PubMed İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/397
Browse
9 results
Search Results
Article Citation - WoS: 28Citation - Scopus: 29Three-Dimensional Au-Coated Electrosprayed Nanostructured BODIPY Films on Aluminum Foil as Surface-Enhanced Raman Scattering Platforms and Their Catalytic Applications(Amer Chemical Soc, 2017-05-16) Yilmaz, Mehmet; Erkartal, Mustafa; Ozdemir, Mehmet; Sen, Unal; Usta, Hakan; Demirel, GokhanThe design and development of three-dimensional (3D) nanostructures with high surface-enhanced Raman scattering (SERS) performances have attracted considerable attention in the fields of chemistry, biology, and materials science. Nevertheless, electrospraying of organic smalt molecules on low-cost flexible substrates has never been studied to realize large-scale SERS-active platforms. Here, we report the facile, efficient, and low-cost fabrication of-Stable and reproducible Au-coated electrosprayed organic semiconductor films (Au@BDY-4TEBDY) on flexible regular aluminum foil at a large scale (5 cm X 5 cm) for practical SERS and catalytic applications. To this end, a well-designed-acceptor-donor-atceptor-type solution-processable molecular semiconductor, BDY-4T-BDY, developed by our group, is used because of its advantageous structural and electrical properties. The morphology of the electrosprayed organic film changes by solution concentration, and two different 3D morphologies with out-of-plane features are obtained. Highly uniform dendritic nanoribbons with sharp needle-like tips and vertically oriented nanoplates (similar to 50 nm thickness) are achieved when electrospraying solution concentrations of 240 and 253% w/v.(mgimL) are, respectively, used. When these electrosprayed organic films are coated with a nanoscopic thin (30 nm) Au layer, the resulting Au@BDY-4T-BDY platforms demonstrate remarkable SERS enhancement factors up to 1.7 X 10(6) with excellent Raman signal reproducibility (relative standard deviation <= 0.13) for methylene blue over the entire film. Finally, Au@BDY-4T-BDY films showed good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with rate constants of 1.3 X 10(-2) and 9.2 X 10(-3) min(-1). Our results suggest that electrospraying of rationally designed organic semiconductor molecules on flexible substrates holds great promise to enable low-cost, solution-processed, SERS-active platforms.Article Citation - WoS: 22Citation - Scopus: 24The Design and Fabrication of Supramolecular Semiconductor Nanowires Formed by Benzothienobenzothiophene (BTBT)-Conjugated Peptides(Royal Soc Chemistry, 2018) Khalily, Mohammad Aref; Usta, Hakan; Ozdemir, Mehmet; Bakan, Gokhan; Dikecoglu, F. Begum; Edwards-Gayle, Charlotte; Guler, Mustafa O.pi-Conjugated small molecules based on a [1]benzothieno[3,2-b]benzothiophene (BTBT) unit are of great research interest in the development of solution-processable semiconducting materials owing to their excellent charge-transport characteristics. However, the BTBT -core has yet to be demonstrated in the form of electro-active one-dimensional (1D) nanowires that are self-assembled in aqueous media for potential use in bioelectronics and tissue engineering. Here we report the design, synthesis, and self-assembly of benzothienobenzothiophene (BTBT)-peptide conjugates, the BTBT-peptide (BTBT-C-3-COHN-Ahx-VVAGKK-Am) and the C-8-BTBT-peptide (C-8-BTBT-C-3-COHN-Ahx-VVAGKK-Am), as -sheet forming amphiphilic molecules, which self-assemble into highly uniform nanofibers in water with diameters of 11-13(+/- 1) nm and micron-size lengths. Spectroscopic characterization studies demonstrate the J-type - interactions among the BTBT molecules within the hydrophobic core of the self-assembled nanofibers yielding an electrical conductivity as high as 6.0 x 10(-6) S cm(-1). The BTBT -core is demonstrated, for the first time, in the formation of self-assembled peptide 1D nanostructures in aqueous media for potential use in tissue engineering, bioelectronics and (opto)electronics. The conductivity achieved here is one of the highest reported to date in a non-doped state.Article Citation - WoS: 1Citation - Scopus: 1Stochastic Orientational Encoding via Hydrogen Bonding Driven Assembly of Woven-Like Molecular Physically Unclonable Functions(Wiley-VCH Verlag GmbH, 2025-07-02) Kayaci, Nilgun; Kiremitler, Nuri Burak; Deneme, Ibrahim; Kalay, Mustafa; Ozbasaran, Aleyna; Zorlu, Yunus; Usta, HakanThe prevention of counterfeiting and the assurance of object authenticity require stochastic encoding schemes based on physically unclonable functions (PUFs). There is an urgent need for exceptionally large encoding capacities and multi-level responses within a molecularly defined, single-material system. Herein, a novel stochastic orientational encoding approach is demonstrated using a facile ambient-atmosphere solution processing of a molecular thin film based on the rod-shaped oligo(p-phenyleneethynylene) (OPE) pi-architecture. The nanoscopic film, derived from the small molecule 2EHO-CF3PyPE with donor, acceptor, and pi-spacer building units, is designed for energetically favorable uniaxial molecular assembly and crystal growth via directional multiple hydrogen-bonding motifs at the molecular termini and short C & horbar;H<middle dot><middle dot><middle dot>pi contacts at the center. A facile solvent vapor annealing induces concurrent dewetting and microscopic 1D random crystallization, yielding a woven-textured random features. Using convolutional neural networks, the rich variations in microcrystal domain properties and stochastic encoding of 1D crystal orientations generate artificial coloration, achieving an encoding capacity reaching (6.5 x 10(4))(2752 x 2208). The results demonstrate an effective strategy for achieving ultrahigh encoding capacities in a thin film composed of a single-material. This approach enables low-cost, solution-processed fabrication for mass production and broad adoption, while opening new opportunities to explore molecular-PUFs through structural design and engineering noncovalent interactions.Article Citation - WoS: 61Citation - Scopus: 74Solution-Processable Bodipy-Based Small Molecules for Semiconducting Microfibers in Organic Thin-Film Transistors(Amer Chemical Soc, 2016-05-23) Ozdemir, Mehmet; Choi, Donghee; Kwon, Guhyun; Zorlu, Yunus; Cosut, Bunyemin; Kim, Hyekyoung; Usta, HakanElectron-deficient pi-conjugated small molecules can function as electron-transporting semiconductors in various optoelectronic applications. Despite their unique structural, optical, and electronic properties, the development of BODIPY-based organic semiconductors has lagged behind that of other pi-deficient units. Here, we report the design and synthesis of two novel solution-proccessable BODIPY-based small molecules (BDY-3T-BDY and BDY-4T-BDY) for organic thin-film transistors (OTFTs). The new semiconductors were fully characterized by H-1/C-13 NMR, mass spectrometry, cyclic voltammetry, UV-vis spectroscopy, photoluminescence, differential scanning calorimetry, and thermogravimetric analysis. The single-crystal X-ray diffraction (XRD) characterization of a key intermediate reveals crucial structural properties. Solution-sheared top-contact/bottom-gate OTFTs exhibited electron mobilities up to 0.01 cm(2)/V center dot s and current on/off ratios of >10(8). Film microstructural and morphological characterizations indicate the formation of relatively long (similar to 0.1 mm) and micrometer-sized (1-2 mu m) crystalline fibers for BDY-4T-BDY-based films along the shearing direction. Fiber-alignment-induced charge-transport anisotropy (mu?/mu approximate to 10) was observed, and higher mobilities were achieved when the microfibers were aligned along the conduction channel, which allows for efficient long-range charge-transport between source and drain electrodes. These OTFT performances are the highest reported to date for a BODIPY-based molecular semiconductor, and demonstrate that BODIPY is a promising building block for enabling solution-processed, electron-transporting semiconductor films.Article Citation - WoS: 11Citation - Scopus: 13Solution-Processable Indenofluorenes on Polymer Brush Interlayer: Remarkable N-Channel Field-Effect Transistor Characteristics Under Ambient Conditions(Amer Chemical Soc, 2023-08-15) Can, Ayse; Deneme, Ibrahim; Demirel, Gokhan; Usta, HakanThe development of solution-processable n-type molecularsemiconductorsthat exhibit high electron mobility (& mu;(e) & GE;0.5 cm(2)/(V & BULL;s)) under ambient conditions, along withhigh current modulation (I (on)/I (off) & GE; 10(6)-10(7)) andnear-zero turn on voltage (V (on)) characteristics,has lagged behind that of other semiconductors in organic field-effecttransistors (OFETs). Here, we report the design, synthesis, physicochemicaland optoelectronic characterizations, and OFET performances of a libraryof solution-processable, low-LUMO (-4.20 eV) 2,2 & PRIME;-(2,8-bis(3-alkylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile small molecules, & beta;,& beta;& PRIME;-C (n) -TIFDMTs, having varied alkyl chain lengths (n = 8, 12, 16). An intriguing correlation is identifiedbetween the solid-isotropic liquid transition enthalpies andthe solubilities, indicating that cohesive energetics, which are tunedby alkyl chains, play a pivotal role in determining solubility. Thesemiconductors were spin-coated under ambient conditions on denselypacked (grafting densities of 0.19-0.45 chains/nm(2)) ultrathin (& SIM;3.6-6.6 nm) polystyrene-brush surfaces.It is demonstrated that, on this polymer interlayer, thermally induceddispersive interactions occurring over a large number of methyleneunits between flexible alkyl chains (i.e., zipper effect) are criticalto achieve a favorable thin-film crystallization with a proper microstructureand morphology for efficient charge transport. While C-8 and C-16 chains show a minimal zipper effect upon thermalannealing, C-12 chains undergo an extended interdigitationinvolving & SIM;6 methylene units. This results in the formationof large crystallites having lamellar stacking ((100) coherence length & SIM;30 nm) in the out-of-plane direction and highly favorablein-plane & pi;-interactions in a slipped-stacked arrangement. Uninterruptedmicrostructural integrity (i.e., no face-on (010)-oriented crystallites)was found to be critical to achieving high mobilities. The excellentcrystallinity of the C-12-substituted semiconductor thinfilm was also evident in the observed crystal lattice vibrations (phonons)at 58 cm(-1) in low-frequency Raman scattering. Two-dimensionalmicrometer-sized (& SIM;1-3 & mu;m), sharp-edged plate-likegrains lying parallel with the substrate plane were observed. OFETsfabricated by the current small molecules showed excellent n-channelbehavior in ambient with & mu;(e) values reaching & SIM;0.9cm(2)/(V & BULL;s), I (on)/I (off) & SIM; 10(7)-10(8), and V (on) & AP; 0 V. Our study notonly demonstrates one of the highest performing n-channel OFET devicesreported under ambient conditions via solution processing but alsoelucidates significant relationships among chemical structures, molecularproperties, self-assembly from solution into a thin film, and semiconductingthin-film properties. The design rationales presented herein may openup new avenues for the development of high-electron-mobility novelelectron-deficient indenofluorene and short-axis substituted donor-acceptor & pi;-architectures via alkyl chain engineering and interface engineering.Article Citation - WoS: 36Citation - Scopus: 36Selective Remanent Ambipolar Charge Transport in Polymeric Field-Effect Transistors for High-Performance Logic Circuits Fabricated in Ambient(Wiley-VCH Verlag GmbH, 2014-10-06) Fabiano, Simone; Usta, Hakan; Forchheimer, Robert; Crispin, Xavier; Facchetti, Antonio; Berggren, MagnusArticle Citation - WoS: 124Citation - Scopus: 127Molecular Engineering of Organic Semiconductors Enables Noble Metal-Comparable SERS Enhancement and Sensitivity(Nature Publishing Group, 2019-12-03) Demirel, Gokhan; Gieseking, Rebecca L. M.; Ozdemir, Resul; Kahmann, Simon; Loi, Maria A.; Schatz, George C.; Usta, HakanNanostructured molecular semiconductor films are promising Surface-Enhanced Raman Spectroscopy (SERS) platforms for both fundamental and technological research. Here, we report that a nanostructured film of the small molecule DFP-4T, consisting of a fully pi-conjugated diperfluorophenyl-substituted quaterthiophene structure, demonstrates a very large Raman enhancement factor (>10(5)) and a low limit of detection (10(-9) M) for the methylene blue probe molecule. This data is comparable to those reported for the best inorganic semiconductor- and even intrinsic plasmonic metal-based SERS platforms. Photoluminescence spectroscopy and computational analysis suggest that both charge-transfer energy and effective molecular interactions, leading to a small but non-zero oscillator strength in the charge-transfer state between the organic semiconductor film and the analyte molecule, are required to achieve large SERS enhancement factors and high molecular sensitivities in these systems. Our results provide not only a considerable experimental advancement in organic SERS figure-of-merits but also a guidance for the molecular design of more sensitive SERS systems.Article Citation - WoS: 63Citation - Scopus: 63Highly Efficient Deep-Blue Electroluminescence Based on a Solution-Processable A-Π Oligo(p-Phenyleneethynylene) Small Molecule(Amer Chemical Soc, 2019-10-14) Usta, Hakan; Alimli, Dilek; Ozdemir, Resul; Dabak, Salih; Zorlu, Yunus; Alkan, Fahri; Can, AyseThe development of solution-processable fluorescent small molecules with highly efficient deep-blue electroluminescence is of growing interest for organic light-emitting diode (OLED) applications. However, high-performance deep-blue fluorescent emitters with external quantum efficiencies (EQEs) over 5% are still scarce in OLEDs. Herein, a novel highly soluble oligo(p-phenyleneethynylene)-based small molecule, 1,4-bis((2-cyanophenyl)ethynyl)-2,5-bis(2-ethylhexyloxy)benzene (2EHO-CNPE), is designed, synthesized, and fully characterized as a wide band gap (2.98 eV) and highly fluorescent (Phi(PL) = 0.90 (solution) and 0.51 (solid-state)) deep-blue emitter. The new molecule is functionalized with cyano (-CN)/2-ethylhexyloxy (-OCH2CH(C2H5)C4H9) electron-withdrawing/-donating substituents, and ethynylene is used as a pi-spacer to form an acceptor (A)-pi-donor (D)-pi-acceptor (A) molecular architecture with hybridized local and charge transfer (HLCT) excited states. Physicochemical and optoelectronic characterizations of the new emitter were performed in detail, and the single-crystal structure was determined. The new molecule adopts a nearly coplanar pi-conjugated framework packed via intermolecular "C-H center dot center dot center dot pi" and "C-H center dot center dot center dot N" hydrogen bonding interactions without any pi-pi stacking. The OLED device based on 2EHO-CNPE shows an EQE(max) of 7.06% (EQE = 6.30% at 200 cd/m(2)) and a maximum current efficiency (CEmax) of 5.91 cd/A (CE = 5.34 cd/A at 200 cd/m(2)) with a deep-blue emission at CIE of (0.15, 0.09). The electroluminescence performances achieved here are among the highest reported to date for a solution-processed deep-blue fluorescent small molecule, and, to the best of our knowledge, it is the first time that a deep-blue OLED is reported based on the oligo(p-phenyleneethynylene) pi-framework. TDDFT calculations point to facile reverse intersystem crossing (RISC) processes in 2EHO-CNPE from high-lying triplet states to the first singlet excited state (T-2/T-3 -> S-1) (hot-exciton channels) that enable a high radiative exciton yield (eta(r) similar to 69%) breaking the theoretical limit of 25% in conventional fluorescent OLEDs. These results demonstrate that properly designed fluorescent oligo(p-phenyleneethynylenes) can be a key player in high-performance deep-blue OLEDs.Article Citation - WoS: 47Citation - Scopus: 45Enabling Three-Dimensional Porous Architectures via Carbonyl Functionalization and Molecular-Specific Organic-SERS Platforms(Nature Portfolio, 2021-10-21) Deneme, Ibrahim; Liman, Gorkem; Can, Ayse; Demirel, Gokhan; Usta, HakanNanostructured films of organic semiconductors with low lying LUMO orbitals can enhance Raman signals via a chemical enhancement mechanism but currently the material choice is limited to fluorinated oligothiophenes. Here, the authors investigate the growth of a porous thienoacene film enabled by carbonyls and demonstrate molecular specific organic-SERS platforms. Molecular engineering via functionalization has been a great tool to tune noncovalent intermolecular interactions. Herein, we demonstrate three-dimensional highly crystalline nanostructured D(C7CO)-BTBT films via carbonyl-functionalization of a fused thienoacene pi-system, and strong Raman signal enhancements in Surface-Enhanced Raman Spectroscopy (SERS) are realized. The small molecule could be prepared on the gram scale with a facile synthesis-purification. In the engineered films, polar functionalization induces favorable out-of-plane crystal growth via zigzag motif of dipolar C = O center dot center dot center dot C = O interactions and hydrogen bonds, and strengthens pi-interactions. A unique two-stage film growth behavior is identified with an edge-on-to-face-on molecular orientation transition driven by hydrophobicity. The analysis of the electronic structures and the ratio of the anti-Stokes/Stokes SERS signals suggests that the pi-extended/stabilized LUMOs with varied crystalline face-on orientations provide the key properties in the chemical enhancement mechanism. A molecule-specific Raman signal enhancement is also demonstrated on a high-LUMO organic platform. Our results demonstrate a promising guidance towards realizing low-cost SERS-active semiconducting materials, increasing structural versatility of organic-SERS platforms, and advancing molecule-specific sensing via molecular engineering.