Dönüs Tuncel's research while affiliated with Bilkent University and other places

Delamination due to an inferior adhesion between reinforcement material and matrix in carbon fiber-reinforced thermoplastic (CFRTP) composites is a crucial problem to be solved. To this end, this study aims to overcome poor wettability between reinforcing phase, i.e., carbon fiber (CF), and thermoplastic matrix, i.e., polyetherether ketone (PEEK). Herein, CF’s surface was tailored by application of different polymeric sizing agents which have different chemical structures. Morphology and topology analyses were performed by Scanning Electron Microscope and 3D laser scanning, respectively. Later, a variety of wettability results were obtained by the sessile drop method used in Contact Angle (CA) measurements for CFs throughout application of each sizing agent applied by dip coating. Sizing materials were designed such that the chemical structure of CF’s surface could exhibit compatibility with the matrix itself. Consequently, complete wettability (CA: 0°) was achieved for CFs sized by HPEEK (CF/hydroxylated PEEK (HPEEK)) and the surface free energy (SFE) of CF was enhanced from 5.43 to 72.8 mJ/m² while the SFE of the PEEK matrix is 40.1 mJ/m². Moreover, sizing by HPEEK improved the average surface roughness of CF by 32% which enables optimized adhesion. Afterward, repetitive tensile tests were carried out to observe effects of improved interfacial interlocking on the mechanical properties of the final CFRTP composite. Stress–strain curves revealed that the tensile strength of CFRTP improved from 473 to 508 MPa through the sizing of CF by HPEEK whereas pristine PEEK has a much smaller tensile strength (98 MPa) than the aforementioned CF-reinforced composites. Graphical abstract The sizing of carbon fiber’s surface by HPEEK resulted in an enhanced adhesion with the PEEK matrix. Since the chemical structure and physical properties of sizing agent and matrix are compatible, potential debonding between them was eliminated. Thus, the improved wettability led to a substantial increase in the mechanical strength of the final TP composite.

Rotaxanes can exhibit stimuli-responsive behavior by allowing positional fluctuations of their rota groups in response to physiochemical conditions such as the changes in solution pH. However, ionic strength of the solution also affects the molecular conformation by altering the charge state of the entire molecule, coupling the stimuli-responsiveness of rotaxanes with their conformation. A molecular-scale investigation on a model system can allow the decoupling and identification of various effects and can greatly benefit applications of such molecular switches. By using atomistic molecular dynamics simulations, we study equilibrium and kinetics properties of various charge states of the [5]rotaxane, which is a supramolecular moiety with four rotaxanes bonded to a porphyrin core. We model various physiochemical charge states, each of which can be realized at various solution pH levels as well as several exotic charge distributions. By analyzing molecular configurations, hydrogen bonding, and energetics of single molecules in salt-free water and its polyrotaxanated network at the interface of water and chloroform, we demonstrate that charge-neutral and negatively charged molecules often tend to collapse in a way that they can expose their porphyrin core. Contrarily, positively charged moieties tend to take more extended molecular configurations blocking the core. Further, sudden changes in the charge states emulating the pH alterations in solution conditions lead to rapid, sub-10 ns level, changes in the molecular conformation of [5]rotaxane via shuttling motion of CB6 rings along axles. Finally, simulations of 2D [5]rotaxane network structures support our previous findings on a few nanometer-thick film formation at oil-water interfaces. Overall, our results suggest that rotaxane-based structures can exhibit a rich spectrum of molecular configurations and kinetics depending on the ionic strength of the solution.

In this study, sulfur‐enriched microporous organic polymer (MOP) was prepared using one‐pot Shiff‐base type polycondensation reaction of thiophendicarboxaldehyde with melamine. With 195.731 m² g⁻¹ surface area and 0.047 cm³ g⁻¹ pore volume, the as‐synthesized MOP has a cotton‐like morphology and a micropore‐dominated pore size distribution. After loading MOP with nickel as a co‐catalyst, we demonstrated that the obtained framework could be used as an efficient and robust electrocatalyst for hydrogen evolution reaction (HER) in an alkaline medium with the optimum composite (Ni2@MOP) exhibiting a low onset potential of −66 mV. Furthermore, the optimum electrocatalyst showed good stability, delivering 91% faradaic efficiency (FE) after a 3.5 h chronoamperometry experiment.

Micrometer-scale monodisperse droplets are produced to generate nanowalled supramolecular microcapsules using microfluidics for high reproducibility and high-throughput manipulation, efficient material consumption, and control over hierarchical structure, shape, and size. In this study, an optimized microfluidic droplet generation technique and a unique liquid–liquid interfacial polymerization method were applied to fabricate the monodisperse polyrotaxane–based supramolecular microcapsules in a fast and simple way. To minimize the uncertainty due to droplet volume variation, the inlet pressures were supplied from the same source while lowering the interfacial tension and the main channel hydrodynamic resistance, which are critical for high monodispersity. The target polyrotaxane network (PN) was simply formed at the interface of the water and oil phases in ultra-monodisperse microdroplets via the cucurbit[6]uril (CB6)-catalyzed azide–alkyne cycloaddition (CB6-AAC) reaction between azido- and alkyne-functionalized tetraphenylporphyrin monomers (TPP-4AZ and TPP-4AL). The thickness of the interfacially assembled PN microcapsules was 20 nm as analyzed by cross-sectional TEM and TEM-EDX techniques. The resultant water-in-oil PN microcapsules were highly monodisperse in size and able to retain target molecules. Here, rhodamine 6G (Rh6G)-loaded PN microcapsules were fabricated, and the release rate of the Rh6G cargo was investigated over time for controlled drug release applications.

We report here the synthesis and characterization of a water dispersible conjugated polymer nanoparticle‐based photosensitizer and its application in the antibacterial and anticancer phototherapies. Nanoparticles (CPPN) were synthesized in one‐pot by nanoprecipitation method, in which a hydrophobic azide functionalized, red‐emitting thiophene‐benzothiodiazole based conjugated polymer (CP‐AZ) was cross‐linked with a hydrophilic, propargylamine functionalized porphyrin (TPP‐4AL) through cucurbit[6]uril (CB6) catalyzed azide‐alkyne cycloaddition (CB6‐AAC) reaction. CPPN demonstrated high stability in aqueous medium for more than a month without any visible aggregation and appeared to be a good photosensitizer with high light‐triggered reactive oxygen species (ROS) generation ability. Consequently, CPPN displayed photo‐induced biocidal activity against Gram‐negative (Escherichia coli, E. coli) and Gram‐positive (Bacillus subtilis, B. subtilis and Staphylococcus aureus, S. aureus) bacteria. When bacteria suspension was incubated with CPPN (20 μg ml⁻¹) and irradiated with white light (22 mW cm⁻²) for 10 min, more than 3.5‐log reduction in colony‐forming units (CFUs) was recorded for the three model bacteria. CPPN demonstrated minimal dark cytotoxicity against the bacteria. Moreover, the cytotoxicity of CPPN on mammalian cell was studied using MCF‐7 breast cancer cell line. The results demonstrated that CPPN is non‐toxic to mammalian cells in the dark even at a high concentration of 112.5 μg ml⁻¹ and this feature makes CPPN an ideal photosensitizer.

Herein, we report the synthesis of a new supramolecular polymeric network (PCN) assembled through crosslinking of propyl bromide substituted tetraphenyl porphyrin with perhydroxy-cucurbit [8]uril and its use in the electrocatalytic hydrogen evaluation reaction after loading with nickel and integrating with in situ-electrochemically reduced graphene oxide (ERGO). Electrode was prepared by first coating graphene oxide on the FTO substrate followed by layering the nickel loaded PCN and finally by applying an appropriate voltage to reduce the graphene oxide in situ electrochemical reaction. The loading of nickel cocatalyst into PCN together with the integration of ERGO layer substantially improved its HER efficiency. Effect of various concentrations of Ni and GO on the HER activity of the developed electrocatalyst were investigated. Therein, ERGO1/Ni2@PCN catalyst containing 41% Ni and 50% GO (with respect to PCN) with only one layer of each component demonstrated excellent HER activity and stability with low onset and overpotentials of −20 mV, η@10 mA cm⁻² of −360 mV, respectively, and remarkable hydrogen generation rate of 27.5 mmol h⁻¹ g⁻¹ in 1 M KOH. This noble-metal-free catalytic system is simple yet highly promising for the efficient hydrogen evolution reaction from water splitting.

In the present study, we describe the synthesis and characterization of a new covalent organic framework (COF-TPP-CB[6]) which was assembled together by clicking perpropargyloxy cucurbit[6]uril (CB[6]) to the azido-functionalized tetraphenylporphyrin (TPP-4N3) through a copper-catalyzed azide–alkyne cycloaddition reaction (CuAAC). Perpropargyloxy CB[6] was synthesized through the direct oxidation of CB[6] to afford perhydroxy CB[6] followed by subsequent O-propargylation using NaH. We also demonstrated that the resulting framework (COF-TPP-CB[6]) can be employed as an efficient and stable electrocatalyst for hydrogen evolution reaction (HER) in alkaline medium upon loading it with a nickel cocatalyst. The effect of TiO2 and different loadings of Ni on the HER performance of TPP-CB[6] was also studied. Herein, 12%Ni@TPP-CB[6] as the optimum catalyst showed an impressive H2 production rate of 18.7 mmol h–1 g–1 with a low onset potential of −250 mV.

Here, we adapt the catalytically self-threading polyrotaxane synthesis for the construction of two-dimensional polymeric thin films using a water–oil interfacial polymerization method. In this method, the polymerization and the rotaxane formation take place simultaneously at the interface because of the presence of catalytically active cucurbit[6]uril (CB6) that can facilitate 1,3-dipolar cycloaddition reaction between alkyne and azide to form polytriazoles. By varying the concentration of the monomers, reaction time, and the size of the reaction vessel, it is possible to control the thickness and the lateral dimensions of the film. The as-synthesized film is free-floating, transparent, and robust enough to be transferred to any substrates. It contains photoactive porphyrin units which are quite appealing as a photosensitizer because of their capability to produce reactive oxygen species in high yield upon visible light irradiation. By taking advantage of these aforementioned features, this film was employed as a broad-spectrum photo-antimicrobial agent whose activity was switched on by light excitation against both Gram-negative and Gram-positive bacterial strains and switched off in the dark.

Herein, hybrid nanoparticles composed of red-emitting conjugated oligomer (COL) and gold nanoparticles (Au-NP) were prepared through a one-pot synthetic method in which oligomer acts as a reducing agent as well as a matrix to wrap the newly formed Au nanoparticles. These hybrid nanoparticles (COL-Au-NP) exhibit photodynamic and photothermal activity against both Gram-positive and Gram-negative bacterial strains. They were also proven to possess high photostability and thermal reversibility. Dark cytotoxicity of COL-Au-NPs towards pathogens and mammalian breast cancer cells (MCF-7) reduced significantly upon complexation with cucurbit[7]uril while preserving their light-induced cytotoxic activity when irradiated by 915 nm laser for photothermal therapy (PTT) and white light for photodynamic therapy (PDT), respectively. Furthermore, these nanoparticles have cellular imaging capability owing to their intrinsic fluorescent characteristics and can be used in the image-guided therapy.