Search results for: chemical and mineral composition and amorphousness
2382 Efficacy of Microwave against Oryzaephilus Mercator Pest Infesting Dried Figs and Evaluation of the Product Color Changes Using an Image Processing Technique
Authors: Reza Sadeghi
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In this study, microwave heating was employed for controlling Oryzaephilus mercator. adults infesting stored Iranian dried fig. For this purpose, the dried fig samples were artificially infested with O. mercator and then heated in a microwave oven (2450 MHz) at the power outputs of 450, 720, and 900 W for 10, 20, 30, and 40 s, respectively. Subsequently, changes in the colors of the product samples under the effects of the varied microwave applications were investigated in terms of lightness (ΔL*), redness (Δa*), and yellowness (Δb*) using an image processing technique. The results revealed that both parameters of microwave power and exposure time had significant impacts on the pest mortality rates (p<0.01). In fact, a direct positive relationship was obtained between the mortality rate and microwave irradiation power. Complete mortality was achieved for the pest at the power of 900 W and exposure time of 40 s. The dried fig samples experienced fewer changes in their color parameters. Considering the successful pest control and acceptable changes in the product quality, microwave irradiation can be introduced as an appropriate alternative to chemical fumigants.Keywords: colorimetric assay, microwave heating, Oryzaephilus mercator, mortality
Procedia PDF Downloads 882381 Impacts of Tillage on Biodiversity of Microarthropod Communities in Two Different Crop Systems
Authors: Leila Ramezani, Mohammad Saeid Mossadegh
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Different uses of land by humans alter the physico chemical characteristics of the soil and affect the soil microhabitat. The objective of this study was to evaluate the influence of tillage in three different human land uses on microarthropods biodiversity in Khuzestan province, southwest of Iran. Three microhabitats including a permanent grassland with old Date-Palms around and no till system, and two wheat fields, one with conservative agricultural practices and low till system and the other with conventional agricultural practices (deep tillage), were compared for the biodiversity of the two main groups of soil microarthropods (Oribatida and Collembola). Soil samples were collected from the top to a depth of 15 cm bimonthly during a period of two years. Significant differences in the biodiversity index of microarthropods were observed between the different tillage systems (F = 36.748, P =0.000). Indeed, analysis of species diversity showed that the diversity index at the conservative field with low till (2.58 ± 0.01) was higher (p < 0.05) than the conventional tilled field (2.45 ± 0.08) and the diversity of natural grassland was the highest (2.79 ± 0.19, p < 0.05). Indeed, the index of biodiversity and population abundance differed significantly in different seasons (p < 0.00).Keywords: biodiversity, Collembola, microarthropods, Oribatida
Procedia PDF Downloads 1752380 Effect of Al Addition on Microstructure and Properties of NbTiZrCrAl Refractory High Entropy Alloys
Authors: Xiping Guo, Fanglin Ge, Ping Guan
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Refractory high entropy alloys are alternative materials expected to be employed at high temperatures. The comprehensive changes of microstructure and properties of NbTiZrCrAl refractory high entropy alloys are systematically studied by adjusting Al content. Five kinds of button alloy ingots with different contents of Al in NbTiZrCrAlX (X=0, 0.2, 0.5, 0.75, 1.0) were prepared by vacuum non-consumable arc melting technology. The microstructure analysis results show that the five alloys are composed of BCC solid solution phase rich in Nb and Ti and Laves phase rich in Cr, Zr, and Al. The addition of Al changes the structure from hypoeutectic to hypereutectic, increases the proportion of Laves phase, and changes the structure from cubic C15 to hexagonal C14. The hardness and fracture toughness of the five alloys were tested at room temperature, and the compressive mechanical properties were tested at 1000℃. The results showed that the addition of Al increased the proportion of Laves phase and decreased the proportion of the BCC phase, thus increasing the hardness and decreasing the fracture toughness at room temperature. However, at 1000℃, the strength of 0.5Al and 0.75Al alloys whose composition is close to the eutectic point is the best, which indicates that the eutectic structure is of great significance for the improvement of high temperature strength of NbTiZrCrAl refractory high entropy alloys. The five alloys were oxidized for 1 h and 20 h in static air at 1000℃. The results show that only the oxide film of 0Al alloy falls off after oxidizing for 1 h at 1000℃. After 20h, the oxide film of all the alloys fell off, but the oxide film of alloys containing Al was more dense and complete. By producing protective oxide Al₂O₃, inhibiting the preferential oxidation of Zr, promoting the preferential oxidation of Ti, and combination of Cr₂O₃ and Nb₂O₅ to form CrNbO₄, Al significantly improves the high temperature oxidation resistance of NbTiZrCrAl refractory high entropy alloys.Keywords: NbTiZrCrAl, refractory high entropy alloy, al content, microstructural evolution, room temperature mechanical properties, high temperature compressive strength, oxidation resistance
Procedia PDF Downloads 842379 A Comparative Study of European Terrazzo and Tibetan Arga Floor Making Techniques
Authors: Hubert Feiglstorfer
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The technique of making terrazzo has been known since ancient times. During the Roman Empire, known as opus signinum, at the time of the Renaissance, known as composto terrazzo marmorino or at the turn of the 19th and 20th centuries, the use of terrazzo experienced a common use in Europe. In Asia, especially in the Himalayas and the Tibetan highlands, a particular floor and roof manufacturing technique is commonly used for about 1500 years, known as arga. The research question in this contribution asks for technical and cultural-historical synergies of these floor-making techniques. The making process of an arga floor shows constructive parallels to the European terrazzo. Surface processing by grinding, burnishing and sealing, in particular, reveals technological similarities. The floor structure itself, on the other hand, shows differences, for example in the use of hydraulic aggregate in the terrazzo, while the arga floor is used without hydraulic material, but the result of both techniques is a tight, water-repellent and shiny surface. As part of this comparative study, the materials, processing techniques and quality features of the two techniques are compared and parallels and differences are analysed. In addition to text and archive research, the methods used are results of material analyses and ethnographic research such as participant observation. Major findings of the study are the investigation of the mineralogical composition of arga floors and its comparison with terrazzo floors. The study of the cultural-historical context in which both techniques are embedded will give insight into technical developments in Europe and Asia, parallels and differences. Synergies from this comparison let possible technological developments in the production, conservation and renovation of European terrazzo floors appear in a new light. By making arga floors without cement-based aggregates, the renovation of historical floors from purely natural products and without using energy by means of a burning process can be considered.Keywords: European and Asian crafts, material culture, floor making technology, terrazzo, arga, Tibetan building traditions
Procedia PDF Downloads 2482378 Structural and Optical Properties of Pr3+ Doped ZnO and PVA:Zn98Pr2O Nanocomposites Free Standing Film
Authors: Pandiyarajan Thangaraj, Mangalaraja Ramalinga Viswanathan, Karthikeyan Balasubramanian, Héctor D. Mansilla, José Ruiz, David Contreras
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We report a systematic study of structural and optical properties of Pr-doped ZnO nanostructures and PVA:Zn98Pr2O polymer matrix nanocomposites free standing films are performed. These particles are synthesized through simple wet chemical route and solution casting technique at room temperature, respectively. Structural studies carried out by X-ray diffraction method, confirms that the prepared pure ZnO and Pr-doped ZnO nanostructures are in hexagonal wurtzite structure and the microstrain is increased upon doping. TEM analysis reveals that the prepared materials are in the sheet-like nature. Absorption spectra show free excitonic absorption band at 370 nm and red shift for the Pr-doped ZnO nanostructures. The PVA:Zn98Pr2O composite film exhibits both free excitonic and PVA absorption bands at 282 nm. Fourier transform infrared spectral studies confirm the presence of A1 (TO) and E1 (TO) modes of Zn-O bond vibration and the formation of polymer composite materials.Keywords: Pr doped ZnO, polymer nanocomposites, optical properties, free standing film
Procedia PDF Downloads 4692377 Electroless Nickel Boron Deposition onto the SiC and B4C Ceramic Reinforced Materials
Authors: I. Kerti, G. Sezen, S. Daglilar
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This present work is focused on studying to improve low wetting behaviour between liquid metal and ceramic particles. Ceramic particles like SiC and B4C have attracted great attention because of their usability as reinforcement for composite materials. However, poor wettability of particles is one of the major drawbacks of metal matrix composite production. Various methods have been studied to enhance the wetting properties between ceramic materials and metal substrates during ceramic reinforced metal matrix composites. Among these methods, autocatalytic nickel deposition is a unique process for the enhancement of the surface properties of ceramic particles. In fact, it is difficult to obtain continuous and uniform metallic coating on ceramic powders. In this study deposition of nickel boron layer on ceramic particles via autocatalytic plating in borohydride baths were investigated. Firstly, powders with different particle sizes were sensitized and activated respectively in order to ensure catalytic properties. Following the pre-treatment operations, particles were transferred into the coating bath containing nickel sulphate or nickel chloride as the Ni2+ source. The results show that a better bonding and uniform coating layer were obtained for Ni-B coatings with the Ni2+ source of NiCl2.6H2O as compared to NiSO4.6H2O. With the progress of the time, both particle surfaces are completely covered by a continuous and thin nickel boron layer. The surface morphology of the coatings that were analysed using scanning electron microscopy (SEM) show that SiC and B4C particles both distributed and different thickness of Ni-B nanolayers have been successfully coated onto the particles. The particles were mounted into a polimeric resin and polished in order to observe the thickness and the continuity of the coating layer. The composition of the coating layers were also evaluated by EDS analyses. The SEM morphologies and the EDS results of the coatings at different reaction times were adopted for detailed discussion of the Ni-B electroless plating mechanism.Keywords: boron carbide, electroless coating, nickel boron deposition, silicon carbide
Procedia PDF Downloads 3482376 Tackling the Decontamination Challenge: Nanorecycling of Plastic Waste
Authors: Jocelyn Doucet, Jean-Philippe Laviolette, Ali Eslami
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The end-of-life management and recycling of polymer wastes remains a key environment issue in on-going efforts to increase resource efficiency and attaining GHG emission reduction targets. Half of all the plastics ever produced were made in the last 13 years, and only about 16% of that plastic waste is collected for recycling, while 25% is incinerated, 40% is landfilled, and 19% is unmanaged and leaks in the environment and waterways. In addition to the plastic collection issue, the UN recently published a report on chemicals in plastics, which adds another layer of challenge when integrating recycled content containing toxic products into new products. To tackle these important issues, innovative solutions are required. Chemical recycling of plastics provides new complementary alternatives to the current recycled plastic market by converting waste material into a high value chemical commodity that can be reintegrated in a variety of applications, making the total market size of the output – virgin-like, high value products - larger than the market size of the input – plastic waste. Access to high-quality feedstock also remains a major obstacle, primarily due to material contamination issues. Pyrowave approaches this challenge with its innovative nano-recycling technology, which purifies polymers at the molecular level, removing undesirable contaminants and restoring the resin to its virgin state without having to depolymerise it. This breakthrough approach expands the range of plastics that can be effectively recycled, including mixed plastics with various contaminants such as lead, inorganic pigments, and flame retardants. The technology allows yields below 100ppm, and purity can be adjusted to an infinitesimal level depending on the customer's specifications. The separation of the polymer and contaminants in Pyrowave's nano-recycling process offers the unique ability to customize the solution on targeted additives and contaminants to be removed based on the difference in molecular size. This precise control enables the attainment of a final polymer purity equivalent to virgin resin. The patented process involves dissolving the contaminated material using a specially formulated solvent, purifying the mixture at the molecular level, and subsequently extracting the solvent to yield a purified polymer resin that can directly be reintegrated in new products without further treatment. Notably, this technology offers simplicity, effectiveness, and flexibility while minimizing environmental impact and preserving valuable resources in the manufacturing circuit. Pyrowave has successfully applied this nano-recycling technology to decontaminate polymers and supply purified, high-quality recycled plastics to critical industries, including food-contact compliance. The technology is low-carbon, electrified, and provides 100% traceable resins with properties identical to those of virgin resins. Additionally, the issue of low recycling rates and the limited market for traditionally hard-to-recycle plastic waste has fueled the need for new complementary alternatives. Chemical recycling, such as Pyrowave's microwave depolymerization, presents a sustainable and efficient solution by converting plastic waste into high-value commodities. By employing microwave catalytic depolymerization, Pyrowave enables a truly circular economy of plastics, particularly in treating polystyrene waste to produce virgin-like styrene monomers. This revolutionary approach boasts low energy consumption, high yields, and a reduced carbon footprint. Pyrowave offers a portfolio of sustainable, low-carbon, electric solutions to give plastic waste a second life and paves the way to the new circular economy of plastics. Here, particularly for polystyrene, we show that styrene monomer yields from Pyrowave’s polystyrene microwave depolymerization reactor is 2,2 to 1,5 times higher than that of the thermal conventional pyrolysis. In addition, we provide a detailed understanding of the microwave assisted depolymerization via analyzing the effects of microwave power, pyrolysis time, microwave receptor and temperature on the styrene product yields. Furthermore, we investigate life cycle environmental impact assessment of microwave assisted pyrolysis of polystyrene in commercial-scale production. Finally, it is worth pointing out that Pyrowave is able to treat several tons of polystyrene to produce virgin styrene monomers and manage waste/contaminated polymeric materials as well in a truly circular economy.Keywords: nanorecycling, nanomaterials, plastic recycling, depolymerization
Procedia PDF Downloads 662375 Anaerobic Co-Digestion of Sewage Sludge and Bagasse for Biogas Recovery
Authors: Raouf Ahmed Mohamed Hassan
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In Egypt, the excess sewage sludge from wastewater Treatment Plants (WWTPs) is rapidly increasing due to the continuous increase of population, urban planning and industrial developments. Also, cane bagasses constitute an important component of Urban Solid Waste (USW), especially at the south of Egypt, which are difficult to degrade under normal composting conditions. These wastes need to be environmentally managed to reduce the negative impacts of its application or disposal. In term of biogas recovery, the anaerobic digestion of sewage sludge or bagasse separately is inefficient, due to the presence of nutrients and minerals. Also, the Carbone-Nitrogen Ratio (C/N) play an important role, sewage sludge has a ratio varies from 6-16, where cane bagasse has a ratio around 150, whereas the suggested optimum C/N ratio for anaerobic digestion is in the range of 20 to 30. The anaerobic co-digestion is presented as a successful methodology that combines several biodegradable organic substrates able to decrease the amount of output wastes by biodegradation, sharing processing facilities, reducing operating costs, while enabling recovery of biogas. This paper presents the study of co-digestion of sewage sludge from wastewater treatment plants as a type of organic wastes and bagasse as agriculture wastes. Laboratory-scale mesophilic and thermophilic digesters were operated with varied hydraulic retention times. Different percentage of sludge and bagasse are investigated based on the total solids (TS). Before digestion, the bagasse was subjected to grinding pretreatment and soaked in distilled water (water pretreatment). The effect of operating parameters (mixing, temperature) is investigated in order to optimize the process in the biogas production. The yield and the composition of biogas from the different experiments were evaluated and the cumulative curves were estimated. The conducted tests did show that there is a good potential to using the co-digestion of wastewater sludge and bagasse for biogas production.Keywords: co-digestion, sewage sludge, bagasse, mixing, mesophilic, thermophilic
Procedia PDF Downloads 5122374 Synthesis and Characterization of Polypyrrole-Coated Non-Conducting Cellulosic Substrate and Modified by Copper Oxide
Authors: A. Hamam, D. Oukil, A. Dib, L. Makhloufi
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The aim of this work is to synthesize modified Polypyrrole films (PPy) containing nanoparticles of copper oxides onto a non conducting cellulosic substrate. Firstly, the chemical polymerization of polypyrrole onto cellulosic substrate is carried out using FeCl3 as an oxidant and Pyrrole as monomer. Different parameters were optimized (monomer concentration, duration of the experiment, nature of supporting electrolyte, temperature, etc.) in order to obtain films with different thickness and different morphologies. Thickness and topography of different PPy deposits were estimated by a profilometer apparatus. The electrochemical reactivity of the obtained electrodes were tested by cyclic voltammetry technique (CV) and electrochemical impedance spectroscopy (EIS). Secondly, the modification of the PPy film surface by incorporation of copper oxide nanonoparticles is conducted by applying a galvanostatic procedure from CuCl2 solution. Surface characterization has been carried out using scanning microscope (SEM) coupled with energy dispersive X-ray analysis (EDX), Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The analysis showed the presence of the copper oxide nanoparticles (CuO) in the polymer films with dimensions less than 50 nm.Keywords: polypyrrole, modified electrode, cellulosic substrate, copper oxide
Procedia PDF Downloads 4512373 Effect of Land Use and Abandonment on Soil Carbon and Nitrogen Depletion by Runoff in Shallow Soils under Semi-Arid Mediterranean Climate
Authors: Mohamed Emran, Giovanni Pardini, Maria Gispert, Mohamed Rashad
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Land use and abandonment in semi-arid degraded ecosystems may cause regressive dynamics in vegetation cover affecting organic matter contents, soil nutrients and structural stability, thus reducing soil resistance to erosion. Mediterranean areas are generally subjected to climatic fluctuations, which modify soil conditions and hydrological processes, such as runoff and water infiltration within the upper soil horizons. Low erosion rates occur in very fragile and shallow soils with minor clay content progressively decrease organic carbon C and nitrogen N pools in the upper soil horizons. Seven soils were selected representing variant context of land use and abandonment at the Cap de Creus Peninsula, Catalonia, NE Spain, from recent cultivated vines and olive groves, mid abandoned forests standing under cork and pine trees, pasture to late abandoned Cistus and Erica scrubs. The aim of this work was to study the effect of changes in land use and abandonment on the depletion of soil organic carbon and nitrogen transported by runoff water in shallow soils after natural rainfall events during two years with different rainfall patterns (1st year with low rainfall and 2nd year with high rainfall) by i) monitoring the most significant soil erosion parameters at recorded rainfall events, ii) studying the most relevant soil physical and chemical characteristics on seasonal basis and iii) analysing the seasonal trends of depleted carbon and nitrogen and their interaction with soil surface compaction parameters. Significant seasonal variability was observed in the relevant soil physical and chemical parameters and soil erosion parameters in all soils to establish their evolution under land use and abandonment during two years of different rainfall patterns (214 and 487 mm per year), giving important indications on soil response to rainfall impacts. Erosion rates decreased significantly with the increasing of soil C and N under low and high rainfall. In cultivated soils, C and N depletion increased by 144% and 115%, respectively by 13% increase in erosion rates during the 1st year with respect to the 2nd year. Depleted C and N were proportionally higher in soils under vines and olive with vulnerable soil structure and low soil resilience leading to degradation, altering nutrients cycles and causing adverse impact on environmental quality. Statistical analysis underlined that, during the 1st year, soil surface was less effective in preserving stocks of organic resources leading to higher susceptibility to erosion with consequent C and N depletion. During the 2nd year, higher organic reserve and water storage occurred despite the increasing of C and N loss with an effective contribution from soil surface compaction parameters. The overall estimation during the two years indicated clear differences among soils under vines, olive, cork and pines, suggesting on the one hand, that current cultivation practices are inappropriate and that reforestation with pines may delay the achievement of better soil conditions. On the other hand, the natural succession of vegetation under Cistus, pasture and Erica suggests the recovery of good soil conditions.Keywords: land abandonment, land use, nutrient's depletion, soil erosion
Procedia PDF Downloads 3462372 [Keynote Speech]: Simulation Studies of Pulsed Voltage Effects on Cells
Authors: Jiahui Song
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In order to predict or explain a complicated biological process, it is important first to construct mathematical models that can be used to yield analytical solutions. Through numerical simulation, mathematical model results can be used to test scenarios that might not be easily attained in a laboratory experiment, or to predict parameters or phenomena. High-intensity, nanosecond pulse electroporation has been a recent development in bioelectrics. The dynamic pore model can be achieved by including a dynamic aspect and a dependence on the pore population density into pore formation energy equation to analyze and predict such electroporation effects. For greater accuracy, with inclusion of atomistic details, molecular dynamics (MD) simulations were also carried out during this study. Besides inducing pores in cells, external voltages could also be used in principle to modulate action potential generation in nerves. This could have an application in electrically controlled ‘pain management’. Also a simple model-based rate equation treatment of the various cellular bio-chemical processes has been used to predict the pulse number dependent cell survival trends.Keywords: model, high-intensity, nanosecond, bioelectrics
Procedia PDF Downloads 2262371 Adsorption of Methylene Blue by Pectin from Durian (Durio zibethinus) Seeds
Authors: Siti Nurkhalimah, Devita Wijiyanti, Kuntari
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Methylene blue is a popular water-soluble dye that is used for dyeing a variety of substrates such as bacteria, wool, and silk. Methylene blue discharged into the aquatic environment will cause health problems for living things. Treatment method for industrial wastewater may be divided into three main categories: physical, chemical, and biological. Among them, adsorption technology is generally considered to be an effective method for quickly lowering the concentration of dissolved dyes in a wastewater. This has attracted considerable research into low-cost alternative adsorbents for adsorbing or removing coloring matter. In this research, pectin from durian seeds was utilized here to assess their ability for the removal of methylene blue. Adsorption parameters are contact time and dye concentration were examined in the batch adsorption processes. Pectin characterization was performed by FTIR spectrometry. Methylene blue concentration was determined by using UV-Vis spectrophotometer. FTIR results show that the samples showed the typical fingerprint in IR spectrogram. The adsorption result on 10 mL of 5 mg/L methylene blue solution achieved 95.12% when contact time 10 minutes and pectin 0.2 g.Keywords: pectin, methylene blue, adsorption, durian seed
Procedia PDF Downloads 1862370 The Effects of Partial Replacement with Sewage Sludge, Calcined Clay, and Waste Marble Powder on Cement Paste Properties
Authors: Abdul Rahim Al Umairi, Hamed Al Kindi
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The cement production process significantly contributes to greenhouse gas emissions, accounting for 25% of total industrial emissions. This study systematically examined new, underutilized materials—sewage sludge ash (SSA), marble waste (MW), and calcined clay (CC)—to evaluate their effects when partially replacing white Portland cement (WPC) in cement paste formulations. Various replacement proportions (10%, 20%, and 30%) were tested, along with different treatment temperatures (600°C, 630°C, 730°C, and 850°C) for SSA and CC. To gain a deeper understanding of the resulting materials, analyses such as XRF, XRD, and SEM were conducted. The highest compressive strength recorded for the 28-day cured cement paste was 91 MPa when 20% SSA (treated at 600°C) was used, compared to just 53 MPa for the control sample. Conversely, CC exhibited minimal enhancement in compressive strength, while MW had detrimental effects. Additionally, replacing WPC with SSA and CC at 9% and 21% resulted in slight improvements in compressive strength. This research highlights the potential of utilizing underexploited materials like SSA to improve the mechanical and chemical properties of cement paste, indicating that further investigation is necessary to enhance environmental sustainability.Keywords: sewage sludge ash, calcined clay, marble waste, cement
Procedia PDF Downloads 202369 Upflow Anaerobic Sludge Blanket Reactor Followed by Dissolved Air Flotation Treating Municipal Sewage
Authors: Priscila Ribeiro dos Santos, Luiz Antonio Daniel
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Inadequate access to clean water and sanitation has become one of the most widespread problems affecting people throughout the developing world, leading to an unceasing need for low-cost and sustainable wastewater treatment systems. The UASB technology has been widely employed as a suitable and economical option for the treatment of sewage in developing countries, which involves low initial investment, low energy requirements, low operation and maintenance costs, high loading capacity, short hydraulic retention times, long solids retention times and low sludge production. Whereas dissolved air flotation process is a good option for the post-treatment of anaerobic effluents, being capable of producing high quality effluents in terms of total suspended solids, chemical oxygen demand, phosphorus, and even pathogens. This work presents an evaluation and monitoring, over a period of 6 months, of one compact full-scale system with this configuration, UASB reactors followed by dissolved air flotation units (DAF), operating in Brazil. It was verified as a successful treatment system, and an issue of relevance since dissolved air flotation process treating UASB reactor effluents is not widely encompassed in the literature. The study covered the removal and behavior of several variables, such as turbidity, total suspend solids (TSS), chemical oxygen demand (COD), Escherichia coli, total coliforms and Clostridium perfringens. The physicochemical variables were analyzed according to the protocols established by the Standard Methods for Examination of Water and Wastewater. For microbiological variables, such as Escherichia coli and total coliforms, it was used the “pour plate” technique with Chromocult Coliform Agar (Merk Cat. No.1.10426) serving as the culture medium, while the microorganism Clostridium perfringens was analyzed through the filtering membrane technique, with the Ágar m-CP (Oxoid Ltda, England) serving as the culture medium. Approximately 74% of total COD was removed in the UASB reactor, and the complementary removal done during the flotation process resulted in 88% of COD removal from the raw sewage, thus the initial concentration of COD of 729 mg.L-1 decreased to 87 mg.L-1. Whereas, in terms of particulate COD, the overall removal efficiency for the whole system was about 94%, decreasing from 375 mg.L-1 in raw sewage to 29 mg.L-1 in final effluent. The UASB reactor removed on average 77% of the TSS from raw sewage. While the dissolved air flotation process did not work as expected, removing only 30% of TSS from the anaerobic effluent. The final effluent presented an average concentration of 38 mg.L-1 of TSS. The turbidity was significantly reduced, leading to an overall efficiency removal of 80% and a final turbidity of 28 NTU.The treated effluent still presented a high concentration of fecal pollution indicators (E. coli, total coliforms, and Clostridium perfringens), showing that the system did not present a good performance in removing pathogens. Clostridium perfringens was the organism which suffered the higher removal by the treatment system. The results can be considered satisfactory for the physicochemical variables, taking into account the simplicity of the system, besides that, it is necessary a post-treatment to improve the microbiological quality of the final effluent.Keywords: dissolved air flotation, municipal sewage, UASB reactor, treatment
Procedia PDF Downloads 3312368 Analyzing the Impact of Board Diversity on Firm Performance: Case Study of the Nigerian Banking Sector
Authors: Data Collete Bob-Manuel
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In light of global financial crisis in 2007-2008 various factors including board diversity, succession planning and board evaluation have been identified as essential ingredients in ensuring board effectiveness. The composition and structure of the board is of outmost importance in assessing a board’s ability and success in achieving its objectives. Following the corporate frauds and accounting scandals such as Enron, WorldCom, Parmalat, Oceanic Bank Nigeria and AfriBank Nigeria, there has been a notable amount of research about the effectiveness of the board of directors in the corporate governance of firms. The need to have an effective board cannot be over emphasized as it results in a more stable and thriving company. There has been an overarching need in the business world for a more diverse workforce and board of directors. Big corporations like Texaco, Ford Motors and DuPont have stated how diversity at every level of the workforce including the board of directors has been cited as a vital element for a company to succeed. Developed countries are also seeking for companies to have a more diverse board. For instance Norway has implemented a 60:40 board ratio to all companies. In West Africa, particularly Nigeria, the topic of diversity has received little attention as most studies conducted have focused on the gender aspect of diversity, which results found to have a negative impact on firm performance. This paper seeks to examine four variables of diversity; age, ethnicity, gender and skills to weigh the positive or negative impact the variables have on firm performance, based on evidence from the Nigerian Financial sector. Information used for this study will be gathered from financial statements and annual reports so as to enable the researcher to reflect on past years to know what is being done differently today. The findings of this study will help the researcher to develop a working definition for ethnicity with regards to the West African context where the issue of “tribe” is a sensitive topic.Keywords: Board of Directors, Board Diversity, Firm Performance, Nigeria
Procedia PDF Downloads 3962367 Flywheel Energy Storage Control Using SVPWM for Small Satellites Application
Authors: Noha El-Gohary, Thanaa El-Shater, A. A. Mahfouz, M. M. Sakr
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Searching for high power conversion efficiency and long lifetime are important goals when designing a power supply subsystem for satellite applications. To fulfill these goals, this paper presents a power supply subsystem for small satellites in which flywheel energy storage system is used as a secondary power source instead of chemical battery. In this paper, the model of flywheel energy storage system is introduced; a DC bus regulation control algorithm for charging and discharging of flywheel based on space vector pulse width modulation technique and motor current control is also introduced. Simulation results showed the operation of the flywheel for charging and discharging mode during illumination and shadowed period. The advantages of the proposed system are confirmed by the simulation results of the power supply system.Keywords: small-satellites, flywheel energy storage system, space vector pulse width modulation, power conversion
Procedia PDF Downloads 4002366 Bacteriocinogenic Strains of Bacillus thuringiensis Isolated from Soil at Northern of Algeria
Authors: R. Gounina-Allouane, I. Moussaoui, N. Boukahel
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Bacillus antimicrobial metabolites, especially those of Bacillus thuringiensis (Bt), are of great interest for research because of health risks generated by the excessive use of chemical additives as well as the propagation of resistant microbial strains, caused by the massive treatment with antibiotics. The objective of this study was the selection of Bt strains producing antimicrobial peptides (bacteriocins), and the partial purification of the most powerful bacteriocins, then the determination of their spectra of antimicrobial action. A collection of twenty one Bt strains isolated from soil at Boumerdès (northern Algeria) was used for screening strains having an antagonistic activity against phylogenetically closed bacteria. Spectra of antagonistic activity of two selected strains was determined against other Bt strains, Gram positive and Gram negative bacterial strains of clinical origin and others from ATCC collection as well as yeasts isolated in human dermatology. Bacteriocins of these two strains were partially purified and their effect on the kinetics of growth of the most sensitive microbial strains was studied. The bacteriocinogenic strains were biochemically characterized and their sensitivity to antibiotics was studied.Keywords: antimicrobial peptides, Bacillus thuringiensis, bacteriocin, partial purification
Procedia PDF Downloads 4352365 A Technical Solution for Micro Mixture with Micro Fluidic Oscillator in Chemistry
Authors: Brahim Dennai, Abdelhak Bentaleb, Rachid Khelfaoui, Asma Abdenbi
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The diffusion flux given by the Fick’s law characterizethe mixing rate. A passive mixing strategy is proposed to enhance mixing of two fluids through perturbed jet low. A numerical study of passive mixers has been presented. This paper is focused on the modeling of a micro-injection systems composed of passive amplifier without mechanical part. The micro-system modeling is based on geometrical oscillators form. An asymmetric micro-oscillator design based on a monostable fluidic amplifier is proposed. The characteristic size of the channels is generally about a few hundred of microns. The numerical results indicate that the mixing performance can be as high as 99 % within a typical mixing chamber of 0.20 mm diameter inlet and 2.0 mm distance of nozzle - spliter. In addition, the results confirm that self-rotation in the circular mixer significantly enhances the mixing performance. The novel micro mixing method presented in this study provides a simple solution to mixing problems in microsystem for application in chemistry.Keywords: micro oscillator, modeling, micro mixture, diffusion, size effect, chemical equation
Procedia PDF Downloads 4302364 Assessment of Carbon Dioxide Separation by Amine Solutions Using Electrolyte Non-Random Two-Liquid and Peng-Robinson Models: Carbon Dioxide Absorption Efficiency
Authors: Arash Esmaeili, Zhibang Liu, Yang Xiang, Jimmy Yun, Lei Shao
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A high pressure carbon dioxide (CO2) absorption from a specific gas in a conventional column has been evaluated by the Aspen HYSYS simulator using a wide range of single absorbents and blended solutions to estimate the outlet CO2 concentration, absorption efficiency and CO2 loading to choose the most proper solution in terms of CO2 capture for environmental concerns. The property package (Acid Gas-Chemical Solvent) which is compatible with all applied solutions for the simulation in this study, estimates the properties based on an electrolyte non-random two-liquid (E-NRTL) model for electrolyte thermodynamics and Peng-Robinson equation of state for the vapor and liquid hydrocarbon phases. Among all the investigated single amines as well as blended solutions, piperazine (PZ) and the mixture of piperazine and monoethanolamine (MEA) have been found as the most effective absorbents respectively for CO2 absorption with high reactivity based on the simulated operational conditions.Keywords: absorption, amine solutions, Aspen HYSYS, carbon dioxide, simulation
Procedia PDF Downloads 1862363 Effects of Spray Dryer Atomizer Speed on Casein Micelle Size in Whole Fat Milk Powder and Physicochemical Properties of White Cheese
Authors: Mohammad Goli, Akram Sharifi, Mohammad Yousefi Jozdani, Seyed Ali Mortazavi
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An industrial spray dryer was used, and the effects of atomizer speed on the physicochemical properties of milk powder, the textural and sensory characteristics of white cheese made from this milk powder, were evaluated. For this purpose, whole milk was converted into powder by using three different speeds (10,000, 11,000, and 12,000 rpm). Results showed that with increasing atomizer speed in the spray dryer, the average size of casein micelle is significantly decreased (p < 0.05), whereas no significant effect is observed on the chemical properties of milk powder. White cheese characteristics indicated that with increasing atomizer speed, texture parameters, such as hardness, mastication, and gumminess, were significantly reduced (p < 0.05). Sensory evaluation also revealed that cheese samples prepared with dried milk produced at 12,000 rpm were highly accepted by panelists. Overall, the findings suggested that 12,000 rpm is the optimal atomizer speed for milk powder production.Keywords: spray drying, powder technology, atomizer speed, particle size, white cheese physical properties
Procedia PDF Downloads 4692362 Identifying Artifacts in SEM-EDS of Fouled RO Membranes Used for the Treatment of Brackish Groundwater Through Raman and ICP-MS Analysis
Authors: Abhishek Soti, Aditya Sharma, Akhilendra Bhushan Gupta
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Fouled reverse osmosis membranes are primarily characterized by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometer (EDS) for a detailed investigation of foulants; however, this has severe limitations on several accounts. Apart from inaccuracy in spectral properties and inevitable interferences and interactions between sample and instrument, misidentification of elements due to overlapping peaks is a significant drawback of EDS. This paper discusses this limitation by analyzing fouled polyamide RO membranes derived from community RO plants of Rajasthan treating brackish water via a combination of results obtained from EDS and Raman spectroscopy and cross corroborating with ICP-MS analysis of water samples prepared by dissolving the deposited salts. The anomalous behavior of different morphic forms of CaCO₃ in aqueous suspensions tends to introduce false reporting of the presence of certain heavy metals and rare earth metals in the scales of the fouled RO membranes used for treating brackish groundwater when analyzed using the commonly adopted techniques like SEM-EDS or Raman spectrometry. Peaks of CaCO₃ reflected in EDS spectra of the membrane were found to be misinterpreted as Scandium due to the automatic assignment of elements by the software. Similarly, the morphic forms merged with the dominant peak of CaCO₃ might be reflected as a single peak of Molybdenum in the Raman spectrum. A subsequent ICP-MS analysis of the deposited salts showed that both Sc and Mo were below detectable levels. It is always essential to cross-confirm the results through a destructive analysis method to avoid such interferences. It is further recommended to study different morphic forms of CaCO₃ scales, as they exhibit anomalous properties like reverse solubility with temperature and hence altered precipitation tendencies, for an accurate description of the composition of scales, which is vital for the smooth functioning of RO systems.Keywords: reverse osmosis, foulant analysis, groundwater, EDS, artifacts
Procedia PDF Downloads 1052361 Effectiveness of Crystallization Coating Materials on Chloride Ions Ingress in Concrete
Authors: Mona Elsalamawy, Ashraf Ragab Mohamed, Abdellatif Elsayed Abosen
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This paper aims to evaluate the effectiveness of different crystalline coating materials concerning of chloride ions penetration. The concrete ages at the coating installation and its moisture conditions were addressed; where, these two factors may play a dominant role for the effectiveness of the used materials. Rapid chloride ions penetration test (RCPT) was conducted at different ages and moisture conditions according to the relevant standard. In addition, the contaminated area and the penetration depth of the chloride ions were investigated immediately after the RCPT test using chemical identifier, 0.1 M silver nitrate AgNO3 solution. Results have shown that, the very low chloride ions penetrability, for the studied crystallization materials, were investigated only with the old age concrete (G1). The significant reduction in chloride ions’ penetrability was illustrated after 7 days of installing the crystalline coating layers. Using imageJ is more reliable to describe the contaminated area of chloride ions, where the distribution of aggregate and heterogeneous of cement mortar was considered in the images analysis.Keywords: chloride permeability, contaminated area, crystalline waterproofing materials, RCPT, XRD
Procedia PDF Downloads 2512360 Controlling the Fluid Flow in Hydrogen Fuel Cells through Material Porosity Designs
Authors: Jamal Hussain Al-Smail
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Hydrogen fuel cells (HFCs) are environmentally friendly, energy converter devices that convert the chemical energy of the reactants (oxygen and hydrogen) to electricity through electrochemical reactions. The level of the electricity production of HFCs mainly increases depending on the oxygen distribution in the HFC’s cathode gas diffusion layer (GDL). With a constant porosity of the GDL, the electrochemical reaction can have a great variation that reduces the cell’s productivity and stability. Our findings bring a methodology in finding porosity designs of the diffusion layer to improve the oxygen distribution such that it results in a stable oxygen-hydrogen reaction. We first introduce a mathematical model involving the mass and momentum transport equations, in which a porosity function of the GDL is incorporated as a control for the fluid flow. We then derive numerical methods for solving the mathematical model. In conclusion, we present our numerical results to show how to design the GDL porosity to result in a uniform oxygen distribution.Keywords: fuel cells, material porosity design, mathematical modeling, porous media
Procedia PDF Downloads 1532359 A Perspective on Allelopathic Potential of Corylus avellana L.
Authors: Tugba G. Isin Ozkan, Yoshiharu Fujii
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One of the most important constrains that decrease the crop yields are weeds. Increased amount and number of chemical herbicides are being utilized every day to control weeds. Chemical herbicides which cause environmental effects, and limitations on implementation of them have led to the nonchemical alternatives in the management of weeds. It is needed increasingly the application of allelopathy as a nonherbicidal innovation to control weed populations in integrated weed management. It is not only because of public concern about herbicide use, but also increased agricultural costs and herbicide resistance weeds. Allelopathy is defined as a common biological phenomenon, direct or indirect interaction which one plant or organism produces biochemicals influence the physiological processes of another neighboring plant or organism. Biochemicals involved in allelopathy are called allelochemicals that influence beneficially or detrimentally the growth, survival, development, and reproduction of other plant or organisms. All plant parts could have allelochemicals which are secondary plant metabolites. Allelochemicals are released to environment, influence the germination and seedling growth of neighbors' weeds; that is the way how allelopathy is applied for weed control. Crop cultivars have significantly different ability for inhibiting the growth of certain weeds. So, a high commercial value crop Corylus avellana L. and its byproducts were chosen to introduce for their allelopathic potential in this research. Edible nut of Corylus avellana L., commonly known as hazelnut is commercially valuable crop with byproducts; skin, hard shell, green leafy cover, and tree leaf. Research on allelopathic potential of a plant by using the sandwich bioassay method and investigation growth inhibitory activity is the first step to develop new and environmentally friendly alternatives for weed control. Thus, the objective of this research is to determine allelopathic potential of C. avellana L. and its byproducts by using sandwich method and to determine effective concentrations (EC) of their extracts for inducing half-maximum elongation inhibition on radicle of test plant, EC50. The sandwich method is reliable and fast bioassay, very useful for allelopathic screening under laboratory conditions. In experiments, lettuce (Lactuca sativa L.) seeds will be test plant, because of its high sensitivity to inhibition by allelochemicals and reliability for germination. In sandwich method, the radicle lengths of dry material treated lettuce seeds and control lettuce seeds will be measured and inhibition of radicle elongation will be determined. Lettuce seeds will also be treated by the methanol extracts of dry hazelnut parts to calculate EC₅₀ values, which are required to induce half-maximal inhibition of growth, as mg dry weight equivalent mL-1. Inhibitory activity of extracts against lettuce seedling elongation will be evaluated, like in sandwich method, by comparing the radicle lengths of treated seeds with that of control seeds and EC₅₀ values will be determined. Research samples are dry parts of Turkish hazelnut, C. avellana L. The results would suggest the opportunity for allelopathic potential of C. avellana L. with its byproducts in plant-plant interaction, might be utilized for further researches, could be beneficial in finding bioactive chemicals from natural products and developing of natural herbicides.Keywords: allelopathy, Corylus avellana L., EC50, Lactuca sativa L., sandwich method, Turkish hazelnut
Procedia PDF Downloads 1752358 Synthesis of Brominated Pyrazoline Derived from Chalcone and Its Antimicrobial Activity
Authors: Annisa I. Reza, Jasril Karim
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Despite the availability of antimicrobial agents in the market, the urge to study and find other chemical compounds with the better potential of replacing them still tempting the scientists. This experiment is in the aim to explore a novel brominated pyrazoline ring which was made from intermediate chalcone as a candidate to answer the challenge. Using green chemistry approach by microwave irradiation from domestic oven, both known chalcone and 5-(2-bromophenyl)-3-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazole were successfully synthesized. Pyrazoline’s structure was confirmed based on UV, IR, ¹H-NMR, ¹³C-NMR and MS and together with its intermediate were examined against some microorganisms (Bacillus subtilis, Escherichia coli, and Candida albicans) under agar diffusion method. The results collected during experiment revealed that both tested compounds showed weak activity on B.subtilis which was proven by a zone of inhibitions, while there was no zone of inhibitions observed in E. coli and C. albicans. This is suggested because of the bulky structure around pyrazoline could not provide the main ring to interact with microbial’s cell wall. The study shows that the proposed compound had the low capability as a promising antimicrobial agent, yet it still enriches the information about pyrazoline ring.Keywords: antimicrobial, chalcone, microwave irradiation, pyrazoline
Procedia PDF Downloads 1512357 Heterogeneous Photocatalytic Degradation of Methylene Blue by Montmorillonite/CuxCd1-xs Nanomaterials
Authors: Horiya Boukhatem, Lila Djouadi, Hussein Khalaf, Rufino Manuel Navarro Yerga, Fernando Vaquero Gonzalez
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Heterogeneous photo catalysis is an alternative method for the removal of organic pollutants in water. The photo excitation of a semi-conductor under ultra violet (UV) irradiation entails the production of hydroxyl radicals, one of the most oxidative chemical species. The objective of this study is the synthesis of nano materials based on montmorillonite and CuxCd1-xS with different Cu concentration (0.3 < x < 0.7) and their application in photocatalysis of a cationic dye: methylene blue. The synthesized nano materials and montmorillonite were characterized by fourier transform infrared (FTIR). Test results of photo catalysis of methylene blue under UV-Visible irradiation show that the photoactivity of nano materials montmorillonite/ CuxCd1-xS increase with the increasing of Cu concentration and it is significantly higher compared to that of sodium montmorillonite alone. The application of the kinetic model of Langmuir-Hinshelwood (L-H) to the photocatalytic test results showed that the reaction rate obeys to the first-order kinetic model.Keywords: heterogeneous photo catalysis, methylene blue, montmorillonite, nano material
Procedia PDF Downloads 3392356 Synthesis, Growth, Characterization and Quantum Chemical Investigations of an Organic Single Crystal: 2-Amino- 4-Methylpyridinium Quinoline- 2-Carboxylate
Authors: Anitha Kandasamy, Thirumurugan Ramaiah
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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation
Procedia PDF Downloads 1222355 Remedying Students' Misconceptions in Learning of Chemical Bonding and Spontaneity through Intervention Discussion Learning Model (IDLM)
Authors: Ihuarulam A. Ikenna
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In the past few decades, the field of chemistry education has grown tremendously and researches indicated that after traditional chemistry instruction students often lacked deep conceptual understanding and failed to integrate their ideas into coherent conceptual framework. For several concepts in chemistry, students at all levels have demonstrated difficulty in changing their initial perceptions. Their perceptions are most often wrong and do not agree with correct scientific concepts. This study explored the effectiveness of intervention discussion sections for a college general chemistry course designed to apply research on students preconceptions, knowledge integration and student explanation. Three interventions discussions lasting three hours on bond energy and spontaneity were done tested and intervention (treatment) students’ performances were compared with that of control group which did not use the experimental pedagogy. Results indicated that this instruction which was capable of identifying students' misconceptions, initial conceptions and integrating those ideas into class discussion led to enhanced conceptual understanding and better achievement for the experimental group.Keywords: remedying, students’ misconceptions, learning, intervention discussion, learning model
Procedia PDF Downloads 4192354 Drug-Drug Interaction Prediction in Diabetes Mellitus
Authors: Rashini Maduka, C. R. Wijesinghe, A. R. Weerasinghe
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Drug-drug interactions (DDIs) can happen when two or more drugs are taken together. Today DDIs have become a serious health issue due to adverse drug effects. In vivo and in vitro methods for identifying DDIs are time-consuming and costly. Therefore, in-silico-based approaches are preferred in DDI identification. Most machine learning models for DDI prediction are used chemical and biological drug properties as features. However, some drug features are not available and costly to extract. Therefore, it is better to make automatic feature engineering. Furthermore, people who have diabetes already suffer from other diseases and take more than one medicine together. Then adverse drug effects may happen to diabetic patients and cause unpleasant reactions in the body. In this study, we present a model with a graph convolutional autoencoder and a graph decoder using a dataset from DrugBank version 5.1.3. The main objective of the model is to identify unknown interactions between antidiabetic drugs and the drugs taken by diabetic patients for other diseases. We considered automatic feature engineering and used Known DDIs only as the input for the model. Our model has achieved 0.86 in AUC and 0.86 in AP.Keywords: drug-drug interaction prediction, graph embedding, graph convolutional networks, adverse drug effects
Procedia PDF Downloads 1002353 Structural Fluxionality of Luminescent Coordination Compounds with Lanthanide Ions
Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo
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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality
Procedia PDF Downloads 199