Delta T%) at near-IR regime between neutral and oxidized states.