Search results for: Cu-Mn-La oxide catalysts
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1782

Search results for: Cu-Mn-La oxide catalysts

882 Iron Oxide Reduction Using Solar Concentration and Carbon-Free Reducers

Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

Abstract:

The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

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881 Electrochemical Performance of Femtosecond Laser Structured Commercial Solid Oxide Fuel Cells Electrolyte

Authors: Mohamed A. Baba, Gazy Rodowan, Brigita Abakevičienė, Sigitas Tamulevičius, Bartlomiej Lemieszek, Sebastian Molin, Tomas Tamulevičius

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Solid oxide fuel cells (SOFC) efficiently convert hydrogen to energy without producing any disturbances or contaminants. The core of the cell is electrolyte. For improving the performance of electrolyte-supported cells, it is desirable to extend the available exchange surface area by micro-structuring of the electrolyte with laser-based micromachining. This study investigated the electrochemical performance of cells micro machined using a femtosecond laser. Commercial ceramic SOFC (Elcogen, AS) with a total thickness of 400 μm was structured by 1030 nm wavelength Yb: KGW fs-laser Pharos (Light Conversion) using 100 kHz repetition frequency and 290 fs pulse length light by scanning with the galvanometer scanner (ScanLab) and focused with a f-Theta telecentric lens (SillOptics). The sample height was positioned using a motorized z-stage. The microstructures were formed using a laser spiral trepanning in Ni/YSZ anode supported membrane at the central part of the ceramic piece of 5.5 mm diameter at active area of the cell. All surface was drilled with 275 µm diameter holes spaced by 275 µm. The machining processes were carried out under ambient conditions. The microstructural effects of the femtosecond laser treatment on the electrolyte surface were investigated prior to the electrochemical characterisation using a scanning electron microscope (SEM) Quanta 200 FEG (FEI). The Novo control Alpha-A was used for electrochemical impedance spectroscopy on a symmetrical cell configuration with an excitation amplitude of 25 mV and a frequency range of 1 MHz to 0.1 Hz. The fuel cell characterization of the cell was examined on open flanges test setup by Fiaxell. Using nickel mesh on the anode side and au mesh on the cathode side, the cell was electrically linked. The cell was placed in a Kittec furnace with a Process IDentifier temperature controller. The wires were connected to a Solartron 1260/1287 frequency analyzer for the impedance and current-voltage characterization. In order to determine the impact of the anode's microstructure on the performance of the commercial cells, the acquired results were compared to cells with unstructured anode. Geometrical studies verified that the depth of the -holes increased linearly according to laser energy and scanning times. On the other hand, it reduced as the scanning speed increased. The electrochemical analysis demonstrates that the open circuit voltage OCV values of the two cells are equal. Further, the modified cell's initial slope reduces to 0.209 from 0.253 of the unmodified cell, revealing that the surface modification considerably decreases energy loss. Plus, the maximum power density for the cell with the microstructure and the reference cell respectively, are 1.45 and 1.16 Wcm⁻².

Keywords: electrochemical performance, electrolyte-supported cells, laser micro-structuring, solid oxide fuel cells

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880 Exploring Tree Growth Variables Influencing Carbon Sequestration in the Face of Climate Change

Authors: Funmilayo Sarah Eguakun, Peter Oluremi Adesoye

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One of the major problems being faced by human society is that the global temperature is believed to be rising due to human activity that releases carbon IV oxide (CO2) to the atmosphere. Carbon IV oxide is the most important greenhouse gas influencing global warming and possible climate change. With climate change becoming alarming, reducing CO2 in our atmosphere has become a primary goal of international efforts. Forest landsare major sink and could absorb large quantities of carbon if the trees are judiciously managed. The study aims at estimating the carbon sequestration capacity of Pinus caribaea (pine)and Tectona grandis (Teak) under the prevailing environmental conditions and exploring tree growth variables that influencesthe carbon sequestration capacity in Omo Forest Reserve, Ogun State, Nigeria. Improving forest management by manipulating growth characteristics that influences carbon sequestration could be an adaptive strategy of forestry to climate change. Random sampling was used to select Temporary Sample Plots (TSPs) in the study area from where complete enumeration of growth variables was carried out within the plots. The data collected were subjected to descriptive and correlational analyses. The results showed that average carbon stored by Pine and Teak are 994.4±188.3 Kg and 1350.7±180.6 Kg respectively. The difference in carbon stored in the species is significant enough to consider choice of species relevant in climate change adaptation strategy. Tree growth variables influence the capacity of the tree to sequester carbon. Height, diameter, volume, wood density and age are positively correlated to carbon sequestration. These tree growth variables could be manipulated by the forest manager as an adaptive strategy for climate change while plantations of high wood density speciescould be relevant for management strategy to increase carbon storage.

Keywords: adaptation, carbon sequestration, climate change, growth variables, wood density

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879 The Application of New Ligands including Different Atoms and Evaluation of Their Nucleophile Effects against Various Metals

Authors: Saman Hajmohamadi, Sohrab Hajmohamadi

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The objectives of this experiment were to investigate the application of new ligands including different atoms and evaluation of their nucleophile effects against various metals. Chemistry researchers are really interested in this field. From among various ligands, there are some ligands with different coordinating ligands as well. There are great number of intermediate complexes and major elements of organic compositions with various atoms. There is a regular adding of new compositions. Complexes are the most important chemical combinations with various catalysts and biological, medicinal and other applications. Those complexes with ligands including different atom givers are really important and their synthesis could solve most of chemical problems. Supplying of new ligands is an important and key part of coordination chemistry which may cause some varieties and different properties in complexes with equal central nucleus. As a result, this research has evaluated new ligands including different coordination atoms, such as oxygen, nitrogen etc. along with their behavior against various metals like copper, nickel, iron etc.

Keywords: ligands, nucleophile, iron, cobalt, copper

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878 Application of Host Factors as Biomarker in Early Diagnosis of Pulmonary Tuberculosis

Authors: Ambrish Tiwari, Sudhasini Panda, Archana Singh, Kalpana Luthra, S. K. Sharma

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Introduction: On the basis of available literature we know that various host factors play a role in outcome of Tuberculosis (TB) infection by modulating innate immunity. One such factor is Inducible Nitric Oxide Synthase enzyme (iNOS) which help in the production of Nitric Oxide (NO), an antimicrobial agent. Expression of iNOS is in control of various host factors in which Vitamin D along with its nuclear receptor Vitamin D receptor (VDR) is one of them. Vitamin D along with its receptor also produces cathelicidin (antimicrobicidal agent). With this background, we attempted to investigate the levels of Vitamin D and NO along with their associated molecules in tuberculosis patients and household contacts as compared to healthy controls and assess the implication of these findings in susceptibility to tuberculosis (TB). Study subjects and methods: 100 active TB patients, 75 household contacts, and 70 healthy controls were taken. VDR and iNOS mRNA levels were studied using real-time PCR. Serum VDR, cathelicidin, iNOS levels were measured using ELISA. Serum Vitamin D levels were measured in serum samples using chemiluminescence based immunoassay. NO was measured using colorimetry based kit. Results: VDR and iNOS mRNA levels were found to be lower in active TB group compared to household contacts and healthy controls (P=0.0001 and 0.005 respectively). The serum levels of Vitamin D were also found to be lower in active TB group as compared to healthy controls (P =0.001). Levels of cathelicidin and NO was higher in patient group as compared to other groups (p=0.01 and 0.5 respectively). However, the expression of VDR and iNOS and levels of vitamin D was significantly (P < 0.05) higher in household contacts compared to both active TB and healthy control groups. Inference: Higher levels of Vitamin D along with VDR and iNOS expression in household contacts as compared to patients suggest that vitamin D might have a protective role against TB which prevents activation of the disease. From our data, we can conclude that decreased vitamin D levels could be implicated in disease progression and we can use cathelicidin and NO as a biomarker for early diagnosis of pulmonary tuberculosis.

Keywords: vitamin D, VDR, iNOS, tuberculosis

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877 Magnetic Properties of Nickel Oxide Nanoparticles in Superparamagnetic State

Authors: Navneet Kaur, S. D. Tiwari

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Superparamagnetism is an interesting phenomenon and observed in small particles of magnetic materials. It arises due to a reduction in particle size. In the superparamagnetic state, as the thermal energy overcomes magnetic anisotropy energy, the magnetic moment vector of particles flip their magnetization direction between states of minimum energy. Superparamagnetic nanoparticles have been attracting the researchers due to many applications such as information storage, magnetic resonance imaging, biomedical applications, and sensors. For information storage, thermal fluctuations lead to loss of data. So that nanoparticles should have high blocking temperature. And to achieve this, nanoparticles should have a higher magnetic moment and magnetic anisotropy constant. In this work, the magnetic anisotropy constant of the antiferromagnetic nanoparticles system is determined. Magnetic studies on nanoparticles of NiO (nickel oxide) are reported well. This antiferromagnetic nanoparticle system has high blocking temperature and magnetic anisotropy constant of order 105 J/m3. The magnetic study of NiO nanoparticles in the superparamagnetic region is presented. NiO particles of two different sizes, i.e., 6 and 8 nm, are synthesized using the chemical route. These particles are characterized by an x-ray diffractometer, transmission electron microscope, and superconducting quantum interference device magnetometry. The magnetization vs. applied magnetic field and temperature data for both samples confirm their superparamagnetic nature. The blocking temperature for 6 and 8 nm particles is found to be 200 and 172 K, respectively. Magnetization vs. applied magnetic field data of NiO is fitted to an appropriate magnetic expression using a non-linear least square fit method. The role of particle size distribution and magnetic anisotropy is taken in to account in magnetization expression. The source code is written in Python programming language. This fitting provides us the magnetic anisotropy constant for NiO and other magnetic fit parameters. The particle size distribution estimated matches well with the transmission electron micrograph. The value of magnetic anisotropy constants for 6 and 8 nm particles is found to be 1.42 X 105 and 1.20 X 105 J/m3, respectively. The obtained magnetic fit parameters are verified using the Neel model. It is concluded that the effect of magnetic anisotropy should not be ignored while studying the magnetization process of nanoparticles.

Keywords: anisotropy, superparamagnetic, nanoparticle, magnetization

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876 Studies on Structural and Electrical Properties of Lanthanum Doped Sr₂CoMoO₆₋δ System

Authors: Pravin Kumar, Rajendra K. Singh, Prabhakar Singh

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A widespread research work on Mo-based double perovskite systems has been reported as a potential application for electrode materials of solid oxide fuel cells. Mo-based double perovskites studied in form of B-site ordered double perovskite materials, with general formula A₂B′B″O₆ structured by alkaline earth element (A = Sr, Ca, Ba) and heterovalent transition metals (B′ = Fe, Co, Ni, Cr, etc. and B″ = Mo, W, etc.), are raising a significant interest as potential mixed ionic-electronic conductors in the temperature range of 500-800 °C. Such systems reveal higher electrical conductivity, particularly those assigned in form of Sr₂CoMoO₆₋δ (M = Mg, Mn, Fe, Co, Ni, Zn etc.) which were studied in different environments (air/H₂/H₂-Ar/CH₄) at an intermediate temperature. Among them, the Sr₂CoMoO₆₋δ system is a potential candidate as an anode material for solid oxide fuel cells (SOFCs) due to its better electrical conductivity. Therefore, Sr₂CoMoO₆₋δ (SCM) system with La-doped on Sr site has been studied to discover the structural and electrical properties. The double perovskite system Sr₂CoMoO₆₋δ (SCM) and doped system Sr₂-ₓLaₓCoMoO₆₋δ (SLCM, x=0.04) were synthesized by the citrate-nitrate combustion synthesis route. Thermal studies were carried out by thermo-gravimetric analysis. Phase justification was confirmed by powder X-ray diffraction (XRD) as a tetragonal structure with space group I4/m. A minor phase of SrMoO₄ (s.g. I41/a) was identified as a secondary phase using JCPDS card no. 85-0586. Micro-structural investigations revealed the formation of uniform grains. The average grain size of undoped (SCM) and doped (SLCM) compositions was calculated by a linear intercept method and found to be ⁓3.8 μm and 2.7 μm, respectively. The electrical conductivity of SLCM is found higher than SCM in the air within the temperature range of 200-600 °C. SLCM system was also measured in reducing atmosphere (pure H₂) in the temperature range 300-600 °C. SLCM has been showed the higher conductivity in the reducing atmosphere (H₂) than in air and therefore it could be a promising anode material for SOFCs.

Keywords: double perovskite, electrical conductivity, SEM, XRD

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875 Electrochemical Study of Ni and/or Fe Based Mono- And Bi- Hydroxides

Authors: H. Benaldjia, N. Habib, F. Djefaflia, A. Nait-Merzoug, A. Harat, J. El-Haskouri, O. Guellati

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Currently, the technology has attracted knowledge of energy storage sources similar to batteries, capacitors and super-capacitors because of its very different applications in many fields with major social and economic challenges. Moreover, hydroxides have attracted much attention as a promising and active material choice in large-scale applications such as molecular adsorption/storage and separation for the environment, ion exchange, nanotechnology, supercapacitor for energy storage and conversion, electro-biosensing, and catalysts, due to their unique properties which are strongly influenced by their composition, microstructure, and synthesis method. In this context, we report in this study the synthesis of hydroxide-based nanomaterials precisely based on Ni and Fe using a simple hydrothermal method with mono and bi precursors at optimized growth conditions (6h-120°C). The obtained products were characterized using different techniques, such as XRD, FTIR, FESEM and BET, as well as electrochemical measurements.

Keywords: energy storage, Supercapacitors, nanocomposites, nanohybride, electro-active materials.

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874 Microwave-Assisted Fabrication of Visible-Light Activated BiOBr-Nanoplate Photocatalyst

Authors: Meichen Lee, Michael K. H. Leung

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In recent years, visible-light activated photocatalysis has become a major field of intense researches for the higher efficiency of solar energy utilizations. Many attempts have been made on the modification of wide band gap semiconductors, while more and more efforts emphasize on cost-effective synthesis of visible-light activated catalysts. In this work, BiOBr nanoplates with band gap of visible-light range are synthesized through a promising microwave solvothermal method. The treatment time period and temperature dependent BiOBr nanosheets of various particle sizes are investigated through SEM. BiOBr synthesized under the condition of 160°C for 60 mins shows the most uniform particle sizes around 311 nm and the highest surface-to-volume ratio on account of its smallest average particle sizes compared with others. It exhibits the best photocatalytic behavior among all samples in RhB degradation.

Keywords: microwave solvothermal process, nanoplates, solar energy, visible-light photocatalysis

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873 Li2o Loss of Lithium Niobate Nanocrystals during High-Energy Ball-Milling

Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis

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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.

Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals

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872 Charge Transport of Individual Thermoelectric Bi₂Te₃ Core-Poly(3,4-Ethylenedioxythiophene):Polystyrenesulfonate Shell Nanowires Determined Using Conductive Atomic Force Microscopy and Spectroscopy

Authors: W. Thongkham, K. Sinthiptharakoon, K. Tantisantisom, A. Klamchuen, P. Khanchaitit, K. Jiramitmongkon, C. Lertsatitthanakorn, M. Liangruksa

Abstract:

Due to demands of sustainable energy, thermoelectricity converting waste heat into electrical energy has become one of the intensive fields of worldwide research. However, such harvesting technology has shown low device performance in the temperature range below 150℃. In this work, a hybrid nanowire of inorganic bismuth telluride (Bi₂Te₃) and organic poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) synthesized using a simple in-situ one-pot synthesis, enhancing efficiency of the nanowire-incorporated PEDOT:PSS-based thermoelectric converter is highlighted. Since the improvement is ascribed to the increased electrical conductivity of the thermoelectric host material, the individual hybrid nanowires are investigated using voltage-dependent conductive atomic force microscopy (CAFM) and spectroscopy (CAFS) considering that the electrical transport measurement can be performed either on insulating or conducting areas of the sample. Correlated with detailed chemical information on the crystalline structure and compositional profile of the nanowire core-shell structure, an electrical transporting pathway through the nanowire and the corresponding electronic-band structure have been determined, in which the native oxide layer on the Bi₂Te₃ surface is not considered, and charge conduction on the topological surface states of Bi₂Te₃ is suggested. Analyzing the core-shell nanowire synthesized using the conventional mixing of as-prepared Bi₂Te₃ nanowire with PEDOT:PSS for comparison, the oxide-removal effect of the in-situ encapsulating polymeric layer is further supported. The finding not only provides a structural information for mechanistic determination of the thermoelectricity, but it also encourages new approach toward more appropriate encapsulation and consequently higher efficiency of the nanowire-based thermoelectric generation.

Keywords: electrical transport measurement, hybrid Bi₂Te₃-PEDOT:PSS nanowire, nanoencapsulation, thermoelectricity, topological insulator

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871 Non-Steroidal Anti-inflammatory Drugs, Plant Extracts, and Characterized Microparticles to Modulate Antimicrobial Resistance of Epidemic Meca Positive S. Aureus of Dairy Origin

Authors: Amjad I. Aqib, Shanza R. Khan, Tanveer Ahmad, Syed A. R. Shah, Muhammad A. Naseer, Muhammad Shoaib, Iqra Sarwar, Muhammad F. A. Kulyar, Zeeshan A. Bhutta, Mumtaz A. Khan, Mahboob Ali, Khadija Yasmeen

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The current study focused on resistance modulation of dairy linked epidemic mec A positive S. aureus for resistance modulation by plant extract (Eucalyptus globolus, Calotropis procera), NSAIDs, and star like microparticles. Zinc oxide {ZnO}c and {Zn (OH)₂} microparticles were synthesized by solvothermal method and characterized by calcination, X-ray diffraction (XRD), and scanning electron microscope (SEM). Plant extracts were prepared by the Soxhlet extraction method. The study found 34% of subclinical samples (n=200) positive for S. aureus from dairy milk having significant (p < 0.05) association of assumed risk factors with pathogen. The antimicrobial assay showed 55, 42, 41, and 41% of S. aureus resistant to oxacillin, ciprofloxacin, streptomycin, and enoxacin. Amoxicillin showed the highest percentage of increase in zone of inhibitions (ZOI) at 100mg of Calotropis procera extract (31.29%) followed by 1mg/mL (28.91%) and 10mg/mL (21.68%) of Eucalyptus globolus. Amoxicillin increased ZOI by 42.85, 37.32, 29.05, and 22.78% in combination with 500 ug/ml with each of diclofenac, aspirin, ibuprofen, and meloxicam, respectively. Fractional inhibitory concentration indices (FICIs) showed synergism of amoxicillin with diclofenac and aspirin and indifferent synergy with ibuprofen and meloxicam. The preliminary in vitro finding of combination of microparticles with amoxicillin proved to be synergistic, giving rise to 26.74% and 14.85% increase in ZOI of amoxicillin in combination with zinc oxide and zinc hydroxide, respectively. The modulated antimicrobial resistance incurred by NSAIDs, plant extracts, and microparticles against pathogenic S. aureus invite immediate attention to probe alternative antimicrobial sources.

Keywords: antimicrobial resistance, dairy milk, nanoparticles, NSIDs, plant extracts, resistance modulation, S. aureus

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870 Refining Waste Spent Hydroprocessing Catalyst and Their Metal Recovery

Authors: Meena Marafi, Mohan S. Rana

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Catalysts play an important role in producing valuable fuel products in petroleum refining; but, due to feedstock’s impurities catalyst gets deactivated with carbon and metal deposition. The disposal of spent catalyst falls under the category of hazardous industrial waste that requires strict agreement with environmental regulations. The spent hydroprocessing catalyst contains Mo, V and Ni at high concentrations that have been found to be economically significant for recovery. Metal recovery process includes deoiling, decoking, grinding, dissolving and treatment with complexing leaching agent such as ethylene diamine tetra acetic acid (EDTA). The process conditions have been optimized as a function of time, temperature and EDTA concentration in presence of ultrasonic agitation. The results indicated that optimum condition established through this approach could recover 97%, 94% and 95% of the extracted Mo, V and Ni, respectively, while 95% EDTA was recovered after acid treatment.

Keywords: atmospheric residue desulfurization (ARDS), deactivation, hydrotreating, spent catalyst

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869 Nanomaterials Based Biosensing Chip for Non-Invasive Detection of Oral Cancer

Authors: Suveen Kumar

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Oral cancer (OC) is the sixth most death causing cancer in world which includes tumour of lips, floor of the mouth, tongue, palate, cheeks, sinuses, throat, etc. Conventionally, the techniques used for OC detection are toluidine blue staining, biopsy, liquid-based cytology, visual attachments, etc., however these are limited by their highly invasive nature, low sensitivity, time consumption, sophisticated instrument handling, sample processing and high cost. Therefore, we developed biosensing chips for non-invasive detection of OC via CYFRA-21-1 biomarker. CYFRA-21-1 (molecular weight: 40 kDa) is secreted in saliva of OC patients which is a non-invasive biological fluid with a cut-off value of 3.8 ng mL-1, above which the subjects will be suffering from oral cancer. Therefore, in first work, 3-aminopropyl triethoxy silane (APTES) functionalized zirconia (ZrO2) nanoparticles (APTES/nZrO2) were used to successfully detect CYFRA-21-1 in a linear detection range (LDR) of 2-16 ng mL-1 with sensitivity of 2.2 µA mL ng-1. Successively, APTES/nZrO2-RGO was employed to prevent agglomeration of ZrO2 by providing high surface area reduced graphene oxide (RGO) support and much wider LDR (2-22 ng mL-1) was obtained with remarkable limit of detection (LOD) as 0.12 ng mL-1. Further, APTES/nY2O3/ITO platform was used for oral cancer bioseneor development. The developed biosensor (BSA/anti-CYFRA-21-1/APTES/nY2O3/ITO) have wider LDR (0.01-50 ng mL-1) with remarkable limit of detection (LOD) as 0.01 ng mL-1. To improve the sensitivity of the biosensing platform, nanocomposite of yattria stabilized nanostructured zirconia-reduced graphene oxide (nYZR) based biosensor has been developed. The developed biosensing chip having ability to detect CYFRA-21-1 biomolecules in the range of 0.01-50 ng mL-1, LOD of 7.2 pg mL-1 with sensitivity of 200 µA mL ng-1. Further, the applicability of the fabricated biosensing chips were also checked through real sample (saliva) analysis of OC patients and the obtained results showed good correlation with the standard protein detection enzyme linked immunosorbent assay (ELISA) technique.

Keywords: non-invasive, oral cancer, nanomaterials, biosensor, biochip

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868 Tri/Tetra-Block Copolymeric Nanocarriers as a Potential Ocular Delivery System of Lornoxicam: Experimental Design-Based Preparation, in-vitro Characterization and in-vivo Estimation of Transcorneal Permeation

Authors: Alaa Hamed Salama, Rehab Nabil Shamma

Abstract:

Introduction: Polymeric micelles that can deliver drug to intended sites of the eye have attracted much scientific attention recently. The aim of this study was to review the aqueous-based formulation of drug-loaded polymeric micelles that hold significant promise for ophthalmic drug delivery. This study investigated the synergistic performance of mixed polymeric micelles made of linear and branched poly (ethylene oxide)-poly (propylene oxide) for the more effective encapsulation of Lornoxicam (LX) as a hydrophobic model drug. Methods: The co-micellization process of 10% binary systems combining different weight ratios of the highly hydrophilic poloxamers; Synperonic® PE/P84, and Synperonic® PE/F127 and the hydrophobic poloxamine counterpart (Tetronic® T701) was investigated by means of photon correlation spectroscopy and cloud point. The drug-loaded micelles were tested for their solubilizing capacity towards LX. Results: Results showed a sharp solubility increase from 0.46 mg/ml up to more than 4.34 mg/ml, representing about 136-fold increase. Optimized formulation was selected to achieve maximum drug solubilizing power and clarity with lowest possible particle size. The optimized formulation was characterized by 1HNMR analysis which revealed complete encapsulation of the drug within the micelles. Further investigations by histopathological and confocal laser studies revealed the non-irritant nature and good corneal penetrating power of the proposed nano-formulation. Conclusion: LX-loaded polymeric nanomicellar formulation was fabricated allowing easy application of the drug in the form of clear eye drops that do not cause blurred vision or discomfort, thus achieving high patient compliance.

Keywords: confocal laser scanning microscopy, Histopathological studies, Lornoxicam, micellar solubilization

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867 Allylation of Active Methylene Compounds with Cyclic Baylis-Hillman Alcohols: Why Is It Direct and Not Conjugate?

Authors: Karim Hrratha, Khaled Essalahb, Christophe Morellc, Henry Chermettec, Salima Boughdiria

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Among the carbon-carbon bond formation types, allylation of active methylene compounds with cyclic Baylis-Hillman (BH) alcohols is a reliable and widely used method. This reaction is a very attractive tool in organic synthesis of biological and biodiesel compounds. Thus, in view of an insistent and peremptory request for an efficient and straightly method for synthesizing the desired product, a thorough analysis of various aspects of the reaction processes is an important task. The product afforded by the reaction of active methylene with BH alcohols depends largely on the experimental conditions, notably on the catalyst properties. All experiments reported that catalysis is needed for this reaction type because of the poor ability of alcohol hydroxyl group to be as a suitable leaving group. Within the catalysts, several transition- metal based have been used such as palladium in the presence of acid or base and have been considered as reliable methods. Furthemore, acid catalysts such as BF3.OEt2, BiX3 (X= Cl, Br, I, (OTf)3), InCl3, Yb(OTf)3, FeCl3, p-TsOH and H-montmorillonite have been employed to activate the C-C bond formation through the alkylation of active methylene compounds. Interestingly a report of a smoothly process for the ability of 4-imethyaminopyridine(DMAP) to catalyze the allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol appeared recently. However, the reaction mechanism remains ambiguous, since the C- allylation process leads to an unexpected product (noted P1), corresponding to a direct allylation instead of conjugate allylation, which involves the most electrophilic center according to the electron withdrawing group CO effect. The main objective of the present theoretical study is to better understand the role of the DMAP catalytic activity as well as the process leading to the end- product (P1) for the catalytic reaction of a cyclic BH alcohol with active methylene compounds. For that purpose, we have carried out computations of a set of active methylene compounds varying by R1 and R2 toward the same alcohol, and we have attempted to rationalize the mechanisms thanks to the acid–base approach, and conceptual DFT tools such as chemical potential, hardness, Fukui functions, electrophilicity index and dual descriptor, as these approaches have shown a good prediction of reactions products.The present work is then organized as follows: In a first part some computational details will be given, introducing the reactivity indexes used in the present work, then Section 3 is dedicated to the discussion of the prediction of the selectivity and regioselectivity. The paper ends with some concluding remarks. In this work, we have shown, through DFT method at the B3LYP/6-311++G(d,p) level of theory that: The allylation of active methylene compounds with cyclic BH alcohol is governed by orbital control character. Hence the end- product denoted P1 is generated by direct allylation.

Keywords: DFT calculation, gas phase pKa, theoretical mechanism, orbital control, charge control, Fukui function, transition state

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866 Development of Boro-Tellurite Glasses Enhanced with HfO2 for Radiation Shielding: Examination of Optical and Physical Characteristics

Authors: Sleman Yahya Rasul

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Due to their transparency, various types of glass are utilized in numerous applications where clear visibility is essential. One such application involves environments where radiography, radiotherapy, and X-ray devices are used, all of which involve exposure to radiation. As is well-known, radiation can be lethal to humans. Consequently, there is a need for glass that can absorb and block these harmful rays in such settings. Effective protection from radiation typically requires materials with high atomic numbers and densities. Currently, lead oxide-infused glasses are commonly used for this purpose, but due to the toxicity of lead oxide, there is a demand for safer alternatives. HfO2 has been selected as an additive for boro-tellurite (M1-M2-M3) glasses intended for radiation shielding because it has a high atomic number, high density, and is non-toxic. In this study, new glasses will be developed as alternatives to leaded glasses by incorporating x mol% HfO2 into the boro-tellurite glass structure. The glass compositions will be melted and quenched using the traditional method in an alumina crucible at temperatures between 900–1100°C. The resulting glasses will be evaluated for their elastic properties (including elastic modulus, shear modulus, bulk modulus, and Poisson ratio), density, hardness, and fracture toughness. X-ray diffraction (XRD) will be used to examine the amorphous nature of the glasses, while Differential Thermal Analysis (DTA) will provide thermal analysis. Optical properties will be assessed through UV-Vis and Photoluminescence Spectroscopy, and structural properties will be studied using Raman spectroscopy and FTIR spectroscopy. Additionally, the radiation shielding capabilities will be investigated by measuring parameters such as mass attenuation coefficient, half-value thickness, mean free path, effective atomic number (Z_eff), and effective electron density (N_e). The aim of this study is to develop new, lead-free glasses with excellent optical properties and high mechanical strength to replace the leaded glasses currently used for radiation shielding.

Keywords: boro-tellurite glasses, hfo2, radiation shielding, mechanical properties, elastic properties, optical properties

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865 Investigating the Steam Generation Potential of Lithium Bromide Based CuO Nanofluid under Simulated Solar Flux

Authors: Tamseela Habib, Muhammad Amjad, Muhammad Edokali, Masome Moeni, Olivia Pickup, Ali Hassanpour

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Nanofluid-assisted steam generation is rapidly attracting attention amongst the scientific community since it can be applied in a wide range of industrial processes. Because of its high absorption rate of solar energy, nanoparticle-based solar steam generation could be a major contributor to many applications, including water desalination, sterilization and power generation. Lithium bromide-based iron oxide nanofluids have been previously studied in steam generation, which showed promising results. However, the efficiency of the system could be improved if a more heat-conductive nanofluid system could be utilised. In the current paper, we report on an experimental investigation of the photothermal conversion properties of functionalised Copper oxide (CuO) nanoparticles used in Lithium Bromide salt solutions. CuO binary nanofluid was prepared by chemical functionalization with polyethyleneimine (PEI). Long-term stability evaluation of prepared binary nanofluid was done by a high-speed centrifuge analyser which showed a 0.06 Instability index suggesting low agglomeration and sedimentation tendencies. This stability is also supported by the measurements from dynamic light scattering (DLS), transmission electron microscope (TEM), and ultraviolet-visible (UV-Vis) spectrophotometer. The fluid rheology is also characterised, which suggests the system exhibits a Newtonian fluid behavior. The photothermal conversion efficiency of different concentrations of CuO was experimentally investigated under a solar simulator. Experimental results reveal that the binary nanofluid in this study can remarkably increase the solar energy trapping efficiency and evaporation rate as compared to conventional fluids due to localized solar energy harvesting by the surface of the nanofluid. It was found that 0.1wt% CuO NP is the optimum nanofluid concentration for enhanced sensible and latent heat efficiencies.

Keywords: nanofluids, vapor absorption refrigeration system, steam generation, high salinity

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864 Agro-Industrial Waste as a Source of Catalyst Production

Authors: Brenda Cecilia Ledesma, Andrea Beltramone

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This work deals with the bio-waste valorization approach for catalyst development, the use of products derived from biomass as raw material and the obtaining of biofuels. In this research, activated carbons were synthesized from the orange peel using different synthesis conditions. With the activated carbons obtained with the best structure and texture, PtIr bimetallic catalysts were prepared. Carbon activation was carried out through a chemical process with phosphoric acid as an activating agent, varying the acid concentration, the ratio substrate/activating agent and time of contact between them. The best support was obtained using a carbonization time of 1 h, the temperature of carbonization of 470oC, the phosphoric acid concentration of 50 wt.% and a BET area of 1429 m2/g. Subsequently, the metallic nanoparticles were deposited in the activated carbon to use the solid as a catalytic material for the hydrogenation of HMF to 2,5-DMF. The catalyst presented an excellent performance for biofuels generation.

Keywords: orange peel, bio-waste valorization, platinum, iridium, 5-hydroxymethylfurfural

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863 Study of the Morphological and Optical Properties of Nanometric NiO

Authors: Nassima Hamzaoui, Mostefa Ghamnia

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Nanoscale thin films of pure and Mn-doped Nickel oxide (NiO) were prepared by dissolving nickel chloride hexahydrate (NiCl2, 6H2O) and manganese chloride tetrahydrate (MnCl2,4H2O) under experimental conditions. The resulting solution was stirred at room temperature for 30 OC minutes in order to obtain homogeneity. The solution was sprayed onto heated glass substrates. The films obtained were characterized by X-ray diffraction to verify crystallinity. Atomic force microscopy (AFM) reveals surface topographical structure. UV-visible spectroscopy shows good transparency of the NiO layers.

Keywords: films, NiO, AFM, X-ray diffraction

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862 Dipicolinate Complex of Oxovanadium(Iv) with 4,4′-Dimethoxy-2,2′-Bipyridyl as a New Generation Ziegler-Natta Precatalyst

Authors: Joanna Drzeżdżon

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Polyvinyl alcohol and its derivatives such as 2-chloro-2-propen-1-ol have found application in many industries. They are mainly used for the production of adhesives, thickeners and stabilizers of emulsion paints, and surgical threads. Moreover, polyvinyl alcohol derivatives are indispensable reagents in the synthesis of hemiacetals. Polyolefins derived from polyvinyl alcohol are obtained by using catalysts belonging to complex compounds of transition metal ions. The aim of the studies is to the synthesis of a new complex, i.e. dipicolinate oxovanadium(IV) complex with 4,4’-dimethoxy-2,2’-bipyridyl, and to determine its catalytic activities. Moreover, the another aim of the studies was to set conditions for 2-chloro-2-propen-1-ol oligomerization. The catalytic system has been based on the dipicolinate complex of oxovanadium(IV) with 4,4’-dimethoxy-2,2’-bipyridyl and MMAO-12. The results of the studies showed that how a new oxovanadium(IV) complex compound effects on the 2-chloro-2-propen-1-ol oligomerization. Moreover, the results revealed that new catalytic material is a highly active catalyst for the investigated oligomerization.

Keywords: 2-chloro-2-propen-1-ol, oligomerization, dipicolinate, vanadium, methylaluminoxane

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861 Experimental Study on Thermomechanical Properties of New-Generation ODS Alloys

Authors: O. Khalaj, B. Mašek, H. Jirková, J. Svoboda

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By using a combination of new technologies together with an unconventional use of different types of materials, specific mechanical properties and structures of the material can be achieved. Some possibilities are enabled by a combination of powder metallurgy in the preparation of a metal matrix with dispersed stable particles achieved by mechanical alloying and hot consolidation. This paper explains the thermomechanical properties of new generation of Oxide Dispersion Strengthened alloys (ODS) within three ranges of temperature with specified deformation profiles. The results show that the mechanical properties of new ODS alloys are significantly affected by the thermomechanical treatment.

Keywords: hot forming, ODS, alloys, thermomechanical, Fe-Al, Al2O3

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860 Brewing in a Domestic Refrigerator Using Freeze-Dried Raw Materials

Authors: Angelika-Ioanna Gialleli, Gousi Mantha, Maria Kanellaki, Bekatorou Argyro, Athanasios Koutinas

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In this study, a new brewing technology with dry raw materials is proposed with potential application in home brewing. Bio catalysts were prepared by immobilization of the psychrotolerant yeast strain Saccharomyces cerevisiae AXAZ-1 on tubular cellulose. Both the word and the biocatalysts were freeze-dried without any cryoprotectants and used for low temperature brewing. The combination of immobilization and freeze-drying techniques was applied successfully, giving a potential for supplying breweries with preserved and ready-to-use immobilized cells. The effect of wort sugar concentration (7°, 8.5°, 10°Be), temperature (2, 5, 7° C) and carrier concentration (5, 10, 20 g/L) on fermentation kinetics and final product quality (volatiles, colour, polyphenols, bitterness) was assessed. The same procedure was repeated with free cells for comparison of the results. The results for immobilized cells were better compared to free cells regarding fermentation kinetics and organoleptic characteristics.

Keywords: brewing, tubular cellulose, low temperature, biocatalyst

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859 Direct Synthesis of Composite Materials Type MCM-41/ZSM-5 by Hydrothermal at Atmospheric Pressure in Sealed Pyrex Tubes

Authors: Zoubida Lounis, Naouel Boumesla, Abd El Kader Bengueddach

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The main objective of this study is to synthesize a composite materials by direct synthesis at atmospheric pression having the MFI structure and MCM-41 by using double structuring. In the first part of this work we are interested in the study of the synthesis parameters, in addition to temperature, the crystallization time and pH. The second part of this work is to vary the ratio of the concentrations of both structuring C9 [C9H19(CH3)3NBr] and C16 [C16H33(CH3)3NBr] and determining the area of formation of the two materials (microporous and mesoporous at same time), for this reason we performed a battery of experiments ranging from 0 to 100% for both structural. To enhance the economic purposes of this study, the experiments were carried out by using very cheap and simple process, the pyrex tubes were used instead of the reactors, and the synthesis were done at atmospheric pressure and moderate temperature. The final products (composite materials) were obtained at high and pure quality.

Keywords: composite materials, syntheisis, catalysts, mesoporous materials, microporous materials

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858 The Effect of Branched-Chain Amino Acids, Arginine, and Citrulline on Repeated Swimming Performance

Authors: Chun-Fang Hsueh, Chen-Kang Chang

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Introduction: Branched-chain amino acids (BCAA) could reduce cerebral uptake of tryptophan, leading to decreased synthesis of serotonin in the brain. Arginine and citrulline could reduce exercise-induced hyperammonemia by increasing nitric oxide synthesis and the urea cycle. The combination of these supplements could reduce exercise-induced central fatigue. The purpose of this study was to examine the effect of BCAA, arginine, and citrulline supplementation on repeated swimming performance in teenage athletes. Methods: Eight male and eight female high school swimmers ingested 0.085 g/kg BCAA, 0.05 g/kg arginine and 0.05 g/kg citrulline (AA trial) or placebo (PL trial) in a randomized cross-over design. One hour after the ingestion, the subjects performed a 50 m sprint with their best style every 2 min for 8 times in an indoor 25 m pool. The subjects were asked to swim with their maximal effort each time. The time, stroke frequency and stroke length in each sprint were recorded. Venous blood samples were collected before and after the exercise. The time for each sprint was analyzed by 2-way analysis of variance with repeated measurement. Results: When all subjects were pooled together, total time for the AA trial was significantly faster than the PL trial (AA: 244.02 ± 22.94 s; PL: 247.55 ± 24.17 s, p < .001). Individual sprint time showed significant trial (p= .001) and trial x time (p= .004) effects. The post-hoc analysis revealed that the AA trial was significantly faster than the PL trial in the 2nd, 5th, and 6th sprint. In female subjects, there is a significant trial effect (p= .004) with the AA trial being faster in the 1st, 2nd, and 5th sprint. On the other hand, the trial effect was not significant (p= .072) in male subjects. Conclusions: The combined supplementation could improve 8 x 50 m performance in high school swimmers. The blood parameters including BCAA, tryptophan, NH₃, nitric oxide, and urea, as well as the stroke frequency and length in each sprint, are being analyzed. The results will be presented in the conference.

Keywords: central fatigue, hyperammonemia, tryptophan, urea

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857 One-Pot Facile Synthesis of N-Doped Graphene Synthesized from Paraphenylenediamine as Metal-Free Catalysts for the Oxygen Reduction Used for Alkaline Fuel Cells

Authors: Leila Samiee, Amir Yadegari, Saeedeh Tasharrofi

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In the work presented here, nitrogen-doped graphene materials were synthesized and used as metal-free electrocatalysts for oxygen reduction reaction (ORR) under alkaline conditions. Paraphenylenediamine was used as N precursor. The N-doped graphene was synthesized under hydrothermal treatment at 200°C. All the materials have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Moreover, for electrochemical evaluation of samples, Rotating Disk electrode (RDE) and Cyclic Voltammetry techniques (CV) were employed. The resulting material exhibits an outstanding catalytic activity for the oxygen reduction reaction (ORR) as well as excellent resistance towards methanol crossover effects, indicating their promising potential as ORR electrocatalysts for alkaline fuel cells.

Keywords: alkaline fuel cell, graphene, metal-free catalyst, paraphenylen diamine

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856 Development of a Cathode-Type Ca1-xSrxMnO3

Authors: A. Guemache, M. Omari

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Oxides with formula Ca1-xSrx MnO3 (0≤x≤0.2) were synthesized using co-precipitation method. The identification of the obtained phase was carried out using infrared spectroscopy and X-ray diffraction. Thermogravimetric and differential analysis was permitted to characterize different transformations of precursors which take place during one heating cycle. The study of electrochemical behavior was carried out by cyclic voltammetry and impedance spectroscopy. The obtained results show that apparent catalytic activity improved when increasing the concentration of strontium. Anodic current densities varies from 1.3 to 5.9 mA/cm2 at the rate scan of 20 mV.s-1 and a potential 0.8 V for oxides with composition x=0 to 0.2.

Keywords: oxide, co-precipitation, electrochemical properties, cathode-type

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855 Development of NO-Ergic Synaptic Transmission in Sympathetic Neurons of Mammals: Immunohistochemical Study

Authors: Konstantin Yu. Moiseev, Antonina F. Budnik, Andrey I. Emanuilov, Petr M. Masliukov

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The vast majority of sympathetic ganglionic neurons are catecholaminergic. Some sympathetic neurons lack catecholamines and mostly use acetylcholine as their main neurotransmitter. Some cholinergic postganglionic neurons also express neuronal nitric oxide synthase (nNOS). Preganglionic sympathetic neurons are cholinergic and most of them are also nNOS-immunoreactive (IR). The purpose of this study was to gain further insight into the neuroplasticity of sympathetic neurons during postnatal ontogenesis by comparing the development of pre- and postganglionic neurons expressing nNOS in different mammals. nNOS was investigated by immunohistochemistry in the sympathetic superior cervical ganglion (SCG), stellate ganglion (SG), celiac ganglion (CG) and spinal cord from rats, mice and cats of different ages (newborn, 10-day-old, 20-day-old, 30-day-old, 2-month-old and 2-year-old). In rats and mice, nNOS-positive neurons were not found in sympathetic ganglia from birth onwards. In cats, non-catecholaminergic nNOS-IR sympathetic ganglionic neurons are present from the moment of birth. In all studied age groups, substantial populations of nNOS-IR cells (up to 8.3%) was found in the SG, with a much smaller population found in the SCG (<1%) and only few cells observed in the CG. The percentage of nNOS-IR neurons in the CG and SCG did not significantly change during development. The proportion of nNOS-IR neuron profiles in the SG increased in first 20 days of life from 2.3±0.15% to 8.3±0.56%. In the SG, percentages of nNOS-IR sympathetic neurons colocalizing vasoactive intestinal peptide increased in the first 20 days of life. Choline acetyltransferase (ChAT)-IR and calcitonin gene-related peptide-IR neurons were not observed in the sympathetic ganglia of newborn animals and did not appear until 10 days after birth. In the SG of newborn and 10-day-old kittens, the majority of NOS-IR neurons were calbindin (CB)-IR, whereas in the SCG and CG of cats of all age groups and in the SG of 30-day-old and older kittens, the vast majority of NOS-IR neurons lacked CB. In newborn mammals, the most of sympathetic preganglionic neurons in the nucleus intermediolateralis thoracolumbalis pars principalis (nucl.ILp) were nNOS-IR. The percentage of nNOS-IR neurons decreased and the same parameter of ChAT-IR neurons increased during the development. We conclude that the development of nNOS-IR preganglionic and ganglionic sympathetic neurons in different mammals has time and species differences.

Keywords: sympathetic neuron, nitric oxide synthase, immunohistochemistry, development

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854 Ammonia Cracking: Catalysts and Process Configurations for Enhanced Performance

Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

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853 Nanoparticles Made from PNIPAM-G-PEO Double Hydrophilic Copolymers for Temperature-Controlled Drug Delivery

Authors: Victoria I. Michailova, Denitsa B. Momekova, Hristiana A. Velichkova, Evgeni H. Ivanov

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The aim of this work is to design and develop thermo-responsive nanosized drug delivery systems based on poly(N-isopropylacrylamide)-g-poly(ethylene oxide) (PNIPAM-g-PEO) double hydrophilic graft copolymers. The PNIPAM-g-PEO copolymers are able to self-assemble in water into nanoparticles above the LCST of the thermo-responsive PNIPAM backbone and to disassemble and rapidly release the entrapped drugs upon cooling. However, their drug delivery applications are often hindered by their low loading capacity as the drugs to be encapsulated do not dissolve in water. In order to overcome this limitation, here we applied a low-temperature procedure with ethanol as an alternative route to the formation and loading a model hydrophobic drug, Indomethacin (IMC), into PNIPAM-g-PEO nanoparticles. The rationale for this approach was that ethanol dissolves both IMC and the copolymer and its mixing with water may induce micellization of PNIPAM-g-PEO at temperatures lower than the LCST. The influence of the volume fraction of ethanol and the temperature on the aggregation characteristics of PNIPAM-g-PEO copolymers (2.7 mol% PEO) was investigated by means of DLS, TEM and rheological dynamic oscillatory tests. The studies showed rich phase behavior at T < LCST, incl. the formation of highly solvated 500-1000 nm complex structures, 30-70 nm micelles and polymersomes as well as giant polymersomes, as the fraction of added ethanol increased. We believe that the PNIPAM-g-PEO self-assembly is favored due to the different solvation of its constituting blocks in ethanol-water mixtures. The incorporation of IMC led to alteration of the physicochemical and morphological characteristics of the blank nanoparticles. In this case, only monodisperse polymersomes and micelles were observed in the solutions with an average diameter less than 65 nm and substantial drug loading (DLC ~117 – 146 wt%). Indomethacin release from the nanoparticles was responsive to temperature changes, being much faster at a temperature of 42oC compared to that of 37oC under otherwise the same conditions. The results obtained suggest that these PNIPAM-g-PEO nanoparticles could be potential in mild hyper-thermic delivery of nonsteroidal anti-inflammatory drugs.

Keywords: drug delivery, nanoparticles, poly(N-isopropylacryl amide)-g-poly(ethylene oxide), thermo-responsive

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