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Article Citation - WoS: 25Citation - Scopus: 28The Pimpled Gold Nanosphere: a Superior Candidate for Plasmonic Photothermal Therapy(Dove Medical Press Ltd, 2020) Nasseri, Behzad; Turk, Mustafa; Kosemehmetoglu, Kemal; Kaya, Murat; Piskin, Erhan; Rabiee, Navid; Webster, Thomas J.Background: The development of highly efficient nanoparticles to convert light to heat for anti-cancer applications is quite a challenging field of research. Methods: In this study, we synthesized unique pimpled gold nanospheres (PGNSs) for plasmonic photothermal therapy (PPTT). The light-to-heat conversion capability of PGNSs and PPTT damage at the cellular level were investigated using a tissue phantom model. The ability of PGNSs to induce robust cellular damage was studied during cytotoxicity tests on colorectal adenocarcinoma (DLD-1) and fibroblast cell lines. Further, a numerical model of plasmonic (COMSOL Multiphysics) properties was used with the PPTT experimental assays. Results: A low cytotoxic effect of thiolated polyethylene glycol (SH-PEG400-SH-) was observed which improved the biocompatibility of PGNSs to maintain 89.4% cell viability during cytometry assays (in terms of fibroblast cells for 24 hrs at a concentration of 300 mu g/mL). The heat generated from the nanoparticle-mediated phantom models resulted in Delta T=30 degrees C, Delta T=23.1 degrees C and Delta T=21 degrees C for the PGNSs, AuNRs, and AuNPs, respectively (at a 300 mu g/mL concentration and for 325 sec). For the in vitro assays of PPTT on cancer cells, the PGNS group induced a 68.78% lethality (apoptosis) on DLD-1 cells. Fluorescence microscopy results showed the destruction of cell membranes and nuclei for the PPTT group. Experiments further revealed a penetration depth of sufficient PPTT damage in a physical tumor model after hematoxylin and eosin (H&E) staining through pathological studies (at depths of 2, 3 and 4 cm). Severe structural damages were observed in the tissue model through an 808-nm laser exposed to the PGNSs. Conclusion: Collectively, such results show much promise for the use of the present PGNSs and photothermal therapy for numerous anti-cancer applications.Master Thesis Poli (n- Metilanilin) Eklenmiş Gümüş Nanopartiküllerin Antibakteriyel Aktivitesinin Araştırılması(2022) Aldarajı, Mostafa Kamıl Maala; İşgör, Sultan Belgin; Kaya, Muratİnsanlar, hayvanlar ve mahsuller, belirli bakteri türlerinin neden olduğu birçok hastalıktan muzdarip olabilir. Bu bakterilerin, karşılaşabilecekleri en uygun araçları belirlemek için derinlemesine araştırılması gerekir. Bu bakteri türleri arasında (Escherichia coli) ve (Staphylococcus aureus) bulunur. Gümüş, bakterileri yok edebilecek bazı kimyasal ve fiziksel özelliklere sahip olduğu için bu bakterilerin yayılmasının tedavisinde kullanılan en önemli mineral elementlerden biridir. Etkinliği incelenen bu özelliklerden biri Nanoteknolojidir. Bunlar 1 ila 100 nanometre arasında değişen parçacıklardır. Bu parçacıkların dış zarlara nüfuz edebildiği ve hücreye girebileceği bulunmuştur. Bunu kullanarak, protein üretimini durdurmak için çalışır ve gümüş nanopartiküller ile bulunan yüksek toksisite nedeniyle canlı hücreyi öldürmeye başlar. Ek olarak, gümüş nanopartiküllere poli (n-metil anilin) ilave edildi. PNMA 0.025 M monomer çözeltisi ile hazırlandı. Elde edilen PNMA kürelerinin boyutu 200-550 nm arasındadır. Poli (N-metil anilin) gümüş nanopartikülleri (PNMA-AGNP'LER) başarıyla hazırlamak için oksidatif kimyasal polimerizasyon ve sıvı emprenye yöntemleri kullanıldı. Elde edilen partikülleri karakterize etmek için SEM, TEM, EDX ve ICP-Oe'ler kullanıldı. Bu bileşiklerin; PNMA ve Ag-Pnma'nın Escherichia coli ve Staphylococcus aureus'a karşı antibakteriyel etkileri incelenmiş ve bu bileşiklerin penisilin/streptomisin ortak antibiyotiği ile etkileri karşılaştırılmıştır.Master Thesis Amin Borandan Hidrojen Üretilmesi için Üzerine Bimetalik Gümüş-bakır Nanoparçacıkları Eklenmiş Silika Kaplı Kobalt Ferrit Manyetik Nanoparçacıkların Hazırlanması(2016) Mohammed, Salma S. Abdalla; Kaya, MuratHidrojen en önemli temiz enerji kaynaklarından biri olarak bilinmektedir ve mobil uygulamalar için hidrojen taşıyıcı sistemler ve bu sistemlerden hidrojen eldesini sağlayacak metodların geliştirilmesi çok önemlidir. Literatürde olarak metal hidrürler, kimyasal hidrürler, organic moleküller, metal organic kafes yapıları ve karbon nanotüpler gibi hidrojen depolama malzemeleri ile ilgili bir çok yayın bulunmaktadır.Bunlar arasında kimyasal hidrürler yüksek hidrojen depolama kapasiteleri sebebi ile büyük ilgi görmektedir. Kararlılığı ve toksik olmaması yanında kütlece 19.6 % oranında hidrojene sahip olması sebebi ile amin boran önemli bir bidrojen depolama malzemesi olarak bilinmektedir. Uygun katalizör kullanımı ile normal şartlarda 1 mol amin borandan 3 mol hidrojen eldesi mümkündür. Amin borandan hidrojen eldesinde kinetic parametrelerin iyileştirilmesi için yüksek etkiye sahip katalizörlerin heliştirilmesi, hidrojen enerjisinin mobil uygulamaları için çok önemlidir. Bunun yanında katalizörün reaksiyon ortamından ayrılması ve tekrar kullanımı, üstesinden gelinmesi gereken diğer önemli konulardır. Bu çalışmada, amin borandan hidrolitik olarak hidrojen eldesin için katalizör olarak manyetik olarak ayrılabilen CoFe2O4@SiO2 destek malzemesine ıslak emdirme yöntemi ile ekelenmiş gümüş-bakır nanoparçacıklarının hazırlanması için kolay bir yöntem rapor edilmiştir. Hazırlanan katalizör oda sıcaklığında amin borandan hidrojen eldesi reaksiyonunda mükemmel katalitik aktivite göstermiştir. İlk çevrim frekansı 146 dk-1 olarak hesaplanmıştır. Buna ek olarak, CoFe2O4@SiO2 destek malzemesi üzerine eklenmiş AgCu nanoparçacıklar, kaydadeğer kararlılık ve tekrar kullanılabilme kabiliyeti göstermiştir ve amin borandan hidrojen eldesinde 10. kullanımda bile tam çevrimde hemen hemen ilk aktivitesini korumuştur.Article Citation - WoS: 35Citation - Scopus: 37Hydroxyapatite-Nanosphere Supported Ruthenium(0) Nanoparticle Catalyst for Hydrogen Generation From Ammonia-Borane Solution: Kinetic Studies for Nanoparticle Formation and Hydrogen Evolution(Royal Soc Chemistry, 2014) Durak, Halil; Gulcan, Mehmet; Zahmakiran, Mehmet; Ozkar, Saim; Kaya, MuratThe development of readily prepared effective heterogeneous catalysts for hydrogen generation from ammonia-borane (AB; NH3BH3) solution under mild conditions still remains a challenge in the field of "hydrogen economy". In this study, we report our finding of an in situ generated, highly active ruthenium nanocatalyst for the dehydrogenation of ammonia-borane in water at room temperature. The new catalyst system consists of ruthenium(0) nanoparticles supported on nanohydroxyapatite (RuNPs@nano-HAp), and can be reproducibly prepared under in situ conditions from the ammonia-borane reduction of Ru3+ ions exchanged into nanohydroxyapatite (Ru3+@nano-HAp) during the hydrolytic dehydrogenation of ammonia-borane at 25 +/- 0.1 degrees C. Nanohydroxyapatite-supported ruthenium(0) nanoparticles were characterized by a combination of advanced analytical techniques. The sum of their results shows the formation of well-dispersed ruthenium(0) nanoparticles with a mean diameter of 2.6 +/- 0.6 nm on the surface of the nanospheres of hydroxyapatite by keeping the host matrix intact. The resulting RuNPs@nano-HAp are highly active catalyst in the hydrolytic dehydrogenation of ammonia-borane with an initial TOF value of 205 min(-1) by generating 3.0 equiv. of H-2 per mole of ammonia-borane at 25 +/- 0.1 degrees C. Moreover, they are sufficiently stable to be isolated and bottled as solid materials, which can be reused as active catalyst under the identical conditions of first run. The work reported here also includes the following results: (i) monitoring the formation kinetics of the in situ generated RuNPs@nano-HAp by hydrogen generation from the hydrolytic dehydrogenation of ammonia-borane as the reporter reaction. The sigmoidal kinetics of catalyst formation and concomitant dehydrogenation fits well to the two-step, slow nucleation, followed by autocatalytic surface growth mechanism, P -> Q (rate constant k(1)) and P + Q -> 2Q (rate constant k(2)), in which P is Ru3+@nano-HAp and Q is the growing, catalytically active RuNPs@nano-HAp; (ii) the compilation of kinetic data for the RuNPs@nano-HAp catalyzed hydrolytic dehydrogenation of ammonia-borane depending on the temperature and catalyst concentration to determine the dependency of reaction rate on catalyst concentration and activation parameters (E-a, Delta H-#, and Delta S-#) of the reaction.Article Citation - WoS: 11Citation - Scopus: 12Ag Nanostructures on a Poly(3,4-Ethylenedioxythiophene) Film Prepared With Electrochemical Route: a Controllable Roughened Sers Substrate With High Repeatability and Stability(Pergamon-elsevier Science Ltd, 2012) Dogan, Uzeyir; Kaya, Murat; Cihaner, Atilla; Volkan, MurvetA simple, reliable and reproducible one-step electrochemical method for the preparation of surface-enhanced Raman-active polymer-mediated silver nanoparticles (Ag NPs) on planar indium tin oxide (ITO) coated glass substrates was reported. Poly(3,4-ethylenedioxythiophene) (PEDOT) film was used as a support material for dispersing nanostructured silver nanostructures on the surface homogeneously, since 3,4-ethylenedioxythiophene (EDOT) monomer polymerizes regioregularly. The optical properties and morphologies of the silver substrates have been investigated by ultraviolet-visible (UV-vis) spectroscopy and field emission scanning electron microscopy (FE-SEM). The UV-vis and FE-SEM results revealed that the Ag nanostructures separately appeared on the PEDOT coated ITO after reduction. The effect of the thickness of PEDOT polymer film, reduction potential of silver, the concentration of silver ion solution and the amount of silver particle on the polymer film on the SERS response were studied as well as repeatability and temporal stability of prepared substrates. Brilliant cresyl blue (BCB) has been used as Raman probes to evaluate the properties of the new SERS substrates. Signals collected over multiple spots within the same substrate resulted in a relative standard deviation (RSD) of 9.34%, while an RSD of 11.05% was measured in signals collected from different substrates. The SERS-active substrates were robust and stable which lost only 5.71% of initial intensity after 1 month. (C) 2012 Elsevier Ltd. All rights reserved.Article Citation - WoS: 28Citation - Scopus: 30Functionalized Polysulfide Copolymers With 4-Vinylpyridine Via Inverse Vulcanization(Elsevier Science Bv, 2019) Berk, Hasan; Balci, Burcu; Ertan, Salih; Kaya, Murat; Cihaner, AtillaA new series of functional polysulfide copolymers called poly(sulfur-random-4-vinylpyridine) (poly(S-r-4VP)) was synthesized via inverse vulcanization technique by ring opening polymerization of elemental sulfur in the presence of 4-vinylpyridine (4VP). The corresponding copolymers can be post functionalized by using amine group in 4VP unit to get polymers bearing various properties. Elemental sulfur was heated up to 160 degrees C and 4VP was added slowly to a clear yellowish orange colored liquid at this temperature. The reaction mixture was vitrified to form a reddish-brown polymeric material at 180 degrees C in 1 h. The products were characterized by using FTIR, NMR, and Raman spectroscopic techniques. Poly(S-r-4VP) copolymers are soluble in common solvents like dichloromethane, chloroform and tetrahydrofuran. Weight-average molecular weights of poly(S-r-4VP) copolymers with different wt% 4VP were measured by using gel permeation chromatography technique. The polysulfide copolymers with different wt% 4VP have high weight-average molecular weights with polydispersity indeces (PDI) in a range from 1.88 to 4.06 measured by gel permeation chromatography. Post functionalization of the copolymer with 50 wt% 4VP as an example was performed successfully by using alkyl bromide to get N-alkyl quaternized 4VP in polymer backbone.Master Thesis Amin Boranın Dehidrojenlenmesi için Bakır Nanoparçacık Eklenmiş Politiyofenin Hazırlanması(2017) Alablaq, Salha; Kaya, MuratNanokatalizörler sahip oldukları büyük yüzey-hacim oranları sebebi ile yüksek katalitik aktivite gösteren malzemeler olarak bilinmektedirler. Koloidal nanoparçacıkların sulu çözeltileri gibi homojen nanokatalizörler ise reaksiyonun oluşması için kullanılan başlangıç maddeleri ve oluşan ürünler ile aynı fazda bulunmaktadır. Bu tip katalizörlerin heterojen katalizörlere karşı başlıca avantajı sahip oldukları yüksek seçicilik olarak sayılabilir. Ancak düşük termal kararlılıkları, ciddi metal kirliliği ve reaksiyon ortamından geri kazanımındaki zorluk homojen katalizörlerin karşılaştığı başlıca zorluklardır. Bu zorlukların üstesinden gelebilmek için heterojen nanokatalizörler yaygın olarak kullanılmaktadır. Bu tür katalizörlerde metal nanoparçacıklar silika, alumiyum ve karbon temelli malzemelerin üzerine sabitlenmektedir. Günümüzde ise bazı polimer destek malzemeleri kolay ve ucuz üretim metodları sebebi ile büyük ilgi toplamaktadır. Hidrojen en önemli temiz enerji kaynaklarından biri olarak bilinmektedir. Bu sebeple metal hidrürler, kimyasal hidrürler, organik moleküller, metal organik kafesler ve karbon nanotüpler gibi hidrojen depolama malazemelerinin üretimi için birçok çalışma yapılmaktadır. Bu hidrojen depolama malzemleri arasında kimyasal hidrürler yüksek hidrojen depolama kapasitesine sahip olmaları sebebi ile büyük ilgi görmektedir. Kimyasal hidrürler arasından amin boran, yüksek hidrojen depolama kapasitesi (kütlece 19.6 %), yüksek kararlılık ve düşük toksisiteye sahip olması sebebi ile büyük önem kazanmıştır. Uygun katalizör kullanımı ile ılımlı şartlarda 1 mol amin borandan 3 mol hidrojen eldesi mümkündür. Amin borandan hidrojen eldesinde kinetik parametrelerin iyileştirilmesi için yüksek etkiye sahip katalizörlerin geliştirilmesi, hidrojen enerjisinin uygulamaları için çok önemlidir. Bu tezde, amin borandan sulu ortamda hidrojen eldesi için politiyofen üzerine bakır nanoparçacıkların eklendiği katalizörün hazırlanması için uygun bir yöntem sunulmaktadır. Bunun için ilk olarak politiyofen destek malzemesi hazırlanmıştır. Daha sonra bakır iyonları ıslak emdirme yöntemi ile polimer destek malzemesinin üzerine eklenmiştir. Bu aşamadan sonra bakır iyonları sodium borohidrür kullanılarak indirgenmiş ve bakır nanoparçacıklar elde edilmiştir. Daha sonra hazırlanan katalizörün katalitik aktivitesi ortaya çıkarılmıştır. İlk çevrim frekansı 11.8 dk-1 olarak bulunmuştur. Buna ek olarak, hazırlanan katalizörün kararlılığı ve tekrar kullanılabilme kapasitesi bulunmuştur. Hazırlanan katalizör oldukça iyi kararlılık ve tekrar kullanılabilme kapasitesine sahiptir. Bakır eklenmiş politiyofen katalizörü amin boranın hidrolitik olarak dehidrojenlenmesindeki beşinci tekrar kullanımından sonra benzer aktivite göstermiştir.Article Citation - WoS: 51Citation - Scopus: 54Atomic Layer Deposition-sio2 Layers Protected Pdconi Nanoparticles Supported on Tio2 Nanopowders: Exceptionally Stable Nanocatalyst for the Dehydrogenation of Formic Acid(Elsevier Science Bv, 2017) Caner, Nurdan; Bulut, Ahmet; Yurderi, Mehmet; Ertas, Ilknur Efecan; Kivrak, Hilal; Kaya, Murat; Zahmakiran, MehmetTiO2 nanopowders supported trimetallic PdCoNi alloy nanoparticles were simply and reproducibly prepared by wet-impregnation followed by simultaneous reduction method, then to enhance their stability against to sintering and leaching atomic layer deposition (ALD) technique was utilized to grow SiO2 layers amongst these surface bound PdCoNi alloy nanoparticles (PdCoNi/TiO2-ALD-SiO2). These new nanomaterials are characterized by the combination of complimentary techniques and sum of their results exhibited that the formation of ALD-SiO2 layers protected well-dispersed and highly crystalline PdCoNi alloy nanoparticles (ca. 3.52 nm) supported on TiO2 nanopowders. The catalytic performance of the resulting PdCoNi/TiO2-ALD-SiO2 in terms of activity, selectivity and stability was investigated in the dehydrogenation of aqueous formic acid (HCOOH), which has recently been suggested as a promising hydrogen storage material with a 4.4 wt% hydrogen capacity, solution under mild conditions. The results collected from our systematic studies revealed that PdCoNi/TiO2-ALD-SiO2 nanomaterial can act as highly active and selective nanocatalyst in the formic acid dehydrogenation at room temperature by providing an initial turnover frequency (TOF) value of 207 mol H-2/mol metal;: h and >99% of dehydrogenation selectivity at almost complete conversion. More importantly, the catalytic reusability experiments separately carried out with PdCoNi/TiO2-ALD-SiO2 and PdCoNi/TiO2 nanocatalysts in the dehydrogenation of formic acid under more forcing conditions pointed out that PdCoNi/TiO2-ALD-SiO2 nanocatalyst displays unprecedented catalytic stability against to leaching and sintering throughout the reusability experiments it retains almost its inherent activity, selectivity and conversion even at 20th reuse, whereas analogous PdCoNi/TiO2 completely lost its catalytic performance. (C) 2017 Elsevier B.V. All rights reserved.Article Citation - WoS: 136Citation - Scopus: 148Palladium(0) Nanoparticles Supported on Silica-Coated Cobalt Ferrite: a Highly Active, Magnetically Isolable and Reusable Catalyst for Hydrolytic Dehydrogenation of Ammonia Borane(Elsevier, 2014) Akbayrak, Serdar; Kaya, Murat; Volkan, Murvet; Ozkar, SaimPalladium(0) nanoparticles supported on silica-coated cobalt ferrite (Pd(0)/SiO2-CoFe2O4) were in situ generated during the hydrolysis of ammonia borane, isolated from the reaction solution by using a permanent magnet and characterized by ICP-OES, XRD, TEM, TEM-EDX, XPS and the N-2 adsorption-desorption techniques. All the results reveal that well dispersed palladium(0) nanoparticles were successfully supported on silica coated cobalt ferrite and the resulting Pd(0)/SiO2-CoFe2O4 are highly active, magnetically isolable, and recyclable catalysts in hydrogen generation from the hydrolysis of ammonia borane with an unprecedented turnover frequency (TOF, calculated on the basis of the total amount of Pd) of 254 mol H-2 (mol Pd min)(-1) at 25 +/- 0.1 degrees C. The reusability tests reveal that Pd(0)/SiO2-CoFe2O4 are still active in the subsequent runs of hydrolysis of ammonia borane providing 100% conversion. Pd(0)/SiO2-CoFe2O4 provide the highest catalytic activity with a TOF value of 198 mol H-2 (mol Pd min)(-1) in the 10th use in hydrogen generation from the hydrolysis of ammonia borane as compared to the other palladium catalysts. The work reported here also includes the kinetic studies depending on the temperature to determine the activation energy of the reaction (E-a = 52 +/- 2 kJ/mol) and the effect of catalyst concentration on the rate of hydrolytic dehydrogenation of ammonia borane, respectively. (C) 2013 Elsevier B.V. All rights reserved.Article Citation - WoS: 23Citation - Scopus: 27Nanocrystalline Metal Organic Framework (mil-101) Stabilized Copper Nanoparticles: Highly Efficient Nanocatalyst for the Hydrolytic Dehydrogenation of Methylamine Borane(Elsevier Science Sa, 2018) Baguc, Ismail Burak; Ertas, Ilknur Efecan; Yurderi, Mehmet; Bulut, Ahmet; Zahmakiran, Mehmet; Kaya, MuratThe copper nanoparticles stabilized by nanocrystalline MIL-101 framework (Cu/nano-MIL-101) was reproducibly prepared by following double solvent method combined with liquid phase chemical reduction technique. The characterization of the resulting new material was done by using various analytical techniques including ICP-OES, P-XRD, N-2-adsorption-desorption, XPS, FE-SEM, SEM-EDX, BFTEM and HAADF-STEM; the summation of their results reveals that the formation of well-dispersed and very small sized (0.8 nm) copper nanoparticles within nanocrystalline MIL-101 framework. The catalytic performance of Cu/nano-MIL-101 in terms of activity and stability was tested in the hydrolytic dehydrogenation of methylamine borane (CH3NH2BH3), which has been considered as one of the attractive materials for the efficient chemical hydrogen storage. Cu/nano-MIL-101 catalyzes the hydrolytic dehydrogenation of methylamine borane with high activity (turnover frequency; TOF = 257 mot H-2/mol Cu x h) and conversion ( > 99%) under air at room temperature. Moreover, these nano-MIL-101 framework stabilized copper nanoparticles show great durability against to sintering and leaching, which make Cu/nano-MIL-101 reusable nanocatalyst in the hydrolytic dehydrogenation of methylamine-borane. Cu/nano-MIL-101 nanocatalyst retains 83% of its inherent activity at complete conversion even at 10th recycle in the hydrolytic dehydrogenation of methylamine borane.
