Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 17Citation - Scopus: 19Strong Coupling of Carbon Quantum Dots in Liquid Crystals(American Chemical Society, 2022) Sarısözen, Sema; Polat, Nahit; Mert Balcı, Fadime; Güvenç, Çetin Meriç; Kocabaş, Çoşkun; Yağlıoğlu, Halime Gül; Balcı, SinanCarbon quantum dots (CDs) have recently received a tremendous amount of interest owing to their attractive optical properties. However, CDs have broad absorption and emission spectra limiting their application ranges. We herein, for the first time, show synthesis of water-soluble red emissive CDs with a very narrow line width (∼75 meV) spectral absorbance and hence demonstrate strong coupling of CDs and plasmon polaritons in liquid crystalline mesophases. The excited state dynamics of CDs has been studied by ultrafast transient absorption spectroscopy, and CDs display very stable and strong photoluminescence emission with a quantum yield of 35.4% and a lifetime of ∼2 ns. More importantly, we compare J-aggregate dyes with CDs in terms of their absorption line width, photostability, and ability to do strong coupling, and we conclude that highly fluorescent CDs have a bright future in the mixed light-matter states for emerging applications in future quantum technologies.Article Citation - WoS: 35Citation - Scopus: 36Understanding Radiative Transitions and Relaxation Pathways in Plexcitons(Cell Press, 2021) Finkelstein-Shapiro, Daniel; Mante, Pierre-Adrien; Sarısözen, Sema; Wittenbecher, Lukas; Minda, Iulia; Balcı, Sinan; Pullerits, TonuMolecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.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: 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: 43Citation - Scopus: 46Glucuronoxylan-Based Quince Seed Hydrogel: a Promising Scaffold for Tissue Engineering Applications(Elsevier, 2021) Güzelgülgen, Meltem; Özkendir İnanç, Dilce; Yıldız, Ümit Hakan; Arslan Yıldız, AhuNatural gums and mucilages from plant-derived polysaccharides are potential candidates for a tissue-engineering scaffold by their ability of gelation and biocompatibility. Herein, we utilized Glucuron-oxylanbased quince seed hydrogel (QSH) as a scaffold for tissue engineering applications. Optimization of QSH gelation was conducted by varying QSH and crosslinker glutaraldehyde (GTA) concentrations. Structural characterization of QSH was done by Fourier Transform Infrared Spectroscopy (MR). Furthermore, morphological and mechanical investigation of QSH was performed by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). The protein adsorption test revealed the suitability of QSH for cell attachment. Biocompatibility of QSH was confirmed by culturing NIH-3T3 mouse fibroblast cells on it. Cell viability and proliferation results revealed that optimum parameters for cell viability were 2 mg mi(-1)of QSH and 0.03 M GTA. SEM and DAPI staining results indicated the formation of spheroids with a diameter of approximately 300 pm. Furthermore, formation of extracellular matrix (ECM) microenvironment was confirmed with the Collagen Type-I staining. Here, it was demonstrated that the fabricated QSH is a promising scaffold for 3D cell culture and tissue engineering applications provided by its highly porous structure, remarkable swelling capacity and high biocompatibility. (C) 2021 Published by Elsevier B.V.Article Citation - WoS: 5Citation - Scopus: 6Toward Single-Layer Janus Crystals: Off-Balance Materials From Synthesis To Nanotechnology Applications(American Institute of Physics, 2021) Oğuztürk, H. Esra; Sözen, Yiğit; Akyol, Cansu; Özkendir İnanç, Dilce; Yıldız, Ümit Hakan; Şahin, HasanThe existence of things is directly related to their structural symmetry in a broad framework ranging from atoms to crystalline materials and from simple cells to complex organisms like humans. However, structural imbalance that occurs through natural or artificial means can provide completely different advantages. Molecules, crystals, and complex structures with structural imbalance constitute the family of Janus-type materials. This perspective provides a comprehensive discussion on the synthesis techniques of Janus-type materials, their use in fields from biology to materials science, and very recent studies on the family of 2D ultrathin graphene-like structures. We believe that, thanks to the advances in experimental techniques, the few-atom-sized off-balanced materials will be indispensable parts of the nanotechnology products that soon will be used in our daily lives.Article Citation - WoS: 25Citation - Scopus: 25Colloidal Bimetallic Nanorings for Strong Plasmon Exciton Coupling(American Chemical Society, 2020) Güvenç, Çetin Meriç; Mert Balcı, Fadime; Sarısözen, Sema; Polat, Nahit; Balcı, SinanNobel-metal nanostructures strongly localize and manipulate light at nanoscale dimension by supporting surface plasmon polaritons. In fact, the optical properties of the nobel-metal nanostructures strongly depend on their morphology and composition. Until now, various metal nanostructures such as nanocubes, nanoprisms, nanorods, and recently hollow nanostructures have been demonstrated. In addition, the plasmonic field can be further enhanced at nanoparticle dimers and aggregates because of highly localized and intense optical fields, which is known as "plasmonic hot spots". However, colloidally synthesized and circular-shaped nanoring nanostructures with plasmonic hot spots are still lacking. We, herein, show for the first time that colloidal bimetallic nanorings with plasmonic nanocavities and tunable plasmon resonance wavelengths can be synthesized via colloidal synthesis and galvanic replacement reactions. In addition, in the strong coupling regime, plasmons in nanorings and excitons in J-aggregates interact strongly and nanoring-shaped colloidal plexcitonic nanoparticles are demonstrated. The results reveal that the optical properties of the nanoring and the onset of strong coupling can be tamed by the galvanic replacement reaction. Further, the plasmonic nanocavity in the nanorings has immense potential for applications in sensing and spectroscopy because of the space, enclosed by the plasmonic nanocavity, is empty and accessible to a variety of molecules, ions, and quantum dots.Article Citation - WoS: 7Citation - Scopus: 7Fabrication of a Postfunctionalizable, Biorepellent, Electroactive Polyurethane Interface on a Gold Surface by Surface-Assisted Polymerization(American Chemical Society, 2020) Özenler, Sezer; Sözen, Yiğit; Şahin, Hasan; Yıldız, Ümit HakanThis study describes surface-assisted (SurfAst) urethane polymerization, providing a modular/postfunctionalizable, biorepellent, electroactive similar to 10 to 100 nm-thick polyurethane (PU) interface on a gold surface. SurfAst is a functionalization methodology based on sequential incubation steps of alkane diisocyanates and alkanediol monomers. The gold surface is functionalized by alkane diisocyanates in the first incubation step, and our theoretical calculations reveal that while the isocyanate group atoms (N, C, and O) at one end of the molecule exhibits strong interactions (similar to 900 meV) with surface atoms, the other end group remains unreacted. After the first incubation step, sequential alkanediol and alkane diisocyanate incubations provide formation of the PU interface. The extensive analysis of the PU interface has been conducted via X-ray photoelectron spectroscopy, and the chemical mapping verifies that the interface is made of PU moieties. The topographical analysis of the surface conducted by the atomic force microscopy shows that the PU interface consists of mostly a nanoporous texture with 150 nm total roughness. The adherence force mapping of the PU interface reveals that the nanoporous matrix exhibits an adhesion force of about 14 nN. The electrostatic force microscopy characterizing long-range electrostatic interactions (40 nm) shows that the PU interface has been attracted by positively charged species as compared to negative objects. Finally, it is demonstrated that the PU interface is readily postfunctionalizable by polyethylene glycol (PEG 1000), serving as a biorepellent interface and preserving electroactivity. We foresee that SurfAst polymerization will have potential for the facile fabrication of a postfunctionalizable and modular biointerface which might be utilized for biosensing and bioelectronic applications.