Browsing by Subject "Surface chemistry"
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Item Open Access Precious metal-Free LaMnO3 perovskite catalyst with an optimized nanostructure for aerobic C–H bond activation reactions: alkylarene oxidation and naphthol dimerization(American Chemical Society, 2021-02-03) Şahin, Yeşim; Sika-Nartey, Abel Tetteh; Ercan, Kerem Emre; Koçak, Yusuf; Senol, Sinem; Özensoy, Emrah; Türkmen, Yunus EmreIn this article, we describe the development of a new aerobic C–H oxidation methodology catalyzed by a precious metal-free LaMnO3 perovskite catalyst. Molecular oxygen is used as the sole oxidant in this approach, obviating the need for other expensive and/or environmentally hazardous stoichiometric oxidants. The electronic and structural properties of the LaMnO3 catalysts were systematically optimized, and a reductive pretreatment protocol was proved to be essential for acquiring the observed high catalytic activities. It is demonstrated that this newly developed method was extremely effective for the oxidation of alkylarenes to ketones as well as for the oxidative dimerization of 2-naphthol to 1,1-binaphthyl-2,2-diol (BINOL), a particularly important scaffold for asymmetric catalysis. Detailed spectroscopic and mechanistic studies provided valuable insights into the structural aspects of the active catalyst and the reaction mechanism.Item Open Access Robust superhydrophilic patterning of superhydrophobic ormosil surfaces for high-throughput on-chip screening applications(Royal Society of Chemistry, 2016) Beyazkilic, P.; Tuvshindorj, U.; Yildirim, A.; Elbuken, C.; Bayındır, MehmetThis article describes a facile method for the preparation of two-dimensionally patterned superhydrophobic hybrid coatings with controlled wettability. Superhydrophobic coatings were deposited from nanostructured organically modified silica (ormosil) colloids that were synthesized via a simple sol-gel method. On the defined areas of the superhydrophobic ormosil coatings, stable wetted micropatterns were produced using Ultraviolet/Ozone (UV/O) treatment which modifies the surface chemistry from hydrophobic to hydrophilic without changing the surface morphology. The degree of wettability can be precisely controlled depending on the UV/O exposure duration; extremely wetted spots with water contact angle (WCA) of nearly 0° can be obtained. Furthermore, we demonstrated high-throughput biomolecular adsorption and mixing using the superhydrophilic patterns. The proposed superhydrophilic-patterned nanostructured ormosil surfaces with their simple preparation, robust and controlled wettability as well as adaptability on flexible substrates, hold great potential for biomedical and chemical on-chip analysis.Item Open Access The role of ligand rebinding and facilitated dissociation on the characterization of dissociation rates by surface plasmon resonance (SPR) and benchmarking performance metrics(Springer, 2022) Erbaş, Aykut; İnci, Fatih; Vanhaelen, QuentinSurface plasmon resonance (SPR) is a real-time kinetic measurement principle that can probe the kinetic interactions between ligands and their binding sites, and lies at the backbone of pharmaceutical, biosensing, and biomolecular research. The extraction of dissociation rates from SPR-response signals often relies on several commonly adopted assumptions, one of which is the exponential decay of the dissociation part of the response signal. However, certain conditions, such as high density of binding sites or high concentration fluctuations near the surface as compared to the bulk, can lead to non-exponential decays via ligand rebinding or facilitated dissociation. Consequently, fitting the data with an exponential function can underestimate or overestimate the measured dissociation rates. Here, we describe a set of alternative fit functions that can take such effects into consideration along with plasmonic sensor design principles with key performance metrics, thereby suggesting methods for error-free high-precision extraction of the dissociation rates.Item Open Access Simulation of water drops on a surface(IEEE, 2008-05) Algan, Eren; Kabak, Mustafa; Özgüç, Bülent; Çapin, TolgaWe have designed and implemented a model for rendering and animating water drops moving on a surface under physical effects such as gravity, surface affinity and wind. For improved rendering, the output of the simulation (i.e. the animation sequence of the drops) is recorded for later offline image generation. ©2008 IEEE.Item Open Access Spectroscopic investigation of nitrate-metal and metal-surfactant interactions in the solid AgNO3/C12EO10 and liquid-crystalline [M(H2O)n](NO3)2/C12EO10 systems(American Chemical Society, 2003) Dag, Ö.; Samarskaya, O.; Tura, C.; Günay, A.; Çelik, Ö.Interactions of the nitrate ions in various metal nitrate salts with CnH2n-1(CH2CH2O)mOH (CnEOm)-type nonionic surfactants have been investigated both in the solid and in the liquid-crystalline (LC) systems. In the ternary system, the mixture of salt/water/CnEOm has a mesophase up to a certain concentration of salt, and the nitrate ions in this phase are usually in a free-ion form. However, upon the evaporation of the water phase, the nitrate ion interacts with the metal center and coordinates as either a bidentate or unidentate ligand. It is this interaction that makes the AgNO3 ternary system undergo a phase separation by releasing solid Ag(CnEOm)xNO3 complex crystals. In contrast, the salt/surfactant systems maintain their stable LC phases for months. Note also that the salt/surfactant systems consist of transition-metal aqua complexes in which the coordinated water molecules play a significant role in the self-assembly and organization of the nonionic surfactant molecules into an LC mesophase. Throughout this work, Fourier transform infrared spectroscopy has been extensively used to investigate the interactions of the nitrate ions with a metal center and the metal ions with the surfactant molecules. Polarized optical microscopy and X-ray diffraction techniques have been applied to investigate the nature of the crystalline and LC phases.Item Open Access Weakly hydrated anions bind to polymers but not monomers in aqueous solutions(Nature Publishing Group, 2021-11-01) Rogers, B. A.; Okur, Halil İbrahim; Yan, C.; Yang, T.; Heyda, J.; Cremer, P. S.Weakly hydrated anions help to solubilize hydrophobic macromolecules in aqueous solutions, but small molecules comprising the same chemical constituents precipitate out when exposed to these ions. Here, this apparent contradiction is resolved by systematically investigating the interactions of NaSCN with polyethylene oxide oligomers and polymers of varying molecular weight. A combination of spectroscopic and computational results reveals that SCN− accumulates near the surface of polymers, but is excluded from monomers. This occurs because SCN− preferentially binds to the centre of macromolecular chains, where the local water hydrogen-bonding network is disrupted. These findings suggest a link between ion-specific effects and theories addressing how hydrophobic hydration is modulated by the size and shape of a hydrophobic entity.