Search results for: nitric oxide (NO)

Authors: Jenny Radeva, Anke-Gundula Roth, Christian Goebbert, Robert Niestroj-Pahl, Lars Daehne, Axel Wolfram, Juergen Wiese

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Ceramic membranes for water purification combine excellent stability with long-life characteristics and high chemical resistance. Layer-by-Layer coating is a well-known technique for customization and optimization of filtration properties of membranes but is mostly used on polymeric membranes. Ceramic membranes comprising a metal oxide filtration layer of Al2O3 or TiO2 are charged and therefore highly suitable for polyelectrolyte adsorption. The high stability of the membrane support allows efficient backwash and chemical cleaning of the membrane. The presented study reports metal oxide/organic composite membrane with an increased rejection of bivalent salts like MgSO4 and the organic micropollutant Diclofenac. A self-build apparatus was used for applying the polyelectrolyte multilayers on the ceramic membrane. The device controls the flow and timing of the polyelectrolytes and washing solutions. As support for the Layer-by-Layer coat, ceramic mono-channel membranes were used with an inner capillary of 8 mm diameter, which is connected to the coating device. The inner wall of the capillary is coated subsequently with polycat- and anions. The filtration experiments were performed with a feed solution of MgSO4 and Diclofenac. The salt content of the permeate was detected conductometrically and Diclofenac was measured with UV-Adsorption. The concluded results show retention values of magnesium sulfate of 70% and diclofenac retention of 60%. Further experimental research studied various parameters of the composite membrane-like Molecular Weight Cut Off and pore size, Zeta potential and its mechanical and chemical robustness.

Keywords: water purification, polyelectrolytes, membrane modification, layer-by-layer coating, ceramic membranes

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Authors: Sang Koo Jeon, Seung Hoon Nahm, Oh Heon Kwon

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The unit cell of solid oxide fuel cell (SOFC) must be stacked as several layers type to obtain the high power. The most of researcher have concerned about the performance of stacked SOFC rather than the structural stability of stacked SOFC and especially interested how to design for reducing the electrical loss and improving the high efficiency. Consequently, the stacked SOFC able to produce the electrical high power and related parts like as manifold, gas seal, bipolar plate were developed to optimize the stack design. However, the unit cell of SOFC was just layered on the interconnector without the adhesion and the hydrogen and oxygen were injected to the interfacial layer in the high temperature. On the operating condition, the interfacial layer can be the one of the weak point in the stacked SOFC. Therefore the evaluation of the structural safety for the failure is essentially needed. In this study, interfacial adhesion between SOFC and metal adhesive was estimated in the high temperature environment. The metal adhesive was used to strongly connect the unit cell of SOFC with interconnector and provide the electrical conductivity between them. The four point bending test was performed to measure the interfacial adhesion. The unit cell of SOFC and SiO2 wafer were diced and then attached by metal adhesive. The SiO2 wafer had the center notch to initiate a crack from the tip of the notch. The modified stereomicroscope combined with the CCD camera and system for measuring the length was used to observe the fracture behavior. Additionally, the interfacial adhesion was evaluated in the high temperature condition because the metal adhesive was affected by high temperature. Also the specimen was exposed in the furnace during several hours and then the interfacial adhesion was evaluated. Finally, the interfacial adhesion energy was quantitatively determined and compared in the each condition.

Keywords: solid oxide fuel cell (SOFC), metal adhesive, adhesion, high temperature

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Authors: Zhibo Zhao, Horst Hahn, Robert Kruk, Abhisheck Sarkar

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High entropy oxides (HEOs), based on the incorporation of multiple-principal cations into the crystal lattice, offer the possibility to explore previously inaccessible oxide compositions and unconventional properties. Here it is demonstrated that despite the chemical complexity of HEOs external stimuli, such as epitaxial strain, can selectively stabilize certain magneto-electronic states. Epitaxial (Co₀.₂Cr₀.₂Fe₀.₂Mn₀.₂Ni₀.₂)₃O₄-HEO thin films are grown in three different strain states: tensile, compressive, and relaxed. A unique coexistence of rocksalt and spinel-HEO phases, which are fully coherent with no detectable chemical segregation, is revealed by transmission electron microscopy. This dual-phase coexistence appears as a universal phenomenon in (Co₀.₂Cr₀.₂Fe₀.₂Mn₀.₂Ni₀.₂)₃O₄ epitaxial films. Prominent changes in the magnetic anisotropy and domain structure highlight the strain-induced bidirectional control of magnetic properties in HEOs. When the films are relaxed, their magnetization behavior is isotropic, similar to that of bulk materials. However, under tensile strain, the hardness of the out-of-plane (OOP) axis increases significantly. On the other hand, compressive straining results in an easy OOP magnetization and a maze-like magnetic domain structure, indicating perpendicular magnetic anisotropy. Generally, this study emphasizes the adaptability of the high entropy design strategy, which, when combined with coherent strain engineering, opens additional prospects for fine-tuning properties in oxides.

Keywords: high entropy oxides, thin film, strain tuning, perpendicular magnetic anistropy

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Authors: V. P. Muhamed Shajudheen, K. Viswanathan, K. Anitha Rani, A. Uma Maheswari, S. Saravana Kumar

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We are reporting a simple and low-cost chemical precipitation method adopted to prepare zinc oxide nanoparticles (ZnO) using polyvinyl pyrrolidone (PVP) as a capping agent. The Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA) was applied on the dried gel sample to record the phase transformation temperature of zinc hydroxide Zn(OH)2 to zinc oxide (ZnO) to obtain the annealing temperature of 800C. The thermal, structure, morphology and optical properties have been employed by different techniques such as DSC-TGA, X-Ray Diffraction (XRD), Fourier Transform Infra-Red spectroscopy (FTIR), Micro Raman spectroscopy, UV-Visible absorption spectroscopy (UV-Vis), Photoluminescence spectroscopy (PL) and Field Effect Scanning Electron Microscopy (FESEM). X-ray diffraction results confirmed the wurtzite hexagonal structure of ZnO nanoparticles. The two intensive peaks at 160 and 432 cm-1 in the Raman Spectrum are mainly attributed to the first order modes of the wurtzite ZnO nanoparticles. The energy band gap obtained from the UV-Vis absorption spectra, shows a blue shift, which is attributed to increase in carrier concentration (Burstein Moss Effect). Photoluminescence studies of the single crystalline ZnO nanoparticles, show a strong peak centered at 385 nm, corresponding to the near band edge emission in ultraviolet range. The mixed shape of grapes, sphere, hexagonal and rock like structure has been noticed in FESEM. The results showed that PVP is a suitable capping agent for the preparation of ZnO nanoparticles by simple chemical precipitation method.

Keywords: ZnO nanoparticles, simple chemical precipitation route, mixed shape morphology, UV-visible absorption, photoluminescence, Fourier transform infra-Red spectroscopy

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Authors: Mahsa Kangazian Kangazi, Ali Akbar Ghareh Aghaji, Majid Montazer

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Nowadays, silica nanofibers are highly regarded among the inorganic nanofibers due to the high reactivity and availability of silicon compounds in nature. Sol-gel process is required for electrospinning of silica nanofibers in which a metal alkoxide is hydrolyzed, and the viscosity is increased. In this study, silica nanofibers containing silver nanoparticles were synthesized and electrospun from a mixture of silica sol with an easy spinnable polymer (PVA) as an additive. The silica sol contains tetraethyl orthosilicate (TEOS), silver nitrate, distilled water, nitric acid, and ethanol. Nanofibers were formed through electrospinning setup. The nanofibers were calcinated to remove the solvent and additive polymer. Consequently, pure silica nanofibers were produced. FTIR analysis indicated entire removal of polyvinyl alcohol from the structure and formation of silan groups. The presence of silver, silica and oxygen was confirmed by EDX. Also, XRD patterns revealed the presence of silver nanoparticles with a mean crystal size of 18 nm. FESEM images showed that adding silver nitrate into the sol-gel, resulted in lower nanofibers diameter from 286 to 136 nm. Furthermore, the electrospun nanofibers were more resistance in acidic media than alkaline media.

Keywords: in situ synthesis of silver nanoparticles, silica nanofibers, sol-gel, tetraethyl orthosilicate

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Authors: Roberta Pecoraro

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The focus of this work was to investigate the potential toxic effect of titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites on nauplii of microcrustacean Artemia sp. In order to assess the nanocomposite’s toxicity, a short-term test was performed by exposing nauplii to solutions containing TiO₂-rGO. To prepare titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites, a green procedure based on solar photoreduction was proposed; it allows to obtain the photocatalysts by exploiting the photocatalytic properties of titania activated by the solar irradiation in order to avoid the high temperatures and pressures required for the standard hydrothermal synthesis. Powders of TiO₂-rGO supplied by the Department of Chemical Sciences (University of Catania) are indicated as TiO₂-rGO at 1% and TiO₂-rGO at 2%. Starting from a stock solution (1mg rGO-TiO₂/10 ml ASPM water) of each type, we tested four different concentrations (serial dilutions ranging from 10⁻¹ to 10⁻⁴ mg/ml). All the solutions have been sonicated for 12 min prior to use. Artificial seawater (called ASPM water) was prepared to guarantee the hatching of the cysts and to maintain nauplii; the durable cysts used in this study, marketed by JBL (JBL GmbH & Co. KG, Germany), were hydrated with ASPM water to obtain nauplii (instar II-III larvae). The hatching of the cysts was carried out in the laboratory by immersing them in ASPM water inside a 500 ml beaker and keeping them constantly oxygenated thanks to an aerator for the insufflation of microbubble air: after 24-48 hours, the cysts hatched, and the nauplii appeared. The nauplii in the second and third stages of development were collected one-to-one, using stereomicroscopes, and transferred into 96-well microplates where one nauplius per well was added. The wells quickly have been filled with 300 µl of each specific concentration of the solution used, and control samples were incubated only with ASPM water. Replication was performed for each concentration. Finally, the microplates were placed on an orbital shaker, and the tests were read after 24 and 48 hours from inoculating the solutions to assess the endpoint (immobility/death) for the larvae. Nauplii that appeared motionless were counted as dead, and the percentages of mortality were calculated for each treatment. The results showed a low percentage of immobilization both for TiO₂-rGO at 1% and TiO₂-rGO at 2% for all concentrations tested: for TiO₂-rGO at 1% was below 12% after 24h and below 15% after 48h; for TiO₂-rGO at 2% was below 8% after 24h and below 12% after 48h. According to other studies in the literature, the results have not shown mortality nor toxic effects on the development of larvae after exposure to rGO. Finally, it is important to highlight that the TiO₂-rGO catalysts were tested in the solar photodegradation of a toxic herbicide (2,4-Dichlorophenoxyacetic acid, 2,4-D), obtaining a high percentage of degradation; therefore, this alternative approach could be considered a good strategy to obtain performing photocatalysts.

Keywords: Nauplii, photocatalytic properties, reduced GO, short-term toxicity test, titanium dioxide

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Authors: Assamen Ayalew Ejigu, Liang-Chiun Chao

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In recent semiconductor and nanotechnology, quality material synthesis, proper characterizations, and productions are the big challenges. As cuprous oxide (Cu2O) is a promising semiconductor material for photovoltaic (PV) and other optoelectronic applications, this study was aimed at to grow and characterize high quality Cu2O nanorods for the improvement of the efficiencies of thin film solar cells and other potential applications. In this study, well-structured cuprous oxide (Cu2O) nanorods were successfully fabricated using IBSD method in which the Cu2O samples were grown on silicon substrates with a substrate temperature of 400°C in an IBSD chamber of pressure of 4.5 x 10-5 torr using copper as a target material. Argon, and oxygen gases were used as a sputter and reactive gases, respectively. The characterization of the Cu2O nanorods (NRs) were done in comparison with Cu2O thin film (TF) deposited with the same method but with different Ar:O2 flow rates. With Ar:O2 ratio of 9:1 single phase pure polycrystalline Cu2O NRs with diameter of ~500 nm and length of ~4.5 µm were grow. Increasing the oxygen flow rates, pure single phase polycrystalline Cu2O thin film (TF) was found at Ar:O2 ratio of 6:1. The field emission electron microscope (FE-SEM) measurements showed that both samples have smooth morphologies. X-ray diffraction and Rama scattering measurements reveals the presence of single phase Cu2O in both samples. The differences in Raman scattering and photoluminescence (PL) bands of the two samples were also investigated and the results showed us there are differences in intensities, in number of bands and in band positions. Raman characterization shows that the Cu2O NRs sample has pronounced Raman band intensities, higher numbers of Raman bands than the Cu2O TF which has only one second overtone Raman signal at 2 (217 cm-1). The temperature dependent photoluminescence (PL) spectra measurements, showed that the defect luminescent band centered at 720 nm (1.72 eV) is the dominant one for the Cu2O NRs and the 640 nm (1.937 eV) band was the only PL band observed from the Cu2O TF. The difference in optical and structural properties of the samples comes from the oxygen flow rate change in the process window of the samples deposition. This gave us a roadmap for further investigation of the electrical and other optical properties for the tunable fabrication of the Cu2O nano/micro structured sample for the improvement of the efficiencies of thin film solar cells in addition to other potential applications. Finally, the novel morphologies, excellent structural and optical properties seen exhibits the grown Cu2O NRs sample has enough quality to be used in further research of the nano/micro structured semiconductor materials.

Keywords: defect levels, nanorods, photoluminescence, Raman modes

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Authors: Vinu Viswanath, Lawrence Dsouza, Ugo Ravon

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Syngas typically and intermediary gas product has a wide range of application of producing various chemical products, such as mixed alcohols, hydrogen, ammonia, Fischer-Tropsch products methanol, ethanol, aldehydes, alcohols, etc. There are several technologies available for the syngas production. An alternative to the conventional processes an attractive route of utilizing carbon dioxide and methane in equimolar ratio to generate syngas of ratio close to one has been developed which is also termed as Dry Reforming of Methane technology. It also gives the privilege to utilize the greenhouse gases like CO2 and CH4. The dry reforming process is highly endothermic, and indeed, ΔG becomes negative if the temperature is higher than 900K and practically, the reaction occurs at 1000-1100K. At this temperature, the sintering of the metal particle is happening that deactivate the catalyst. However, by using this strategy, the methane is just partially oxidized, and some cokes deposition occurs that causing the catalyst deactivation. The current research work was focused to mitigate the main challenges of dry reforming process such coke deposition, and metal sintering at high temperature.To achieve these objectives, we employed three different strategies of catalyst development. 1) Use of bulk catalysts such as olivine and pyrochlore type materials. 2) Use of metal doped support materials, like spinel and clay type material. 3) Use of core-shell model catalyst. In this approach, a thin layer (shell) of redox metal oxide is deposited over the MgAl2O4 /Al2O3 based support material (core). For the core-shell approach, an active metal is been deposited on the surface of the shell. The shell structure formed is a doped metal oxide that can undergo reduction and oxidation reactions (redox), and the core is an alkaline earth aluminate having a high affinity towards carbon dioxide. In the case of metal-doped support catalyst, the enhanced redox properties of doped CeO2 oxide and CO2 affinity property of alkaline earth aluminates collectively helps to overcome coke formation. For all of the mentioned three strategies, a systematic screening of the metals is carried out to optimize the efficiency of the catalyst. To evaluate the performance of them, the activity and stability test were carried out under reaction conditions of temperature ranging from 650 to 850 ̊C and an operating pressure ranging from 1 to 20 bar. The result generated infers that the core-shell model catalyst showed high activity and better stable DR catalysts under atmospheric as well as high-pressure conditions. In this presentation, we will show the results related to the strategy.

Keywords: carbon dioxide, dry reforming, supports, core shell catalyst

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Authors: Hilal Köse, Şeyma Dombaycıoğlu, Ali Osman Aydın, Hatem Akbulut

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Rechargeable lithium-ion batteries (LIBs) have become promising power sources for a wide range of applications, such as mobile communication devices, portable electronic devices and electrical/hybrid vehicles due to their long cycle life, high voltage and high energy density. Graphite, as anode material, has been widely used owing to its extraordinary electronic transport properties, large surface area, and high electrocatalytic activities although its limited specific capacity (372 mAh g-1) cannot fulfil the increasing demand for lithium-ion batteries with higher energy density. To settle this problem, many studies have been taken into consideration to investigate new electrode materials and metal oxide/graphene composites are selected as a kind of promising material for lithium ion batteries as their specific capacities are much higher than graphene. Among them, SnO₂, an n-type and wide band gap semiconductor, has attracted much attention as an anode material for the new-generation lithium-ion batteries with its high theoretical capacity (790 mAh g-1). However, it suffers from large volume changes and agglomeration associated with the Li-ion insertion and extraction processes, which brings about failure and loss of electrical contact of the anode. In addition, there is also a huge irreversible capacity during the first cycle due to the formation of amorphous Li₂O matrix. To obtain high capacity anode materials, we studied on the synthesis and characterization of SnO₂-Graphene nanocomposites and investigated the capacity of this free-standing anode material in this work. For this aim, firstly, graphite oxide was obtained from graphite powder using the method described by Hummers method. To prepare the nanocomposites as free-standing anode, graphite oxide particles were ultrasonicated in distilled water with SnO2 nanoparticles (1:1, w/w). After vacuum filtration, the GO-SnO₂ paper was peeled off from the PVDF membrane to obtain a flexible, free-standing GO paper. Then, GO structure was reduced in hydrazine solution. Produced SnO2- graphene nanocomposites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), and X-ray diffraction (XRD) analyses. CR2016 cells were assembled in a glove box (MBraun-Labstar). The cells were charged and discharged at 25°C between fixed voltage limits (2.5 V to 0.2 V) at a constant current density on a BST8-MA MTI model battery tester with 0.2C charge-discharge rate. Cyclic voltammetry (CV) was performed at the scan rate of 0.1 mVs-1 and electrochemical impedance spectroscopy (EIS) measurements were carried out using Gamry Instrument applying a sine wave of 10 mV amplitude over a frequency range of 1000 kHz-0.01 Hz.

Keywords: SnO₂-graphene, nanocomposite, anode, Li-ion battery

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Authors: Atef Y. Shenouda, Anton A. Momchilov

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Graphene and CdO with different stoichiometric ratios of Cd(CH₃COO)₂ and graphene samples were prepared by hydrothermal reaction. The crystalline phases of pure CdO and 3CdO:1graphene were identified by X-ray diffraction (XRD). The particle morphology was studied with SEM. Furthermore, impedance measurements were applied. Galvanostatic measurements for the cells were carried out using potential limits between 0.01 and 3 V vs. Li/Li⁺. The current cycling intensity was 10⁻⁴ A. The specific discharge capacity of 3CdO-1G cell was about 450 Ah.Kg⁻¹ up to more than 100 cycles.

Keywords: CdO, graphene, negative electrode, lithium battery

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Authors: Nusaiba Al-Nemrawi, Belal Al-Husein

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Methotrexate (MTX) is a stoichiometric inhibitor of dihydrofolate reductase, which is essential for DNA synthesis. MTX is a chemotherapeutic agent used for treating many types of cancer cells. However, cells’ resistant to MTX is very common and its pharmacokinetic behavior is highly problematic. of MTX within tumor cells, we propose encapsulation of antitumor drugs in nanoparticulated systems. Chitosan (CS) is a naturally occurring polymer that is biocompatibe, biodegradable, non-toxic, cationic and bioadhesive. CS nanoparticles (CS-NPs) have been used as drug carrier for targeted delivery. Titanium dioxide (TiO2), a natural mineral oxide, which is used in biomaterials due to its high stability and antimicrobial and anticorrosive properties. TiO2 showed a potential as a tumor suppressor. In this study a new formulation of MTX loaded in CS NPs (CS-MTX NPs) and coated with Titanium oxide (TiO2) was prepared. The mean particle size, zeta potential, polydispersity index were measured. The interaction between CS NPs and TiO2 NPs was confirmed using FTIR and XRD. CS-MTX NPs was studied in vitro using the tumor cell line MCF-7 (human breast cancer). The results showed that CS-MTX has a size around 169 nm and as they were coated with TiO2, the size ranged between and depending on the ratio of CS-MTX to TiO2 ratio used in the preparation. All NPs (uncoated and coated carried positive charges and were monodispersed. The entrapment efficacy was around 65%. Both FTIR and XRD proved that TiO2 interacted with CS-MTX NPs. The drug invitro release was controlled and sustained over days. Finally, the studied in vitro using the tumor cell line MCF-7 suggested that combining nanomaterials with anticancer drugs CS-MTX NPs may be more effective than free MTX for cancer treatment. In conclusion, the combination of CS-MTX NPs and TiO2 NPs showed excellent time-dependent in vitro antitumor behavior, therefore, can be employed as a promising anticancer agent to attain efficient results towards MCF-7 cells.

Keywords: Methotrexate, Titanium dioxide, Chitosan nanoparticles, cancer

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Authors: Diptiman Dinda, Shyamal Kumar Saha

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In the 21st century, sensitive and selective detection of trace amounts of explosives has become a serious problem. Generally, nitro compound and its derivatives are being used worldwide to prepare different explosives. Recently, TNP (2, 4, 6 trinitrophenol) is the most commonly used constituent to prepare powerful explosives all over the world. It is even powerful than TNT or RDX. As explosives are electron deficient in nature, it is very difficult to detect one separately from a mixture. Again, due to its tremendous water solubility, detection of TNP in presence of other explosives from water is very challenging. Simple instrumentation, cost-effective, fast and high sensitivity make fluorescence based optical sensing a grand success compared to other techniques. Graphene oxide (GO), with large no of epoxy grps, incorporate localized nonradiative electron-hole centres on its surface to give very weak fluorescence. In this work, GO is functionalized with 2, 6-diamino pyridine to remove those epoxy grps. through SN2 reaction. This makes GO into a bright blue luminescent fluorophore (DAP/rGO) which shows an intense PL spectrum at ∼384 nm when excited at 309 nm wavelength. We have also characterized the material by FTIR, XPS, UV, XRD and Raman measurements. Using this as fluorophore, a large fluorescence quenching (96%) is observed after addition of only 200 µL of 1 mM TNP in water solution. Other nitro explosives give very moderate PL quenching compared to TNP. Such high selectivity is related to the operation of FRET mechanism from fluorophore to TNP during this PL quenching experiment. TCSPC measurement also reveals that the lifetime of DAP/rGO drastically decreases from 3.7 to 1.9 ns after addition of TNP. Our material is also quite sensitive to 125 ppb level of TNP. Finally, we believe that this graphene based luminescent material will emerge a new class of sensing materials to detect trace amounts of explosives from aqueous solution.

Keywords: graphene, functionalization, fluorescence quenching, FRET, nitroexplosive detection

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Authors: Awadhesh Kishore

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The goal of the study was to determine how different non-metallic nutrients are partitioned from feed in various physiological contexts and how buffer addition in ruminant nutrition affects these processes. Six lactating crossbred dairy cows were selected and divided into three groups on the basis of their phenotypic and productive features (374±14 kg LW). Two treatments, T1 and T2, were randomly assigned to one animal from each group. Animals under T1 and T2 were moved to T2 and T1, respectively, after 30 days. T2 was the only group to receive buffers containing magnesium oxide and sodium bicarbonate at 0.0 and 0.01% of LW (the real amounts are equivalent to 75.3±4.0 and 30 7.7±2.0 g/d, respectively). T1 was used as the control. Wheat straw and berseem were part of the base diet, whereas wheat grain and mustard cake were part of the concentrate mixture. Following a 21-day feeding period, metabolic and milk production trials were carried out for seven consecutive days. The Kearl equation used the urine's calorific value to determine its volume. Chemical analyses were performed to determine the levels of nitrogen, carbohydrates, calories, and phosphorus in samples of feed, waste, buffer, mineral mixture, water, feces, urine, and milk that were collected. The information was analyzed statistically. Notable results included decreased nitrogen and carbohydrate partitioning to feces from feed, while increased calorie partitioning to milk and body storage, and increased carbohydrate partitioning to body storage. Phosphorus balance was significantly better in T2. The application of buffers in ruminant diets was found to increase the output of calories in milk, as well as the number of calories and carbohydrates stored in the body, while decreasing the amount of nitrogen in faeces. As a result, it may be advised to introduce buffers to feed crossbred dairy cattle.

Keywords: cattle, Magnesium oxide, non-metallic nutrients, partitioning, Sodium bicarbonate

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Authors: Usman B.M., Basheer O. B., . Ahmed A., Amali N. U., Taufeeq O.

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This study presents an investigation into the improvement of strength properties of concrete using egg shell powder (ESP) and groundnut husk ash (GHA) as additives so as to reduce its high cost and find alternative disposal method for agricultural waste. A standard consistency test was carried out on the egg shell powder and groundnut husk ash. A prescribed concrete mix ratio of 1:2:4 concrete cubes (150mm by 150mm) and water-cement ratio of 0.6 were casted. A total of One hundred and forty four (144) cubes were cast and cured for 3, 7 and 28 days and compressive strength subsequently determined in comparison with the relevant specifications. Consistency test on the cement paste at the various concentrations exhibited an increase in the setting time as the concentration increases with the highest value recorded at 5% egg shell powder and groundnut husk ash concentration as 219 minutes for the initial setting time and 275 minutes for the final setting time as against the control specimen of 159 minutes and 234 minutes for both initial and final setting times respectively. The results of the investigations showed that GHA was predominantly of Silicon oxide (56.73%) and a combined SiO₂, Al₂O₃ and Fe₂O₃ content of 66.75%; and the result of the investigations showed that ESP was predominantly of Calcium oxide (52.75%) and a combined SiO₂, Al₂O₃ and Fe₂O₃ content of 3.86%. The addition of GHA and ESP in concrete showed slight different in compressive strength with increase in GHA and ESP additive up to 5% and high decrease in compressive strength with further increase in GHA and ESP content. The 28 days compressive strength of the concrete cubes; compared with that of the control; showed a slight increase. Thus the use of GHA and ESP as partial replacement of cement will provide an economic use of by-product and consequently produce a cheaper concrete construction without comprising its strength

Keywords: additive, concrete, eggshell powder, groundnut husk ash compressive strength

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Authors: Nour S. Abdelrahman, Seunghyun Hong, Hassan A. Arafat, Daniel Choi, Faisal Al Marzooqi

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Abstract—The advancement of lithium extraction methods from water sources, particularly saltwater brine, is gaining prominence in the lithium recovery industry due to its cost-effectiveness. Traditional techniques like recrystallization, chemical precipitation, and solvent extraction for metal recovery from seawater or brine are energy-intensive and exhibit low efficiency. Moreover, the extensive use of organic solvents poses environmental concerns. As a result, there's a growing demand for environmentally friendly lithium recovery methods. Membrane-based separation technology has emerged as a promising alternative, offering high energy efficiency and ease of continuous operation. In our study, we explored the potential of lithium-selective sieve channels constructed from layers of 2D graphene oxide and MXene (transition metal carbides and nitrides), integrated with surface – SO₃₋ groups. The arrangement of these 2D sheets creates interplanar spacing ranging from 0.3 to 0.8 nm, which forms a barrier against multivalent ions while facilitating lithium-ion movement through nano capillaries. The introduction of the sulfonate group provides an effective pathway for Li⁺ ions, with a calculated binding energy of Li⁺ – SO³⁻ at – 0.77 eV, the lowest among monovalent species. These modified membranes demonstrated remarkably rapid transport of Li⁺ ions, efficiently distinguishing them from other monovalent and divalent species. This selectivity is achieved through a combination of size exclusion and varying binding affinities. The graphene oxide channels in these membranes showed exceptional inter-cation selectivity, with a Li⁺/Mg²⁺ selectivity ratio exceeding 104, surpassing commercial membranes. Additionally, these membranes achieved over 94% rejection of MgCl₂.

Keywords: ion permeation, lithium extraction, membrane-based separation, nanotechnology

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Authors: Bedarnia Ishak

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In the recent years, the dry reforming of methane has received considerable attention from an environmental view point because it consumes and eliminates two gases (CH4 and CO2) responsible for global warming by greenhouse effect. Many catalysts containing noble metal (Rh, Ru, Pd, Pt and Ir) or transition metal (Ni, Co and Fe) have been reported to be active in this reaction. Compared to noble metals, Ni-materials are cheap but very easily deactivated by coking. Ni-based mixed oxides structurally well-defined like perovskites and spinels are being studied because they possibly make solid solutions and allow to vary the composition and thus the performances properties. In this work, nano-sized nickel ferrite oxides are synthesized using three different methods: Co-precipitation (CP), hydrothermal (HT) and sol gel (SG) methods and characterized by XRD, Raman, XPS, BET, TPR, SEM-EDX and TEM-EDX. XRD patterns of all synthesized oxides showed the presence of NiFe2O4 spinel, confirmed by Raman spectroscopy. Hematite was present only in CP sample. Depending on the synthesis method, the surface area, particle size, as well as the surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied. The materials were tested in methane dry reforming with CO2 at 1 atm and 650-800 °C. The catalytic activity of the spinel samples was not very high (XCH4 = 5-20 mol% and XCO2 = 25-40 mol %) when no pre-reduction step was carried out. A significant contribution of RWGS explained the low values of H2/CO ratio obtained. The reoxidation step of the catalyst carried out after reaction showed little amounts of coke deposition. The reducing pretreatment was particularly efficient in the case of SG (XCH4 = 80 mol% and XCO2 = 92 mol%, at 800 °C), with H2/CO > 1. In conclusion, the influence of preparation was strong for most samples and the catalytic behavior could be interpreted by considering the distribution of cations among octahedral (Oh) and tetrahedral (Td) sites as in (Ni2+1-xFe3+x) Td (Ni2+xFe3+2-x) OhO2-4 influenced the reducibility of materials and thus their catalytic performance.

Keywords: NiFe2O4, dry reforming of methane, spinel oxide, oxide zenc

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Authors: Ligang Wang, Theodoros Damartzis, Stefan Diethelm, Jan Van Herle, François Marechal

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Biogas production from anaerobic digestion of organic sludge from wastewater treatment as well as various urban and agricultural organic wastes is of great significance to achieve a sustainable society. Two upgrading approaches for cleaned biogas can be considered: (1) direct H₂ injection for catalytic CO₂ methanation and (2) CO₂ separation from biogas. The first approach usually employs electrolysis technologies to generate hydrogen and increases the biogas production rate; while the second one usually applies commercially-available highly-selective membrane technologies to efficiently extract CO₂ from the biogas with the latter being then sent afterward for compression and storage for further use. A straightforward way of utilizing the captured CO₂ is on-site catalytic CO₂ methanation. From the perspective of system complexity, the second approach may be questioned, since it introduces an additional expensive membrane component for producing the same amount of methane. However, given the circumstance that the sustainability of the produced biogas should be retained after biogas upgrading, renewable electricity should be supplied to drive the electrolyzer. Therefore, considering the intermittent nature and seasonal variation of renewable electricity supply, the second approach offers high operational flexibility. This indicates that these two approaches should be compared based on the availability and scale of the local renewable power supply and not only the technical systems themselves. Solid-oxide electrolysis generally offers high overall system efficiency, and more importantly, it can achieve simultaneous electrolysis of CO₂ and H₂O (namely, co-electrolysis), which may bring significant benefits for the case of CO₂ separation from the produced biogas. When taking co-electrolysis into account, two additional upgrading approaches can be proposed: (1) direct steam injection into the biogas with the mixture going through the SOE, and (2) CO₂ separation from biogas which can be used later for co-electrolysis. The case study of integrating SOE to a wastewater treatment plant is investigated with wind power as the renewable power. The dynamic production of biogas is provided on an hourly basis with the corresponding oxygen and heating requirements. All four approaches mentioned above are investigated and compared thermo-economically: (a) steam-electrolysis with grid power, as the base case for steam electrolysis, (b) CO₂ separation and co-electrolysis with grid power, as the base case for co-electrolysis, (c) steam-electrolysis and CO₂ separation (and storage) with wind power, and (d) co-electrolysis and CO₂ separation (and storage) with wind power. The influence of the scale of wind power supply is investigated by a sensitivity analysis. The results derived provide general understanding on the economic competitiveness of SOE for sustainable biogas upgrading, thus assisting the decision making for biogas production sites. The research leading to the presented work is funded by European Union’s Horizon 2020 under grant agreements n° 699892 (ECo, topic H2020-JTI-FCH-2015-1) and SCCER BIOSWEET.

Keywords: biogas upgrading, solid-oxide electrolyzer, co-electrolysis, CO₂ utilization, energy storage

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Authors: Nikolai A. Khlebnikov, Vladimir N. Krasilnikov, Evgenii V. Polyakov, Anastasia A. Maltceva

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Carbon materials with advanced surfaces are widely used both in modern industry and in environmental protection. The physical-chemical nature of these materials is determined by the morphology of primary atomic and molecular carbon structures, which are the basis for synthesizing the following materials: zero-dimensional (fullerenes), one-dimensional (fiber, tubes), two-dimensional (graphene) carbon nanostructures, three-dimensional (multi-layer graphene, graphite, foams) with unique physical-chemical and functional properties. Experience shows that the microscopic morphological level is the basis for the creation of the next mesoscopic morphological level. The dependence of the morphology on the chemical way and process prehistory (crystallization, colloids formation, liquid crystal state and other) is the peculiarity of the last called level. These factors determine the consumer properties of carbon materials, such as specific surface area, porosity, chemical resistance in corrosive environments, catalytic and adsorption activities. Based on the developed ideology of thin precursor synthesis, the authors discuss one of the approaches of the porosity control of carbon-containing materials with a given aggregates morphology. The low-temperature thermolysis of precursors in a gas environment of a given composition is the basis of the above-mentioned idea. The processes of carbothermic precursor synthesis of two different compounds: tungsten carbide WC:nC and zinc oxide ZnO:nC containing an impurity phase in the form of free carbon were selected as subjects of the research. In the first case, the transition metal (tungsten) forming carbides was the object of the synthesis. In the second case, there was selected zinc that does not form carbides. The synthesis of both kinds of transition metals compounds was conducted by the method of precursor carbothermic synthesis from the organic solution. ZnO:nC composites were obtained by thermolysis of succinate Zn(OO(CH2)2OO), formate glycolate Zn(HCOO)(OCH2CH2O)1/2, glycerolate Zn(OCH2CHOCH2OH), and tartrate Zn(OOCCH(OH)CH(OH)COO). WC:nC composite was synthesized from ammonium paratungstate and glycerol. In all cases, carbon structures that are specific for diamond- like carbon forms appeared on the surface of WC and ZnO particles after the heat treatment. Tungsten carbide and zinc oxide were removed from the composites by selective chemical dissolution preserving the amorphous carbon phase. This work presents the results of investigating WC:nC and ZnO:nC composites and carbon nanopowders with tubular, tape, plate and onion morphologies of aggregates that are separated by chemical dissolution of WC and ZnO from the composites by the following methods: SEM, TEM, XPA, Raman spectroscopy, and BET. The connection between the carbon morphology under the conditions of synthesis and chemical nature of the precursor and the possibility of regulation of the morphology with the specific surface area up to 1700-2000 m2/g of carbon-structured materials are discussed.

Keywords: carbon morphology, composite materials, precursor synthesis, tungsten carbide, zinc oxide

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Authors: Tom S. Owens, Tom A. Calverley, Benjamin S. Stacey, Christopher J. Marley, George Rose, Lewis Fall, Gareth L. Jones, Priscilla Williams, John P. R. Williams, Martin Steggall, Damian M. Bailey

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Introduction and aims: Sports-related concussion (SRC) represents a significant and growing public health concern in rugby union, yet remains one of the least understood injuries facing the health community today. Alongside increasing SRC incidence rates, there is concern that prior recurrent concussion may contribute to long-term neurologic sequelae in later-life. This may be due to an accelerated decline in cerebral perfusion, a major risk factor for neurocognitive decline and neurodegeneration, though the underlying mechanisms remain to be established. The present study hypothesised that recurrent concussion in current professional rugby union players would result in elevated systemic oxidative-nitrosative stress, reflected by a free radical-mediated reduction in nitric oxide (NO) bioavailability and impaired cerebrovascular and cognitive function. Methodology: A longitudinal study design was adopted across the 2017-2018 rugby union season. Ethical approval was obtained from the University of South Wales Ethics Committee. Data collection is ongoing, and therefore the current report documents result from the pre-season and first half of the in-season data collection. Participants were initially divided into two subgroups; 23 professional rugby union players (aged 26 ± 5 years) and 22 non-concussed controls (27 ± 8 years). Pre-season measurements were performed for cerebrovascular function (Doppler ultrasound of middle cerebral artery velocity (MCAv) in response to hypocapnia/normocapnia/hypercapnia), cephalic venous concentrations of the ascorbate radical (A•-, electron paramagnetic resonance spectroscopy), NO (ozone-based chemiluminescence) and cognition (neuropsychometric tests). Notational analysis was performed to assess contact in the rugby group throughout each competitive game. Results: 1001 tackles and 62 injuries, including three concussions were observed across the first half of the season. However, no associations were apparent between number of tackles and any injury type (P > 0.05). The rugby group expressed greater oxidative stress as indicated by increased A•- (P < 0.05 vs. control) and a subsequent decrease in NO bioavailability (P < 0.05 vs. control). The rugby group performed worse in the Ray Auditory Verbal Learning Test B (RAVLT-B, learning, and memory) and the Grooved Pegboard test using both the dominant and non-dominant hands (visuomotor coordination, P < 0.05 vs. control). There were no between-group differences in cerebral perfusion at baseline (MCAv: 54 ± 13 vs. 59 ± 12, P > 0.05). Likewise, no between-group differences in CVRCO2Hypo (2.58 ± 1.01 vs. 2.58 ± 0.75, P > 0.05) or CVRCO2Hyper (2.69 ± 1.07 vs. 3.35 ± 1.28, P > 0.05) were observed. Conclusion: The present study identified that the rugby union players are characterized by impaired cognitive function subsequent to elevated systemic-oxidative-nitrosative stress. However, this appears to be independent of any functional impairment in cerebrovascular function. Given the potential long-term trajectory towards accelerated cognitive decline in populations exposed to SRC, prophylaxis to increase NO bioavailability warrants consideration.

Keywords: cognition, concussion, mild traumatic brain injury, rugby

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Authors: Mohamed S. Selim, Nesreen A. Fatthallah, Shimaa A. Higazy, Zhifeng Hao, Ping Jing Mo

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As marine fouling-release (FR) surfaces, two new superhydrophobic nanocomposite series of polydimethylsiloxane (PDMS) loaded with reduced graphene oxide (RGO) and graphene oxide/boehmite nanorods (GO-γ-AlOOH) nanofillers were created. The self-cleaning and antifouling capabilities were modified by controlling the nanofillers' shapes and distribution in the silicone matrix. With an average diameter of 10-20 nm and a length of 200 nm, γ-AlOOH nanorods showed a single crystallinity. RGO was made using a hydrothermal process, whereas GO-γ-AlOOH nanocomposites were made using a chemical deposition method for use as fouling-release coating materials. These nanofillers were disseminated in the silicone matrix using the solution casting method to explore the synergetic effects of graphene-based materials on the surface, mechanical, and FR characteristics. Water contact angle (WCA), scanning electron, and atomic force microscopes were used to investigate the surface's hydrophobicity and antifouling capabilities (SEM and AFM). The roughness, superhydrophobicity, and surface mechanical characteristics of coatings all increased the homogeneity of the nanocomposite dispersion. To examine the antifouling effects of the coating systems, laboratory tests were conducted for 30 days using specified bacteria.PDMS/GO-γ-AlOOH nanorod composite demonstrated superior antibacterial efficacy against several bacterial strains than PDMS/RGO nanocomposite. The high surface area and stabilizing effects of the GO-γ-AlOOH hybrid nanofillers are to blame for this. The biodegradability percentage of the PDMS/GO-γ-AlOOH nanorod composite (3 wt.%) was the lowest (1.6%), while the microbial endurability percentages for gram-positive, gram-negative, and fungi were 86.42%, 97.94%, and 85.97%, respectively. The homogeneity of the GO-γ-AlOOH (3 wt.%) dispersion, which had a WCA of 151° and a rough surface, was the most profound superhydrophobic antifouling nanostructured coating.

Keywords: superhydrophobic nanocomposite, fouling release, nanofillers, surface coating

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Authors: Shigenori Togashi, Yukako Asano

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We developed an effective microfluidic device for photoreactions with low reflectance and good heat conductance. The performance of this microfluidic device was tested by carrying out a photoreactive synthesis of benzopinacol and acetone from benzophenone and 2-propanol. The yield reached 36% with an irradiation time of 469.2 s and was improved by more than 30% when compared to the values obtained by the batch method. Therefore, the microfluidic device was found to be effective for improving the yields of photoreactions.

Keywords: microfluidic device, photoreaction, black aluminum oxide, benzophenone, yield improvement

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Authors: Hossein Anaraki-Ardakani

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A green and efficient one-pot synthesis of benzylamino coumarin derivatives by a three-component condensation of 4-hydroxycoumarin, cyclic secondary amine, and aromatic aldehyde in the presence of ZrO2 nanoparticles (NPs) as a heterogeneous catalyst in water at room temperature has been reported.

Keywords: 3-benzyl substituted coumarin derivative, ZrO2 nanoparticles (NPs), green synthesis, multicomponent reaction

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Authors: M. Saidi, I. Djefour, F. Ait Medjber, A. Melouane, A. Gacem

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The objective of this research is to study the physical and mechanical properties and durability of self-compacting mortars prepared by substituting a part of cement up to a percentage of 30% pozzolan according to different Blaine specific surface area (SSB1=7000 cm²/g and SSB=9000 cm²/g)). Order to evaluate durability, mortars were subjected to chemical attacks in various aggressive environments, a solution of a mixture of nitric acid and ammonium nitrate (HNO₃ + NH₄NO₃) and a magnesium sulfate salt solution (MgSO₄)) with a concentration of 10%, for a period of one month. This study is complemented by a comparative study of the durability of mortars elaborated with sulphate resistant cement (SRC). The results show that these mortars develop long-term, mechanical and chemical resistance better than mortars based Portland cement with 5% gypsum (CEM 1) and SRC. We found that the mass losses are lowest in mortars elaborated with pozzolanic cement (30% substitution with SSB₂) in both of chemical attack solutions (3.28% in the solution acid and 1.16% in the salt solution) and the compressive strength gains of 14.68% and 8.5% respectively in the two media. This is due to the action of pozzolan which fixes portlandite to form hydrated calcium silicate (CSH) from the hydration of tricalcic silicate (C₃S).

Keywords: aggressive environments, durability, mechanical strengths, pozzolanic cement, self-compacting mortar

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Authors: Victor S. Klimin, Alexey A. Rezvan, Maxim S. Solodovnik, Oleg A. Ageev

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In this paper, the problems of existing methods of profiling and surface modification of nanoscale arsenide-gallium structures are analyzed. The use of a combination of methods of local anodic oxidation and plasma chemical etching to solve this problem is considered. The main features that make this technology one of the promising areas of modification and profiling of near-surface layers of solids are demonstrated. In this paper, we studied the effect of formation stress and etching time on the geometrical parameters of the etched layer and the roughness of the etched surface. Experimental dependences of the thickness of the etched layer on the time and stress of formation were obtained. The surface analysis was carried out using atomic force microscopy methods, the corresponding profilograms were constructed from the obtained images, and the roughness of the etched surface was studied accordingly. It was shown that at high formation voltage, the depth of the etched surface increased, this is due to an increase in the number of active particles (oxygen ions and hydroxyl groups) formed as a result of the decomposition of water molecules in an electric field, during the formation of oxide nanostructures on the surface of gallium arsenide. Oxide layers were used as negative masks for subsequent plasma chemical etching by the STE ICPe68 unit. BCl₃ was chosen as the chlorine-containing gas, which differs from analogs in some parameters for the effect of etching of nanostructures based on gallium arsenide in the low-temperature plasma. The gas mixture of reaction chamber consisted of a buffer gas NAr = 100 cm³/min and a chlorine-containing gas NBCl₃ = 15 cm³/min at a pressure P = 2 Pa. The influence of these methods modes, which are formation voltage and etching time, on the roughness and geometric parameters, and corresponding dependences are demonstrated. Probe nanotechnology was used for surface analysis.

Keywords: nanostructures, GaAs, plasma chemical etching, modification structures

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Authors: P. Michael Preetam Raj, Souri Banerjee, Souvik Kundu

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Oxide based memristors were fabricated in order to establish its potential applications in analog/digital electronics. BaTiO₃-BiFeO₃ (BT-BFO) was employed as an active material, whereas platinum (Pt) and Nb-doped SrTiO₃ (Nb:STO) were served as a top and bottom electrodes, respectively. Piezoelectric force microscopy (PFM) was utilized to present the ferroelectricity and repeatable polarization inversion in the BT-BFO, demonstrating its effectiveness for resistive switching. The fabricated memristors exhibited excellent electrical characteristics, such as hysteresis current-voltage (I-V), high on/off ratio, high retention time, cyclic endurance, and low operating voltages. The band-alignment between the active material BT-BFO and the substrate Nb:STO was experimentally investigated using X-Ray photoelectron spectroscopy, and it attributed to staggered heterojunction alignment. An energy band diagram was proposed in order to understand the electrical transport in BT-BFO/Nb:STO heterojunction. It was identified that the I-V curves of these memristors have several discontinuities. Curve fitting technique was utilized to analyse the I-V characteristic, and the obtained I-V equations were found to be parabolic. Utilizing this analysis, a non-linear BT-BFO memristors equivalent circuit model was developed. Interestingly, the obtained equivalent circuit of the BT-BFO memristors mimics the identical electrical performance, those obtained in the fabricated devices. Based on the developed equivalent circuit, a finite state machine (FSM) design was proposed. Efforts were devoted to fabricate the same FSM, and the results were well matched with those in the simulated FSM devices. Its multilevel noise filtering and immunity to external noise characteristics were also studied. Further, the feature of variable negative resistance was established by controlling the current through the memristor.

Keywords: band alignment, finite state machine, polarization inversion, resistive switching

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Authors: Aleksander Ejsmont, Stefan Wuttke, Joanna Goscianska

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Gaining control over particle shape, size and crystallinity is an ongoing challenge for many materials. Especially metalorganic frameworks (MOFs) are recently widely studied. Besides their remarkable porosity and interesting topologies, morphology has proven to be a significant feature. It can affect the further material application. Thus seeking new approaches that enable MOF morphology modulation is important. MOFs are reticular structures, where building blocks are made up of organic linkers and metallic nodes. The most common strategy of ensuring metal source is using salts, which usually exhibit high solubility and hinder morphology control. However, there has been a growing interest in using metal oxides as structure-directing agents towards MOFs due to their very low solubility and shape preservation. Metal oxides can be treated as a metal reservoir during MOF synthesis. Up to now, reports in which receiving MOFs from metal oxides mostly present ZnO conversion to ZIF-8. However, there are other oxides, for instance, Co₃O₄, which often is overlooked due to their structural stability and insolubility in aqueous solutions. Cobalt-based materials are famed for catalytic activity. Therefore the development of their efficient synthesis is worth attention. In the presented work, an optimized Co₃O₄transition to Co-MOFviaa solvothermal approach was proposed. The starting point of the research was the synthesis of Co₃O₄ flower petals and needles under hydrothermal conditions using different cobalt salts (e.g., cobalt(II) chloride and cobalt(II) nitrate), in the presence of urea, and hexadecyltrimethylammonium bromide (CTAB) surfactant as a capping agent. After receiving cobalt hydroxide, the calcination process was performed at various temperatures (300–500 °C). Then cobalt oxides as a source of cobalt cations were subjected to reaction with trimesic acid in solvothermal environment and temperature of 120 °C leading to Co-MOF fabrication. The solution maintained in the system was a mixture of water, dimethylformamide, and ethanol, with the addition of strong acids (HF and HNO₃). To establish how solvents affect metal oxide conversion, several different solvent ratios were also applied. The materials received were characterized with analytical techniques, including X-ray powder diffraction, energy dispersive spectroscopy,low-temperature nitrogen adsorption/desorption, scanning, and transmission electron microscopy. It was confirmed that the synthetic routes have led to the formation of Co₃O₄ and Co-based MOF varied in shape and size of particles. The diffractograms showed receiving crystalline phase for Co₃O₄, and also for Co-MOF. The Co₃O₄ obtained from nitrates and with using low-temperature calcination resulted in smaller particles. The study indicated that cobalt oxide particles of different size influence the efficiency of conversion and morphology of Co-MOF. The highest conversion was achieved using metal oxides with small crystallites.

Keywords: Co-MOF, solvothermal synthesis, morphology control, core-shell

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Authors: Saba Didarataee, Abbas Ali Khodadadi, Yadollah Mortazavi, Fatemeh Mousavi

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Photocatalytic water splitting is one of the most attractive alternative methods for hydrogen evolution. A variety of nanoparticle engineering techniques were introduced to improve the activity of semiconductor photocatalysts. Among these methods, heterojunction formation is an appealing method due to its ability to effectively preventing electron-hole recombination and improving photocatalytic activity. Reaching an optimal ratio of the two target semiconductors for the formation of heterojunctions is still an open question. Considering environmental issues as well as the cost and availability, ZnS and ZnO are frequently studied as potential choices. In this study, first, the ZnS nanoparticle was synthesized in a hydrothermal process; the formation of ZnS nanorods with a diameter of 14-30 nm was confirmed by field emission scanning electron microscope (FESEM). Then two different methods, partial oxidation and chemical precipitation were employed to construct ZnS/ZnO core-shell heterojunction. X-ray diffraction (XRD), BET, and diffuse reflectance spectroscopy (DRS) analysis were carried out to determine crystallite phase, surface area, and bandgap of photocatalysts. Furthermore, the temperature of oxidation was specified by a temperature programmed oxidation (TPO) and was fixed at 510℃, at which mild oxidation occurred. The bandgap was calculated by the Kubelka-Munk method and decreased by increasing oxide content from 3.53 (pure ZnS) to 3.18 (pure ZnO). The optimal samples were determined by testing the photocatalytic activity of hydrogen evolution in a quartz photoreactor with side irradiation of UVC lamps with a wavelength of 254 nm. In both procedures, it was observed that the photocatalytic activity of the ZnS/ZnO composite was sensibly higher than the pure ZnS and ZnO, which is attributed to forming a type-II heterostructure. The best ratio of oxide to sulfide was 0.24 and 0.37 in partial oxidation and chemical precipitation, respectively. The highest hydrogen evolution was 1081 µmol/gr.h, gained from partial oxidizing of ZnS nanoparticles at 510℃ for 30 minutes.

Keywords: heterostructure, hydrogen, partial oxidation, photocatalyst, water splitting, ZnS

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Authors: Sahin Yakut, H. Kemal Ulutas, Deniz Deger

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Plasma Assisted Physical Vapor Deposition (PAPVD) method used to produce Poly(ethylene oxide) (pPEO) thin films. Depositions were progressed at various plasma discharge powers as 0, 2, 5 and 30 W for pPEO at 500nm film thicknesses. The capacitance and dielectric dissipation of the thin films were measured at 0,1-107 Hz frequency range and 173-353 K temperature range by an impedance analyzer. Then, alternative conductivity (σac) and activation energies were derived from capacitance and dielectric dissipation. σac of conventional PEO (PEO precursor) was measured to determine the effect of plasma discharge. Differences were observed between the alternative conductivity of PEO’s and pPEO’s depending on plasma discharge power. By this purpose, structural characterization techniques such as Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) were applied on pPEO thin films. Structural analysis showed that density of crosslinking is plasma power dependent. The crosslinking density increases with increasing plasma discharge power and this increase is displayed as increasing dynamic glass transition temperatures at DSC results. Also, shifting of frequencies of some type of bond vibrations, belonging to bond vibrations produced after fragmentation because of plasma discharge, were observed at FTIR results. The dynamic glass transition temperatures obtained from alternative conductivity results for pPEO consistent with the results of DSC. Activation energies exhibit Arrhenius behavior. Activation energies decrease with increasing plasma discharge power. This behavior supports the suggestion expressing that long polymer chains and long oligomers are fragmented into smaller oligomers or radicals.

Keywords: activation energy, dielectric spectroscopy, organic thin films, plasma polymer

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Authors: Syed Kamran Sami, Saqib Siddiqui

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In recent times, flexible supercapacitors retaining high electrochemical performance and steadiness along with mechanical endurance has developed as a spring of attraction due to the exponential progress and innovations in energy storage devices. To meet the rampant increasing demand of energy storage device with the small form factor, a unique, low cost and high-performance supercapacitor with considerably higher capacitance and mechanical robustness is required to recognize their real-life applications. Here in this report, synthesis route of electrode materials with low rigidity and high charge storage performance is reported using 1D-1D hybrid structure of zinc oxide (ZnO) nanorods, and conductive polymer smeared polyvinylidene fluoride–trifluoroethylene (P(VDF–TrFE)) electrospun nanofibers. The ZnO nanorods were uniformly grown on poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) coated P(VDF-TrFE) nanofibers using hydrothermal growth to manufacture light weight, permeable electrodes for supercapacitor. The PEDOT: PSS coated P(VDF-TrFE) porous web of nanofibers act as framework with high surface area. The incorporation of ZnO nanorods further boost the specific capacitance by 59%. The symmetric device using the fabricated 1D-1D hybrid electrodes reveals fairly high areal capacitance of 1.22mF/cm² at a current density of 0.1 mA/cm² with a power density of more than 1600 W/Kg. Moreover, the fabricated electrodes show exceptional flexibility and high endurance with 90% and 76% specific capacitance retention after 1000 and 5000 cycles respectively signifying the astonishing mechanical durability and long-term stability. All the properties exhibited by the fabricated electrode make it convenient for making flexible energy storage devices with the low form factor.

Keywords: ZnO nanorods, electrospinning, mechanical endurance, flexible supercapacitor

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Authors: Kuladip Jana

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Benzo(a)pyrene [B(a)P] is an environmental toxicant present mostly in cigarette smoke and car exhaust, is an aryl hydrocarbon receptor (AhR) ligand that exerts its toxic effects on both male and female reproductive systems. In this study, the effect of B(a)P at different doses (0.1, 0.25, 0.5, 1 and 5 mg /kg body weight) was studied on male reproductive system of rat. A significant decrease in cauda epididymal sperm count and motility along with the presence of sperm head abnormalities and altered epididymal and testicular histology were documented following B(a)P treatment. B(a)P treatment resulted apoptotic sperm cells as observed by TUNEL and Annexin V-PI assay with increased ROS, altered sperm mitochondrial membrane potential (ΔΨm) with a simultaneous decrease in the activity of antioxidant enzymes and GSH status. TUNEL positive apoptotic cells also observed in testis as well as isolated germ and Leydig cells following B(a)P exposure. Western Blot analysis revealed the activation of p38MAPK, cytosolic translocation of cytochrome-c, up-regulation of Bax and inducible nitric oxide synthase (iNOS) with cleavage of PARP and down-regulation of BCl2 in testis upon B(a)P treatment. The protein and mRNA levels of testicular key steroidogenesis regulatory proteins like StAR, cytochrome P450 IIA1 (CYPIIA1), 3β HSD, 17β HSD showed a significant decrease in a dose dependent manner while an increase in the expression of cytochrome P450 1A1 (CYP1A1), Aryl hydrocarbon Receptor (AhR), active caspase- 9 and caspase- 3 following B(a)P exposure. We conclude that exposure of benzo(a)pyrene caused testicular gamatogenic and steroidogenic disorders by induction of oxidative stress, inhibition of StAR and other steroidogenic enzymes along with activation of p38MAPK and initiated caspase-3 mediated germ and Leydig cell apoptosis.The possible protective role of naturally occurring phytochemicals against B(a)P induced testicular toxicity needs immediate consideration. Curcumin and resveratrol separately were found to protect against B(a)P induced germ cell apoptosis, and their combinatorial effect was more significant. Our present study in isolated testicular germ cell population from adult male Wistar rats, highlighted their synergistic protective effect against B(a)P induced germ cell apoptosis. Curcumin-resveratrol co-treatment decreased the expression of pro-apoptotic proteins like cleaved caspase 3,8,9, cleaved PARP, Apaf1, FasL, tBid. Curcumin-resveratrol co-treatment decreased Bax/Bcl2 ratio, mitochondria to cytosolic translocation of cytochrome c and activated the survival protein Akt. Curcumin-resveratrol decreased the expression of p53 dependent apoptotic genes like Fas, FasL, Bax, Bcl2, Apaf1.Curcumin-resveratrol co-treatment thus prevented B(a)P induced germ cell apoptosis. B(a)P induced testicular ROS generation and oxidative stress were significantly ameliorated with curcumin and resveratrol. Curcumin-resveratrol co-treatment prevented B(a)P induced nuclear translocation of AhR and CYP1A1 production. The combinatorial treatment significantly inhibited B(a)P induced ERK 1/2, p38 MAPK and JNK 1/2 activation. B(a)P treatment increased the expression of p53 and its phosphorylation (p53 ser 15). Curcumin-resveratrol co-treatment significantly decreased p53 level and its phosphorylation (p53 ser 15). The study concludes that curcumin-resveratrol synergistically modulated MAPKs and p53, prevented oxidative stress, regulated the expression of pro and anti-apoptotic proteins as well as the proteins involved in B(a)P metabolism thus protected germ cells from B(a)P induced apoptosis.

Keywords: benzo(a)pyrene, germ cell, apoptosis, oxidative stress, resveratrol, curcumin

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