Chemical Engineering / Kimya Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/14
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Article Citation - WoS: 13Citation - Scopus: 11Bottom-Up Synthesis of Platinum Dual-Atom Catalysts on Cerium Oxide(American Chemical Society, 2024) Mekkering, Martijn J.; Laan, Petrus C. M.; Troglia, Alessandro; Bliem, Roland; Kızılkaya, Ali Can; Rothenberg, Gadi; Yan, NingWe present here the synthesis and performance of dual-atom catalysts (DACs), analogous to well-known single-atom catalysts (SACs). DACs feature sites containing pairs of metal atoms and can outperform SACs due to their additional binding possibilities. Yet quantifying the improved catalytic activity in terms of proximity effects remains difficult, as it requires both high-resolution kinetic data and an understanding of the reaction pathways. Here, we use an automated bubble counter setup for comparing the catalytic performance of ceria-supported platinum SACs and DACs in ammonia borane hydrolysis. The catalysts were synthesized by wet impregnation and characterized using SEM, HAADF-STEM, XRD, XPS, and CO-DRIFTS. High-precision kinetic studies of ammonia borane hydrolysis in the presence of SACs show two temperature-dependent regions, with a transition point at 43 degrees C. Conversely, the DACs show only one regime. We show that this is because DACs preorganize both ammonia borane and water at the dual-atom active site. The additional proximal Pt atom improves the reaction rate 3-fold and enables faster reactions at lower temperatures. We suggest that the DACs enable the activation of the water-O-H bond as well as increase the hydrogen spillover effect due to the adjacent Pt site. Interestingly, using ammonia borane hydrolysis as a benchmark reaction gives further insight into hydrogen spillover mechanisms, above what is known from the CO oxidation studies.Article Citation - WoS: 14Citation - Scopus: 163D Bioprinting of mouse pre-osteoblasts and human MSCs using bioinks consisting of gelatin and decellularized bone particles(Iop Publishing Ltd, 2024) Kara, Aylin; Distler, Thomas; Akkineni, Ashwini Rahul; Tihminlioglu, Funda; Gelinsky, Michael; Boccaccini, Aldo R.One of the key challenges in biofabrication applications is to obtain bioinks that provide a balance between printability, shape fidelity, cell viability, and tissue maturation. Decellularization methods allow the extraction of natural extracellular matrix, preserving tissue-specific matrix proteins. However, the critical challenge in bone decellularization is to preserve both organic (collagen, proteoglycans) and inorganic components (hydroxyapatite) to maintain the natural composition and functionality of bone. Besides, there is a need to investigate the effects of decellularized bone (DB) particles as a tissue-based additive in bioink formulation to develop functional bioinks. Here we evaluated the effect of incorporating DB particles of different sizes (<= 45 and <= 100 mu m) and concentrations (1%, 5%, 10% (wt %)) into bioink formulations containing gelatin (GEL) and pre-osteoblasts (MC3T3-E1) or human mesenchymal stem cells (hTERT-MSCs). In addition, we propose a minimalistic bioink formulation using GEL, DB particles and cells with an easy preparation process resulting in a high cell viability. The printability properties of the inks were evaluated. Additionally, rheological properties were determined with shear thinning and thixotropy tests. The bioprinted constructs were cultured for 28 days. The viability, proliferation, and osteogenic differentiation capacity of cells were evaluated using biochemical assays and fluorescence microscopy. The incorporation of DB particles enhanced cell proliferation and osteogenic differentiation capacity which might be due to the natural collagen and hydroxyapatite content of DB particles. Alkaline phosphatase activity is increased significantly by using DB particles, notably, without an osteogenic induction of the cells. Moreover, fluorescence images display pronounced cell-material interaction and cell attachment inside the constructs. With these promising results, the present minimalistic bioink formulation is envisioned as a potential candidate for bone tissue engineering as a clinically translatable material with straightforward preparation and high cell activity.Article Citation - WoS: 2Citation - Scopus: 2Further Developments of the Extended Quadrature Method of Moments To Solve Population Balance Equations(Cell Press, 2023) Turan, Meltem; Dutta, AbhishekDeveloping numerical methods to solve polydispersed flows using a Population Balance Equation (PBE) is an active research topic with wide engineering applications. The Extended Quadrature Method of Moments (EQMOM) approximates the number density as a positive mixture of Kernel Density Functions (KDFs) that allows physical source terms in the PBEs to compute continuous or point-wise form according to the moments. The moment-inversion procedure used in EQMOM has limitations such as the inability to calculate certain roots even if it is defined, absence of consistent result when multiple roots exist or when the roots are nearly equal. To address these limitations, the study proposes a modification of the moment-inversion procedure to solve the PBE based on the proposed Halley-Ridder (H-R) method. Although there is no significant improvement in the extent of variability relative to the mean of the tested shape parameter cr values, an increase in the number of floating point operations (FLOPS) is observed which the proposed algorithm responds in limitations mentioned above. The total number of FLOPS for all the kernels used for the approximation increased by around 30%. This is an improvement towards the development of a more reliable and robust moment-inversion procedure.Article Citation - WoS: 15Citation - Scopus: 19Immobilization of Esterase From Bacillus Subtilis on Halloysite Nanotubes and Applications on Dibutyl Phthalate Degradation(Elsevier, 2023) Rosales, Emilio; Pazos, Marta; Sanroman, Maria Angeles; Balcı, Esin; Sofuoğlu, AysunDibutyl phthalate (DBP) is one of the listed phthalic acid esters (PAEs) known as the priority toxicants which exhibit carcinogenic and teratogenic properties and is responsible for endocrine disruption. Therefore, its removal has become a matter to tackle with. In this work, the feasibility of DBP degradation by esterase and lipase enzymes obtained from various microorganisms and the immobilization of the most effective in a clayey material were investigated. Esterase from Bacillus subtilis exhibited the highest degradation efficiency reaching a complete degradation. Its immobilization onto halloysite nanotubes (HNTs) by adsorption method was studied by response surface methodology using a central composite design face-centered. The four selected factors that affect the HNT-enzyme composite generation were: pH, adsorption time, enzyme/HNT (E/H) ratio, and adsorption temperature, and the optimal conditions were determined (pH 7, time 360 min, E/H ratio 0.2, temperature 30oC). Consequently, the activity did not significantly decrease by immobilization, and the adsorption efficiency and relative activity were determined to be 73.15% and 82.7%, respectively. Besides, the immobilization enhanced thermal and storage stability. As for enzyme reusability, after 7 continuous cycles, the composite maintained almost 75% of its initial activity. Both the free enzyme (1 mg/mL) and the composite degraded 100 mg/L DBP with 100% efficiency and several byproducts were detected. Moreover, the composite could be reused for 7 cycles keeping a remarkable catalytic activity. Overall, this study indicated that the HNT-enzyme composite may be used as an effective candidate for remediation of the environmental media contaminated with DBP and other PAEs.(c) 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).Article Citation - WoS: 9Citation - Scopus: 10Cvd Deposited Epoxy Copolymers as Protective Coatings for Optical Surfaces(MDPI, 2023) Karabıyık, Merve; Cihanoğlu, Gizem; Ebil, ÖzgençCopolymer thin films of glycidyl methacrylate (GMA), ethylene glycol dimethacrylate (EGDMA) and 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (V4D4) were synthesized via initiated chemical vapor deposition (iCVD) as protective coatings for optical surfaces. Chemical durability in various solvents, corrosion resistance, adhesion to substrate, thermal resistance and optical transmittance of the films were evaluated. Crosslinked thin films exhibited high chemical resistance to strong organic solvents and excellent adhesion to substrates. Poly(GMA-co-EGDMA) and poly(GMA-co-V4D4) copolymers demonstrated protection against water (<1% thickness loss), high salt resistance (<1.5% thickness loss), and high optical transparency (~90% in visible spectrum) making them ideal coating materials for optical surfaces. Combining increased mechanical properties of GMA and chemical durability V4D4, the iCVD process provides a fast and low-cost alternative for the fabrication of protective coatings.Article Citation - WoS: 4Citation - Scopus: 5Continuous Treatment of Diethyl Hexyl and Dibutyl Phthalates by Fixed-Bed Reactor: Comparison of Two Esterase Bionanocomposites(Elsevier, 2022) Sanroman, Maria Angeles; Balcı, Esin; Rosales, Emilio; Pazos, Marta; Sofuoğlu, AysunThe removal of Diethyl hexyl phthalate (DEHP) and Dibutyl phthalate (DBP) is of great importance due to their potential adverse effects on the environment and human health. In this study, two bionanocomposites prepared by immobilization of Bacillus subtilis esterase by crosslinking to halloysite and supported in chitosan and alginate beads were studied and proposed as a green approach. The esterase immobilization was confirmed by physical-chemical characterization. Bionanocomposite using chitosan showed the best degradation levels in batch tests attaining complete degradation of DBP and around 90% of DEHP. To determine the operational stability and efficiency of the system, two fixed bed reactors filled with both bionanocomposites were carried out operating in continuous mode. Chitosan based bionanocomposite showed the best performance being able to completely remove DBP and more than 85% of DEHP at the different flowrates. These results proved the potential of these synthesized bionanocomposites to effectively remove Phthalic Acid Esters.Article Citation - WoS: 40Citation - Scopus: 47Boron in Geothermal Energy: Sources, Environmental Impacts, and Management in Geothermal Fluid(Elsevier, 2022) Mott, A.; Baba, Alper; Hadi Mosleh, Mojgan; Ökten, Hatice Eser; Babaei, Masoud; Gören, Ayşegül Yağmur; Feng, C.; Recepoğlu, Yaşar Kemal; Uzelli, Taygun; Uytun, Hüseyin; Morata, Diego; Yüksel Özşen, AslıThe problem of hazardous chemicals in geothermal fluid is a critical environmental concern in geothermal energy developments. Boron is among the hazardous contaminants reported to be present at high concentrations in geothermal fluids in various countries. Poor management and inadequate treatment of geothermal fluids can release excessive boron to the environment that has toxic effects on plants, humans, and animals. Despite the importance of boron management in geothermal fluid, limited and fragmented resources exist that provide a comprehensive understanding of its sources, transport and fate, and the treatment strategies in geothermal energy context. This paper presents the first critical review from a systematic and comprehensive review on different aspects of boron in geothermal fluid including its generation, sources, toxicity, ranges and the management approaches and treatment technologies. Our research highlights the origin of boron in geothermal water to be mainly from historical water-rock interactions and magmatic intrusion. Excessive concentrations of boron in geothermal fluids have been reported (over 500 mg/L in some case studies). Our review indicated that possible boron contamination in geothermal sites are mostly due to flawed construction of production/re-injection wells and uncontrolled discharge of geothermal water to surface water. The dominancy of non-ionic H3BO3 species makes the selection of the suitable treatment method for geothermal waters limited. Combining boron selective resins and membrane technologies, hybrid systems have provided effluents suitable for irrigation. However, their high energy consumption and course structure of boron selective resins encourage further research to develop cost-effective and environmentally friendly alternatives.Article Citation - WoS: 12Citation - Scopus: 12Biofouling-Resistant Ultrafiltration Membranes Via Codeposition of Dopamine and Cetyltrimethylammonium Bromide With Retained Size Selectivity and Water Flux(American Chemical Society, 2022) Cihanoğlu, Aydın; Schiffman, Jessica D.; Alsoy Altınkaya, SacideBiofouling is a serious problem in ultrafiltration (UF) membrane applications. Modifying the surface of membranes with low molecular weight, commercially available antibacterial chemistries is an excellent strategy to mitigate biofouling. Herein, we report a new strategy to impart antibacterial and anti-biofouling behavior without changing the support membrane’s size selectivity and pure water permeance (PWP). To this end, a strong antibacterial agent, cetyltrimethylammonium bromide (CTAB), was codeposited with dopamine onto commercial polyethersulfone (PES) UF membranes in the presence of nitrogen (N2) gas backflow. The PWP and pore size of the support membrane did not change with codeposition, confirming the benefit of N2 backflow in mitigating the solution intrusion phenomenon. X-ray photoelectron spectroscopy (XPS), surface ζ potentials, and contact angle measurements confirmed the successful codeposition of polydopamine (PDA) and CTAB onto the membrane. Among three different CTAB concentrations systematically investigated, the membrane functionalized with CTAB at the critical micelle concentration (CMC) provided the best anti-biofouling activity against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and retained its surface ζ potential after being stored in 1 M NaCl (pH = 6.8) for 3 months. Our results demonstrate the potential of using a facile, one-step approach to modify commercial UF membranes without compromising their pore size or flux, while simultaneously endowing antibacterial activity.Article Citation - WoS: 51Citation - Scopus: 583d Printed Gelatin/Decellularized Bone Composite Scaffolds for Bone Tissue Engineering: Fabrication, Characterization and Cytocompatibility Study(Elsevier, 2022) Kara, Aylin; Distler, Thomas; Polley, Christian; Schneidereit, Dominik; Seitz, Hermann; Friedrich, Oliver; Tıhmınlıoğlu, Funda; Boccaccini, Aldo RThree-dimensional (3D) printing technology enables the design of personalized scaffolds with tunable pore size and composition. Combining decellularization and 3D printing techniques provides the opportunity to fabricate scaffolds with high potential to mimic native tissue. The aim of this study is to produce novel decellularized bone extracellular matrix (dbECM)-reinforced composite-scaffold that can be used as a biomaterial for bone tissue engineering. Decellularized bone particles (dbPTs, ∼100 μm diameter) were obtained from rabbit femur and used as a reinforcement agent by mixing with gelatin (GEL) in different concentrations. 3D scaffolds were fabricated by using an extrusion-based bioprinter and crosslinking with microbial transglutaminase (mTG) enzyme, followed by freeze-drying to obtain porous structures. Fabricated 3D scaffolds were characterized morphologically, mechanically, and chemically. Furthermore, MC3T3-E1 mouse pre-osteoblast cells were seeded on the dbPTs reinforced GEL scaffolds (GEL/dbPTs) and cultured for 21 days to assess cytocompatibility and cell attachment. We demonstrate the 3D-printability of dbPTs-reinforced GEL hydrogels and the achievement of homogenous distribution of the dbPTs in the whole scaffold structure, as well as bioactivity and cytocompatibility of GEL/dbPTs scaffolds. It was shown that Young's modulus and degradation rate of scaffolds were enhanced with increasing dbPTs content. Multiphoton microscopy imaging displayed the interaction of cells with dbPTs, indicating attachment and proliferation of cells around the particles as well as into the GEL-particle hydrogels. Our results demonstrate that GEL/dbPTs hydrogel formulations have potential for bone tissue engineering.Article Citation - WoS: 42Citation - Scopus: 44Boron Carbon Nitride Nanosheets in Water and Wastewater Treatment: a Critical Review(Elsevier, 2022) Recepoğlu, Yaşar Kemal; Gören, Ayşegül Yağmur; Vatanpour, Vahid; Yoon, Yeojoon; Khataee, AlirezaThe availability and accessibility of clean and secure water supplies are pressing technological and scientific issues worldwide. As a result of global water constraints, wastewater treatment and reuse are being evaluated as feasible alternatives to fresh water for agricultural irrigation and domestic and industrial purposes. Boron carbon nitride (BCN) nanosheets have been studied intensively in the last decade in batteries, biosensors, and capacitors, and for use as catalysts, and they have recently been used in wastewater treatment. BCN materials, along with their synthesis processes, characteristics, and application areas in water and wastewater treatment, are discussed thoroughly in this paper. Additionally, synthesis processes for ternary BCN compounds, including chemical vapor deposition, ion beam-aided deposition, magnetron sputtering, and pulsed laser deposition, are described. BCN materials have also been explored because of their flexible electrical features, excellent mechanical strength, outstanding unreactivity, and significant stability, which make them appropriate for a range of severe environment applications. Thus, the use of BCN materials as photocatalysts and adsorbents and in electrochemical reduction and capacitive deionization are also discussed thoroughly. The highest ammonia production of 172,226.5 μg/h.mg.cat and faradic efficiency of 95.3% have been obtained using the BCN@Cu/CNT catalyst, whereas the ammonia production and FE values for metal-free BCN are 7.75 μg/h.mg.cat and 13.8%. Moreover, the maximum attained adsorption capacities of BCN nanosheets for Pb2+ and Hg2+ are 210 and 625 mg/g, respectively. Overall, this review indicates that essential work on BCN nanosheets is still needed. Future research should focus on the development of BCN nanostructures to encourage multidisciplinary research.