Browsing by Subject "Alcohols"
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Item Open Access Comparative analysis of reactant and product adsorption energies in the selective oxidative coupling of alcohols to esters on Au (111)(Springer, 2016) Şenozan, S.; Ustunel, H.; Karatok, M.; Vovk, E. I.; Shah, A. A.; Ozensoy, E.; Toffoli, D.Gold-based heterogeneous catalysts have attracted significant attention due to their selective partial oxidation capabilities, providing promising alternatives for the traditional industrial homogeneous catalysts. In the current study, the energetics of adsorption/desorption of alcohols (CH3OH/methanol, CH3CH2OH/ethanol, CH3CH2CH2OH/n-propanol) and esters (HCOOCH3/methyl formate, CH3COOCH3/methyl acetate, and CH3COOCH2CH3/ethyl acetate) on a planar Au(111) surface was investigated in conjunction with oxidative coupling reactions by means of temperature programmed desorption (TPD) and dispersion-corrected density functional theory (DFT) calculations. The results reveal a complex interplay between inter-molecular and surface-molecule interactions, both mediated by weak van der Waals forces, which dictates their relative stability on the gold surface. Both experimental and theoretical adsorption/desorption energies of the investigated esters are lower than those of the alcohols from which they originate through oxidative coupling reactions. This result can be interpreted as an important indication in favor of the selectivity of Au surfaces in alcohol oxidative coupling/partial oxidation reactions, allowing facile removal of partial oxidation products immediately after their generation preventing their complete oxidation to higher oxygenates.Item Open Access Electrospinning of cyclodextrin/linalool-inclusion complex nanofibers: fast-dissolving nanofibrous web with prolonged release and antibacterial activity(Elsevier, 2017-09) Aytac Z.; Yildiz, Z. I.; Kayaci-Senirmak, F.; Tekinay, T.; Uyar, TamerThe volatility and limited water solubility of linalool is a critical issue to be solved. Here, we demonstrated the electrospinning of polymer-free nanofibrous webs of cyclodextrin/linalool-inclusion complex (CD/linalool-IC-NFs). Three types of modified cyclodextrin (HPβCD, MβCD, and HPγCD) were used to electrospin CD/linalool-IC-NFs. Free-standing CD/linalool-IC-NFs facilitate maximum loading of linalool up to 12% (w/w). A significant amount of linalool (45–89%) was preserved in CD/linalool-IC-NFs, due to enhancement in the thermal stability of linalool by cyclodextrin inclusion complexation. Remarkably, CD/linalool-IC-NFs have shown fast-dissolving characteristics in which these nanofibrous webs dissolved in water within two seconds. Furthermore, linalool release from CD/linalool-IC-NFs inhibited growth of model Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria to a great extent. Briefly, characteristics of liquid linalool have been preserved in a solid nanofiber form and designed CD/linalool-IC-NFs confer high loading capacity, enhanced shelf life and strong antibacterial activity of linalool.Item Open Access Novel size-tunable and straightforward ultra-small nanoparticle synthesis in a varying concentration range of glycerol as a green reducing solvent(American Chemical Society, 2023-08-08) Munir, Iqra; Yeşilöz, GürkanDespite all the possibilities available so far for the synthesis of nanoparticles (NPs), synthesizing ultra-small (<10 nm) monodispersed particles is still demanding. Getting a particular size with a straightforward method is a trial-and-error approach. To explore this prospective, in the current study, we have introduced a protocol which offers a varying concentration range of glycerol to successfully generate the NPs of repeatable and consistent particle size in each synthesis, thus giving an alternative from lengthy tentative preparations and/or testing protocols. Since synthesizing controlled sized nanoparticles in aqueous medium is somewhat difficult as the balance of particle growth and nucleation is challenging to control, herein, we used a polyol method with glycerol both as a solvent medium as well as reducing species for silver nitrate, as an example model ion source, to execute the nanoparticle synthesis. In order to maintain the stability of the synthesized NPs, polyvinylpyrolidone (PVP) was added as a stabilizer. The synthesis, monodispersity, and stability were confirmed using techniques such as UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), and X-ray powder diffraction (XRD), while morphological analysis and ultra-small size validation were conducted using TEM, SEM, and AFM. Interestingly, in the various concentrations of glycerol solution used (10–100%), we have observed a tunable linear size range to obtain ultra-small nanoparticles (<10 nm) up to 60% glycerol, while further increasing the glycerol component increased the size approximately to ∼160 nm, providing tunable properties in this synthesis procedure. Hence, this study provides a distinct possibility to obtain ultra-small nanoparticles with a tunable size feature for further applications in numerous fields.Item Open Access Rapid access to hydroxyfluoranthenes via a domino Suzuki–Miyaura/intramolecular Diels–Alder/ring-opening reactions sequence(American Chemical Society, 2022-04-07) Ahmadli, Dilgam; Şahin, Yeşim; Çalıkyılmaz, Eylül; Şahin, Onur; Türkmen, Yunus E.In this work, we developed an efficient method for the rapid construction of fluoranthene skeleton to access a variety of substituted hydroxyfluoranthenes. The 1-iodo-8-alkynylnaphthalene derivatives, which serve as substrates for the key fluoranthene-forming step, were prepared via selective monoalkynylative Sonogashira reactions of 1,8-diiodonaphthalene. The domino reaction sequence which involves a sequential Suzuki–Miyaura coupling, an intramolecular Diels–Alder reaction, and an aromatization-driven ring-opening isomerization has been shown to give substituted hydroxyfluoranthenes in up to 92% yield. This work demonstrates the utility of designing new domino reactions for rapid access to substituted polycyclic aromatic hydrocarbons (PAHs).