PubMed İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/397
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Article Citation - WoS: 19Citation - Scopus: 19Understanding and Tailoring Excited State Properties in Solution-Processable Oligo(p-Phenyleneethynylene)s: Highly Fluorescent Hybridized Local and Charge Transfer Character via Experiment and Theory(Amer Chemical Soc, 2021-10-13) Usta, Hakan; Cosut, Bunyemin; Alkan, FahriRod-shaped oligo(p-phenyleneethynylene) (OPE) offers an attractive p-framework for the development of solution-processable highly fluorescent molecules having tunable hybridized local and charge transfer (HLCT) excited states and (reverse) intersystem crossing ((R)ISC) channels. Herein, an HLCT oligo(p-phenyleneethynylene) library was studied for the first time in the literature in detail systematically via experiment and theory. The design, synthesis, and full characterization of a new highly fluorescent (Phi(PL-solution) similar to 1) sky blue emissive 4',4 ''-((2,5-bis((2-ethylhexyl)oxy)-1,4-phenylene)bis(ethyne-2,1-diyl))bis(N,N-diphenyl-[1,1'-bi-phenyl]-4-amine) (2EHO-TPA-PE) was also reported. The new molecule consists of a D'-Ar-pi-D-pi-Ar-D' molecular architecture with an extended pi-spacer and no acceptor unit, and detailed structural, physicochemical, single-crystal, and optoelectronic characterizations were performed. A high solid-state quantum efficiency (Phi(PL-solution) similar to 0.8) was achieved as a result of suppressed exciton-phonon/vibronic couplings (no pi-pi interactions and multiple (14 per dimeric form) strong C-H center dot center dot center dot pi interactions). Strong solution-phase/solid-state dipole-dependent tunable excited state behavior (local excited (LE) -> HLCT -> charge transfer (CT)) and decay dynamics covering a wide spectral region were demonstrated, and the CT state was observed to be highly fluorescent despite extremely large Stokes shift (similar to 130 nm)/fwhm (similar to 125 nm) and significant charge separation (0.75 charge.nm). Employing the Lippert-Mataga model, along with detailed photophysical studies and TDDFT calculations, key relationships between molecular design-electronic structure-exciton characteristics were elucidated with regards to HLCT and hot exciton channel formations. The interstate coupling between CT and LE states and the interplay of this coupling with respect to medium polarity were explored. A key relationship between excited-state symmetry breaking process and the formation of HLCT state was discussed for TPA-ended rod-shaped OPE p-systems. (R)ISC-related delayed fluorescence (tau similar to 2-6 ns) processes were evident following the prompt decays (similar to 0.4-0.9 ns) both in the solution and in the solid-state. As a unique observation, the delayed fluorescence could be tuned and facilitated via small dielectric changes in the medium. Our results and the molecular engineering perspectives presented in this study may provide unique insights into the structural and electronic factors governing tunable excited state and hot-exciton channel formations in OPEs for (un)conventional solution-processed luminescence applications.Article Citation - WoS: 4Citation - Scopus: 4Transparent Films Made of Highly Scattering Particles(Amer Chemical Soc, 2020-01-13) Erdem, Talha; Yang, Lan; Xu, Peicheng; Altintas, Yemliha; O'Neil, Thomas; Caciagli, Alessio; Eiser, ErikaToday, colloids are widely employed in various products from creams and coatings to electronics. The ability to control their chemical, optical, or electronic features by controlling their size and shape explains why these materials are so widely preferred. Nevertheless, altering some of these properties may also lead to some undesired side effects, one of which is an increase in optical scattering upon concentration. Here, we address this strong scattering issue in films made of binary colloidal suspensions. In particular, we focus on raspberry-type polymeric particles made of a spherical polystyrene core decorated by small hemispherical domains of acrylate with an overall positive charge, which display an unusual stability against aggregation in aqueous solutions. Their solid films display a brilliant red color due to Bragg scattering but appear completely white on account of strong scattering otherwise. To suppress the scattering and induce transparency, we prepared films by hybridizing them with oppositely charged PS particles with a size similar to that of the bumps on the raspberries. We report that the smaller PS particles prevent raspberry particle aggregation in solid films and suppress scattering by decreasing the spatial variation of the refractive index inside the film. We believe that the results presented here provide a simple strategy to suppress strong scattering of larger particles to be used in optical coatings.Article Citation - WoS: 27Citation - Scopus: 29Revisiting the Role of Charge Transfer in the Emission Properties of Carborane-Fluorophore Systems: A TDDFT Investigation(Amer Chemical Soc, 2022-06-05) Tahaoglu, Duygu; Usta, Hakan; Alkan, FahriIn this study, we performed a detailed investigation of the S-1 potential energy surface (PES) of o-carborane-anthracene (o-CB-Ant) with respect to the C-C bond length on o-CB and the dihedral angle between o-CB and Ant moieties. The effects of different substituents (F, Cl, CN, and OH) on carbon- or boron-substituted o-CB, along with a pi-extended acene-based fluorophore, pentacene, on the nature and energetics of S-1 -> S-0 transitions are evaluated. Our results show the presence of a non-emissive S-1 state with an almost pure charge transfer (CT) character for all systems as a result of significant C-C bond elongation (C-C = 2.50-2.56 angstrom) on o-CB. In the case of unsubstituted o-CB-Ant, the adiabatic energy of this CT state corresponds to the global minimum on the S-1 PES, which suggests that the CT state could be involved in emission quenching. Despite large deformations on the o-CB geometry, predicted energy barriers are quite reasonable (0.3-0.4 eV), and the C-C bond elongation can even occur without a noticeable energy penalty for certain conformations. With substitution, it is shown that the dark CT state becomes even more energetically favorable when the substituent shows -M effects (e.g., -CN), whereas substituents showing +M effects (e.g., -OH) can result in an energy increase for the CT state, especially for partially stretched C-C bond lengths. It is also shown that the relative energy of the CT state on the PES depends strongly on the LUMO level of the fluorophore as this state is found to be energetically less favorable compared to other conformations when anthracene is replaced with pi-extended pentacene. To our knowledge, this study shows a unique example of a detailed theoretical analysis on the PES of the S-1 state in o-CB-fluorophore systems with respect to substituents or fluorophore energy levels. Our findings could guide future experimental work in emissive o-CB-fluorophore systems and their sensing/optoelectronic applications.Article Citation - WoS: 1Citation - Scopus: 1Osmotic-Pressure Nematic Ordering in Suspensions of Laponite and Carboxy Methyl Cellulose(Amer Chemical Soc, 2020-10-12) Xu, Peicheng; Yazici, Ahmet F.; Erdem, Talha; Lekkerkerker, Henk N. W.; Mutlugun, Evren; Eiser, ErikaLaponite is a synthetic clay that is known to form gels in aqueous suspensions at low concentrations (0.01 g/cm(3)) Although it is expected to form lyotropic liquid crystals, such phases usually do not form, as a consequence of laponite's tendency to form gels at concentrations below the threshold for liquid crystal formation. Here we show that macroscopic, birefringent phases of laponite can be prepared through osmotic compression of a laponite solution by an aqueous solution of carboxy methyl cellulose (CMC). We present polarization imaging studies showing how the initially dilute, isotropic laponite phase shrinks while developing typical birefringence colors between crossed polarizers. Using the MichelLevy interference charts, we were able to extract the refractive index and orientation of the laponite nanodisks in the compressed region. Our observations allow us to propose a tentative state diagram, indicating the concentration regions for which we obtain optically anisotropic gels.Article Citation - WoS: 35Citation - Scopus: 36In Situ Synthesis of Horseradish Peroxidase Nanoflower@Carbon Nanotube Hybrid Nanobiocatalysts With Greatly Enhanced Catalytic Activity(Amer Chemical Soc, 2023-03-21) Dadi, Seyma; Temur, Nimet; Gul, O. Tolga; Yilmaz, Vedat; Ocsoy, IsmailOrganic-inorganic hybrid nanoflowers (NFs) consisting of horseradish peroxidase (HRP) and copper II (Cu2+) are successfully synthesized with the involvement of carbon nanotubes (CNTs) by in situ and post-modification methods. Catalytic activities of in situ synthesized HRP-NF@CNT (HRP-NF@CNT-Is) and post-modification-synthesized HRP-NF@CNTs (HRP-NF@CNT-Pm) are systematically examined. The 30 mg CNTs incorporated HRP-NF@CNT-Is (HRP-NF@ CNT-30Is) exhibits greatly increased catalytic activity and stability toward 3,3 ',5,5 '-tetramethylbenzidine (TMB), thanks to the synergistic effect between HRP-NF and CNTs and the peroxidase-like activity of CNTs in the presence of hydrogen peroxide (H2O2). While HRP-NF@CNT-30Is retains almost 85% of its initial activity even after 10 cycles, HRP-NF (without CNTs) loses half of its initial activity at the same experimental conditions. We study how two experimental parameters, the pH values and temperatures, influence the catalytic activity of HRP-NF@CNT-30Is, in addition to the fact that HRP-NF@CNT-30Is is employed to detect the presence of H2O2 and glutathione (GSH) with colorimetric and spectrophotometric readouts. For instance, HRP-NF@CNT-30Is is used to sensitively detect H2O2 in the range of 20 to 300 mu M with an LOD of 2.26 mu M. The catalytic activity of HRP-NF@CNT-30Is is suppressed in the presence of GSH, and then an obvious color change from blue to nearly colorless is observed. Using this strategy, GSH is also sensitively determined in the range of 20-200 mu M with an LOD of 11.2 mu M. We expect that HRP-NF@CNTs can be used as a promising and novel nanobiocatalyst for various biomedical and industrial applications in the near future.Article Citation - WoS: 38Citation - Scopus: 40Effect of Molecular Architecture on Cell Interactions and Stealth Properties of PEG(Amer Chemical Soc, 2017-08-25) Ozer, Imran; Tomak, Aysel; Zareie, Hadi M.; Baran, Yusuf; Bulmus, VolgaPEGylation, covalent attachment of PEG to therapeutic biomolecules, in which suboptimal pharmacokinetic profiles limiting their therapeutic utility are of concern, is a widely applied technology. However, this technology has been challenged by reduced bioactivity of biomolecules upon PEGylation and immunogenicity of PEG triggering immune response and abrogating clinical efficacy, which collectively necessitate development of stealth polymer alternatives. Here we demonstrate that comb-shape poly[oligo(ethylene glycol) methyl ether methacrylate](POEGMA); a stealth polymer alternative, has a more compact structure than PEG and self-organize into nanoparticles in a molecular weight dependent manner. Most notably, we show that comb shape POEGMA promotes significantly higher cellular uptake and exhibits less steric hindrance imposed on the conjugated biomolecule than PEG. Collectively, comb-shape POEGMA offers a versatile alternative to PEG for stealth polymer-biomolecule conjugation applications.