Browsing by Author "Topuz, F."

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Open Access
Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons
(Academic Press Inc., 2017) Topuz, F.; Uyar, T.
Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitous environmental contaminants, and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65 mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon.
Open Access
Electrospinning of gelatin with tunable fiber morphology from round to flat/ribbon
(Elsevier, 2017) Topuz, F.; Uyar, T.
The electrospinning of gelatin with tunable fiber morphology from round to flat/ribbon was shown, and the detailed studies were conducted to correlate the fiber morphology with electrospinning process parameters and gelatin concentration in electrospinning solution. Particularly, variations in the applied voltage and the concentration of gelatin led to the transition of fiber shape from round to flat/ribbon. The formation of flat-shaped fibers was attributed to rapid evaporation of the solvent (formic acid) from the fiber matrix with increasing the applied voltage and gelatin concentration. On the other hand, round fibers were due to the steady evaporation of formic acid throughout the cross-section of fibers. WAXS analysis revealed that the loss of triple-helical crystalline structure in gelatin after the electrospinning process. The gelatin fibers were cross-linked through treatment with toluene 2,4-diisocyanate (TDI) in a mixed solution of acetone and pyridine, and XPS confirmed the cross-linking of the fibers over an increased carbon content on the elemental composition of the fiber surface due to the incorporated TDI moieties. Overall, this study focuses on morphological tuning of gelatin electrospun fibers towards a flat/ribbon-like structure by variation of electrospinning parameters and polymer concentration, and thus, the proposed concept can be adapted towards flattened/ribbon-like fibers of other protein-based systems by electrospinning.
Open Access
Fast-dissolving antibacterial nanofibers of cyclodextrin/antibiotic inclusion complexes for oral drug delivery
(Elsevier, 2020) Topuz, F.; Kılıç, M. E.; Durgun, Engin
Hypothesis The widespread use of antibacterial electrospun nanofibers is mostly restricted due to their low loading capacity to carry antibiotics and the need to use toxic organic solvents to boost the antibiotic loading capacity. Nanofibers based on natural excipients, such as cyclodextrin (CD)-based nanofibers, can carry larger amounts of antibiotics while achieving better stability via inclusion complexation. Experiments Nanofibers were produced by electrospinning and analyzed by electron microscopy to investigate the morphology of fibers. The formation of inclusion-complexation was analyzed by 1H NMR, FTIR, and XRD. Thermal analysis of the fibers was done using TGA. Ab initio modeling studies were done to calculate the complexation energies of antibiotics with CD. A disk-diffusion assay was used to test the antibacterial activity of the fibers. Findings Bead-free antibacterial nanofibers with mean diameters between 340 and 550 nm were produced. The formation of inclusion complexes (IC) between the CD and the antibiotics was confirmed by FTIR and 1H NMR, which was further verified by the disappearance of the crystalline peaks of antibiotics as determined by XRD analysis. Thermal analysis of the nanofibers revealed that the formulations showed good antibiotic encapsulation (45–90%). Ab initio simulations revealed that gentamicin had the highest complexation energy, followed by kanamycin, chloramphenicol, and ampicillin. The antibacterial nanofibers rapidly dissolved in water and artificial saliva, successfully releasing the CD antibiotic complexes. The nanofibers showed high antibacterial activity against Gram-negative Escherichia coli.
Open Access
Influence of hydrogen-bonding additives on electrospinning of cyclodextrin nanofibers
(American Chemical Society, 2018) Topuz, F.; Uyar, Tamer
The electrospinning of highly concentrated solutions of cyclodextrin (CD) leads to bead-free nanofibers without the need of a polymeric carrier. The occurrence of numerous hydrogen bonds among CD molecules is the main driving force for their electrospinning, and hence, additives with hydrogen-bonding potential can disturb the aggregation of CD molecules and affect their electrospinning. In this study, we systematically investigated the influence of five different hydrogen-bonding additives, i.e., methylamine (MA), ethylenediamine (ED), urea, 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), on the solution behavior of hydroxypropyl-β-CD (HP-β-CD) by rheology, conductivity, and NMR analyses, and the morphology of the electrospun HP-β-CD nanofibers by scanning electron microscopy. The 1H NMR chemical shifts of the HP-β-CD protons in D2O were observed with the incorporation of hydrogen-bonding molecules due to the occurrence of intermolecular associations between HP-β-CD and additives. Dynamic light scattering measurements revealed a clear decrease in the aggregate size with the introduction of additives. Unlike other additives, which showed a general decreasing trend in viscosity with increasing additive content, the addition of MA led to a significant increase in the viscosity with increasing concentration and gave rise to HP-β-CD nanofibers at lower concentrations. The addition of low concentrations of ED, urea, TFE, and HFIP led to thinner nanofibers due to the lower viscosity of the respective solutions. Increasing additive content deteriorated the electrospinnability of HP-β-CD solutions, resulting in beaded fibers. A systematic relationship was found between the solution viscosity and morphology of the respective electrospun fibers. Overall, this study, for the first time, reports the influence of hydrogen bonding on the polymer-free electrospinning of CD molecules and shows a correlation between solution properties and morphology of their electrospun nanofibers.
Open Access
Nanoencapsulation of menthol/cyclodextrin inclusion complexes in rapidly dissolving electrospun gelatin nanofibers
(American Chemical Society, 2024-01-26) Yıldız, Zehra İrem; Topuz, F.; Aboelkheir, M.; Kılıç, Mehmet Emin; Durgun, Engin; Uyar, Tamer
Menthol, a minty phytochemical found in peppermint and spearmint plants, is used in various products. However, it may have poor stability, especially when exposed to factors such as light and heat. In this context, this study reports the nanoencapsulation of menthol in electrospun gelatin fibers to improve its stability and release. First, inclusion complexes (ICs) of menthol were prepared with α-, β-, and γ-cyclodextrins (CDs) and then mixed with gelatin and electrospun into nanofibers. The molecular modeling study showed the inclusion complexation between CDs and menthol. Scanning electron microscopy analysis revealed the formation of a bead-free morphology in gelatin/menthol CD IC fibers. Fourier transform infrared analysis confirmed the presence of menthol in the resulting nanofibers, while 1H nuclear magnetic resonance spectroscopy determined the menthol content in ICs, which varied between 54 and 100% depending on the CD type. Thermal analysis of the fibers revealed increased stability of menthol in the fibers, which dissolved quickly upon contact with water, suggesting their possible use as fast-dissolving dietary supplements.
Open Access
One-Step Fabrication of Biocompatible Multifaceted Nanocomposite Gels and Nanolayers
(American Chemical Society, 2017) Topuz, F.; Bartneck, M.; Pan, Y.; Tacke, F.
Nanocomposite gels are a fascinating class of polymeric materials with an integrative assembly of organic molecules and organic/inorganic nanoparticles, offering a unique hybrid network with synergistic properties. The mechanical properties of such networks are similar to those of natural tissues, which make them ideal biomaterial candidates for tissue engineering applications. Existing nanocomposite gel systems, however, lack many desirable gel properties, and their suitability for surface coatings is often limited. To address this issue, this article aims at generating multifunctional nanocomposite gels that are injectable with an appropriate time window, functional with bicyclononynes (BCN), biocompatible and slowly degradable, and possess high mechanical strength. Further, the in situ network-forming property of the proposed system allows the fabrication of ultrathin nanocomposite coatings in the submicrometer range with tunable wettability and roughness. Multifunctional nanocomposite gels were fabricated under cytocompatible conditions (pH 7.4 and T = 37 °C) using laponite clays, isocyanate (NCO)-terminated sP(EO-stat-PO) macromers, and clickable BCN. Several characterization techniques were employed to elucidate the structure-property relationships of the gels. Even though the NCO-sP(EO-stat-PO) macromers could form a hydrogel network in situ on contact with water, the incorporation of laponite led to significant improvement of the mechanical properties. BCN motifs with carbamate links were used for a metal-free click ligation with azide-functional molecules, and the subsequent gradual release of the tethered molecules through the hydrolysis of carbamate bonds was shown. The biocompatibility of the hydrogels was examined through murine macrophages, showing that the material composition strongly affects cell behavior.
Open Access
Pd nanocube decoration onto flexible nanofibrous mats of core-shell polymer-ZnO nanofibers for visible light photocatalysis
(Royal Society of Chemistry, 2017) Arslan, O.; Topuz, F.; Eren, H.; Bıyıklı, Necmi; Uyar, Tamer
Plasmonic enhancement for electron-hole separation efficiency and visible light photocatalysis was achieved by Pd nanocube decoration on a ZnO nanolayer coated onto electrospun polymeric (polyacrylonitrile (PAN)) nanofibers. Since exciton formation and sustainable electron-hole separation have a vital importance for realizing better solar energy in photovoltaic and photocatalytic devices, we achieved visible light photocatalysis by Pd nanocube decoration onto well designed core-shell nanofibers of ZnO@PAN-NF. By controlling the cubic Pd nanoparticle size and the thickness of the crystalline ZnO nanolayer deposited onto electrospun PAN nanofibers via atomic layer deposition (ALD), defect mediated visible light photocatalysis efficiency can be increased. By utilizing nanofabrication techniques such as thermal decomposition, electrospinning and ALD, this fabricated template became an efficient, defect mediated, Pd nanocube plasmon enhanced photocatalytic system. Due to the enhanced contact features of the Pd nanocubes, an increase was observed for the visible light photocatalytic activity of the flexible and nanofibrous mat of Pd@ZnO@PAN-NF.
Open Access
Poly-cyclodextrin cryogels with aligned porous structure for removal of polycyclic aromatic hydrocarbons (PAHs) from water
(Elsevier, 2017-08) Topuz, F.; Uyar, Tamer
Cyclodextrins (CDs) are sugar-based cyclic oligosaccharides, which form inclusion complexes with small guest molecules through their hydrophobic cavity. Here we successfully synthesized highly porous poly-cyclodextrin (poly-CD) cryogels, which were produced under cryogenic conditions by the cross-linking of amine-functional CDs with PEG-based diepoxide cross-linker. The poly-CD cryogels showed aligned porous network structures owing to the directional freezing of the matrix, of which the pore size and architecture exposed variations depending on the composition of the reactants. The cryogels were employed for the removal of genotoxic polycyclic aromatic hydrocarbons (PAHs) from aqueous solutions. They reached PAH sorption capacities as high as 1.25 mg PAH per gram cryogel. This high sorption performance is due to interactions between PAHs and the complete swollen network, and thus, is not restricted by interfacial adsorption. Given that the hydrophilic nature of the components, the sorption performance could only be attributed to the inclusion complex formation of CDs with PAH molecules. The poly-CD cryogels could be recycled with an exposure to ethanol and reused without any significant loss in the sorption capacity of PAHs.