Search results for: atomic hydrogen
Commenced in January 2007
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Edition: International
Paper Count: 1590

Search results for: atomic hydrogen

90 Investigation of Alumina Membrane Coated Titanium Implants on Osseointegration

Authors: Pinar Erturk, Sevde Altuntas, Fatih Buyukserin

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In order to obtain an effective integration between an implant and a bone, implant surfaces should have similar properties to bone tissue surfaces. Especially mimicry of the chemical, mechanical and topographic properties of the implant to the bone is crucial for fast and effective osseointegration. Titanium-based biomaterials are more preferred in clinical use, and there are studies of coating these implants with oxide layers that have chemical/nanotopographic properties stimulating cell interactions for enhanced osseointegration. There are low success rates of current implantations, especially in craniofacial implant applications, which are large and vital zones, and the oxide layer coating increases bone-implant integration providing long-lasting implants without requiring revision surgery. Our aim in this study is to examine bone-cell behavior on titanium implants with an aluminum oxide layer (AAO) on effective osseointegration potential in the deformation of large zones with difficult spontaneous healing. In our study, aluminum layer coated titanium surfaces were anodized in sulfuric, phosphoric, and oxalic acid, which are the most common used AAO anodization electrolytes. After morphologic, chemical, and mechanical tests on AAO coated Ti substrates, viability, adhesion, and mineralization of adult bone cells on these substrates were analyzed. Besides with atomic layer deposition (ALD) as a sensitive and conformal technique, these surfaces were coated with pure alumina (5 nm); thus, cell studies were performed on ALD-coated nanoporous oxide layers with suppressed ionic content too. Lastly, in order to investigate the effect of the topography on the cell behavior, flat non-porous alumina layers on silicon wafers formed by ALD were compared with the porous ones. Cell viability ratio was similar between anodized surfaces, but pure alumina coated titanium and anodized surfaces showed a higher viability ratio compared to bare titanium and bare anodized ones. Alumina coated titanium surfaces, which anodized in phosphoric acid, showed significantly different mineralization ratios after 21 days over other bare titanium and titanium surfaces which anodized in other electrolytes. Bare titanium was the second surface that had the highest mineralization ratio. Otherwise, titanium, which is anodized in oxalic acid electrolyte, demonstrated the lowest mineralization. No significant difference was shown between bare titanium and anodized surfaces except AAO titanium surface anodized in phosphoric acid. Currently, osteogenic activities of these cells on the genetic level are investigated by quantitative real-time polymerase chain reaction (qRT-PCR) analysis results of RUNX-2, VEGF, OPG, and osteopontin genes. Also, as a result of the activities of the genes mentioned before, Western Blot will be used for protein detection. Acknowledgment: The project is supported by The Scientific and Technological Research Council of Turkey.

Keywords: alumina, craniofacial implant, MG-63 cell line, osseointegration, oxalic acid, phosphoric acid, sulphuric acid, titanium

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89 Organic Permeation Properties of Hydrophobic Silica Membranes with Different Functional Groups

Authors: Sadao Araki, Daisuke Gondo, Satoshi Imasaka, Hideki Yamamoto

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The separation of organic compounds from aqueous solutions is a key technology for recycling valuable organic compounds and for the treatment of wastewater. The wastewater from chemical plants often contains organic compounds such as ethyl acetate (EA), methylethyl ketone (MEK) and isopropyl alcohol (IPA). In this study, we prepared hydrophobic silica membranes by a sol-gel method. We used phenyltrimethoxysilane (PhTMS), ethyltrimethoxysilan (ETMS), Propyltrimethoxysilane (PrTMS), N-butyltrimethoxysilane (BTMS), N-Hexyltrimethoxysilane (HTMS) as silica sources to introduce each functional groups on the membrane surface. Cetyltrimethyl ammonium bromide (CTAB) was used as a molecular template to create suitable pore that enable the permeation of organic compounds. These membranes with five different functional groups were characterized by SEM, FT-IR, and permporometry. Thicknesses and pore diameters of silica layer for all membrane were about 1.0 μm and about 1 nm, respectively. In other words, functional groups had an insignificant effect on the membrane thicknesses and the formation of the pore by CTAB. We confirmed the effect of functional groups on the flux and separation factor for ethyl acetate (EA), methyl ethyl ketone, acetone and 1-butanol (1-BtOH) /water mixtures. All membranes showed a high flux for ethyl acetate compared with other compounds. In particular, the hydrophobic silica membrane prepared by using BTMS showed 0.75 kg m-2 h-1 of flux for EA. For all membranes, the fluxes of organic compounds showed the large values in the order corresponding to EA > MEK > acetone > 1-BtOH. On the other hand, carbon chain length of functional groups among ETMS, PrTMS, BTMS, PrTMS and HTMS did not have a major effect on the organic flux. Although we confirmed the relationship between organic fluxes and organic molecular diameters or fugacity of organic compounds, these factors had a low correlation with organic fluxes. It is considered that these factors affect the diffusivity. Generally, permeation through membranes is based on the diffusivity and solubility. Therefore, it is deemed that organic fluxes through these hydrophobic membranes are strongly influenced by solubility. We tried to estimate the organic fluxes by Hansen solubility parameter (HSP). HSP, which is based on the cohesion energy per molar volume and is composed of dispersion forces (δd), intermolecular dipole interactions (δp), and hydrogen-bonding interactions (δh), has recently attracted attention as a means for evaluating the resolution and aggregation behavior. Evaluation of solubility for two substances can be represented by using the Ra [(MPa)1/2] value, meaning the distance of HSPs for both of substances. A smaller Ra value means a higher solubility for each substance. On the other hand, it can be estimated that the substances with large Ra value show low solubility. We established the correlation equation, which was based on Ra, of organic flux at low concentrations of organic compounds and at 295-325 K.

Keywords: hydrophobic, membrane, Hansen solubility parameter, functional group

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88 Mesoporous BiVO4 Thin Films as Efficient Visible Light Driven Photocatalyst

Authors: Karolina Ordon, Sandrine Coste, Malgorzata Makowska-Janusik, Abdelhadi Kassiba

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Photocatalytic processes play key role in the production of a new source of energy (as hydrogen), design of self-cleaning surfaces or for the environment preservation. The most challenging task deals with the purification of water distinguished by high efficiency. In the mentioned process, organic pollutants in solutions are decomposed to the simple, non-toxic compounds as H2O and CO2. The most known photocatalytic materials are ZnO, CdS and TiO2 semiconductors with a particular involvement of TiO2 as an efficient photocatalysts even with a high band gap equal to 3.2 eV which exploit only UV radiation from solar emitted spectrum. However, promising material with visible light induced photoactivity was searched through the monoclinic polytype of BiVO4 which has energy gap about 2.4 eV. As required in heterogeneous photocatalysis, the high contact surface is required. Also, BiVO4 as photocatalyst can be optimized by increasing its surface area by achieving the mesoporous structure synthesize. The main goal of the present work consists in the synthesis and characterization of BiVO4 mesoporous thin film. The synthesis method based on sol-gel was carried out using a standard surfactants such as P123 and F127. The thin film was deposited by spin and dip coating method. Then, the structural analysis of the obtained material was performed thanks to X-ray diffraction (XRD) and Raman spectroscopy. The surface of resulting structure was investigated using a scanning electron microscopy (SEM). The computer simulations based on modeling the optical and electronic properties of bulk BiVO4 by using DFT (density functional theory) methodology were carried out. The semiempirical parameterized method PM6 was used to compute the physical properties of BiVO4 nanostructures. The Raman and IR absorption spectra were also measured for synthesized mesoporous material, and the results were compared with the theoretical predictions. The simulations of nanostructured BiVO4 have pointed out the occurrence of quantum confinement for nanosized clusters leading to widening of the band gap. This result overcame the relevance of nanosized objects to harvest wide part of the solar spectrum. Also, a balance was searched experimentally through the mesoporous nature of the films devoted to enhancing the contact surface as required for heterogeneous catalysis without to lower the nanocrystallite size under some critical sizes inducing an increased band gap. The present contribution will discuss the relevant features of the mesoporous films with respect to their photocatalytic responses.

Keywords: bismuth vanadate, photocatalysis, thin film, quantum-chemical calculations

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87 Ternary Organic Blend for Semitransparent Solar Cells with Enhanced Short Circuit Current Density

Authors: Mohammed Makha, Jakob Heier, Frank Nüesch, Roland Hany

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Organic solar cells (OSCs) have made rapid progress and currently achieve power conversion efficiencies (PCE) of over 10%. OSCs have several merits over other direct light-to-electricity generating cells and can be processed at low cost from solution on flexible substrates over large areas. Moreover, combining organic semiconductors with transparent and conductive electrodes allows for the fabrication of semitransparent OSCs (SM-OSCs). For SM-OSCs the challenge is to achieve a high average visible transmission (AVT) while maintaining a high short circuit current (Jsc). Typically, Jsc of SM-OSCs is smaller than when using an opaque metal top electrode. This is because the non-absorbed light during the first transit through the active layer and the transparent electrode is forward-transmitted out of the device. Recently, OSCs using a ternary blend of organic materials have received attention. This strategy was pursued to extend the light harvesting over the visible range. However, it is a general challenge to manipulate the performance of ternary OSCs in a predictable way, because many key factors affect the charge generation and extraction in ternary solar cells. Consequently, the device performance is affected by the compatibility between the blend components and the resulting film morphology, the energy levels and bandgaps, the concentration of the guest material and its location in the active layer. In this work, we report on a solvent-free lamination process for the fabrication of efficient and semitransparent ternary blend OSCs. The ternary blend was composed of PC70BM and the electron donors PBDTTT-C and an NIR cyanine absorbing dye (Cy7T). Using an opaque metal top electrode, a PCE of 6% was achieved for the optimized binary polymer: fullerene blend (AVT = 56%). However, the PCE dropped to ~2% when decreasing (to 30 nm) the active film thickness to increase the AVT value (75%). Therefore we resorted to the ternary blend and measured for non-transparent cells a PCE of 5.5% when using an active polymer: dye: fullerene (0.7: 0.3: 1.5 wt:wt:wt) film of 95 nm thickness (AVT = 65% when omitting the top electrode). In a second step, the optimized ternary blend was used of the fabrication of SM-OSCs. We used a plastic/metal substrate with a light transmission of over 90% as a transparent electrode that was applied via a lamination process. The interfacial layer between the active layer and the top electrode was optimized in order to improve the charge collection and the contact with the laminated top electrode. We demonstrated a PCE of 3% with AVT of 51%. The parameter space for ternary OSCs is large and it is difficult to find the best concentration ratios by trial and error. A rational approach for device optimization is the construction of a ternary blend phase diagram. We discuss our attempts to construct such a phase diagram for the PBDTTT-C: Cy7T: PC70BM system via a combination of using selective Cy7T selective solvents and atomic force microscopy. From the ternary diagram suitable morphologies for efficient light-to-current conversion can be identified. We compare experimental OSC data with these predictions.

Keywords: organic photovoltaics, ternary phase diagram, ternary organic solar cells, transparent solar cell, lamination

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86 The Concept of Path in Original Buddhism and the Concept of Psychotherapeutic Improvement

Authors: Beth Jacobs

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The landmark movement of Western clinical psychology in the 20th century was the development of psychotherapy. The landmark movement of clinical psychology in the 21st century will be the absorption of meditation practices from Buddhist psychology. While millions of people explore meditation and related philosophy, very few people are exposed to the materials of original Buddhism on this topic, especially to the Theravadan Abhidharma. The Abhidharma is an intricate system of lists and matrixes that were used to understand and remember Buddha’s teaching. The Abhidharma delineates the first psychological system of Buddhism, how the mind works in the universe of reality and why meditation training strengthens and purifies the experience of life. Its lists outline the psychology of mental constructions, perception, emotion and cosmological causation. While the Abhidharma is technical, elaborate and complex, its essential purpose relates to the central purpose of clinical psychology: to relieve human suffering. Like Western depth psychology, the methodology rests on understanding underlying processes of consciousness and perception. What clinical psychologists might describe as therapeutic improvement, the Abhidharma delineates as a specific pathway of purified actions of consciousness. This paper discusses the concept of 'path' as presented in aspects of the Theravadan Abhidharma and relates this to current clinical psychological views of therapy outcomes and gains. The core path in Buddhism is the Eight-Fold Path, which is the fourth noble truth and the launching of activity toward liberation. The path is not composed of eight ordinal steps; it’s eight-fold and is described as opening the way, not funneling choices. The specific path in the Abhidharma is described in many steps of development of consciousness activities. The path is not something a human moves on, but something that moments of consciousness develop within. 'Cittas' are extensively described in the Abhidharma as the atomic-level unit of a raw action of consciousness touching upon an object in a field, and there are 121 types of cittas categorized. The cittas are embedded in the mental factors, which could be described as the psychological packaging elements of our experiences of consciousness. Based on these constellations of infinitesimal, linked occurrences of consciousness, citta are categorized by dimensions of purification. A path is a chain of citta developing through causes and conditions. There are no selves, no pronouns in the Abhidharma. Instead of me walking a path, this is about a person working with conditions to cultivate a stream of consciousness that is pure, immediate, direct and generous. The same effort, in very different terms, informs the work of most psychotherapies. Depth psychology seeks to release the bound, unconscious elements of mental process into the clarity of realization. Cognitive and behavioral psychologies work on breaking down automatic thought valuations and actions, changing schemas and interpersonal dynamics. Understanding how the original Buddhist concept of positive human development relates to the clinical psychological concept of therapy weaves together two brilliant systems of thought on the development of human well being.

Keywords: Abhidharma, Buddhist path, clinical psychology, psychotherapeutic outcome

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85 Mechanical Response Investigation of Wafer Probing Test with Vertical Cobra Probe via the Experiment and Transient Dynamic Simulation

Authors: De-Shin Liu, Po-Chun Wen, Zhen-Wei Zhuang, Hsueh-Chih Liu, Pei-Chen Huang

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Wafer probing tests play an important role in semiconductor manufacturing procedures in accordance with the yield and reliability requirement of the wafer after the backend-of-the-line process. Accordingly, the stable physical and electrical contact between the probe and the tested wafer during wafer probing is regarded as an essential issue in identifying the known good die. The probe card can be integrated with multiple probe needles, which are classified as vertical, cantilever and micro-electro-mechanical systems type probe selections. Among all potential probe types, the vertical probe has several advantages as compared with other probe types, including maintainability, high probe density and feasibility for high-speed wafer testing. In the present study, the mechanical response of the wafer probing test with the vertical cobra probe on 720 μm thick silicon (Si) substrate with a 1.4 μm thick aluminum (Al) pad is investigated by the experiment and transient dynamic simulation approach. Because the deformation mechanism of the vertical cobra probe is determined by both bending and buckling mechanisms, the stable correlation between contact forces and overdrive (OD) length must be carefully verified. Moreover, the decent OD length with corresponding contact force contributed to piercing the native oxide layer of the Al pad and preventing the probing test-induced damage on the interconnect system. Accordingly, the scratch depth of the Al pad under various OD lengths is estimated by the atomic force microscope (AFM) and simulation work. In the wafer probing test configuration, the contact phenomenon between the probe needle and the tested object introduced large deformation and twisting of mesh gridding, causing the subsequent numerical divergence issue. For this reason, the arbitrary Lagrangian-Eulerian method is utilized in the present simulation work to conquer the aforementioned issue. The analytic results revealed a slight difference when the OD is considered as 40 μm, and the simulated is almost identical to the measured scratch depths of the Al pad under higher OD lengths up to 70 μm. This phenomenon can be attributed to the unstable contact of the probe at low OD length with the scratch depth below 30% of Al pad thickness, and the contact status will be being stable when the scratch depth over 30% of pad thickness. The splash of the Al pad is observed by the AFM, and the splashed Al debris accumulates on a specific side; this phenomenon is successfully simulated in the transient dynamic simulation. Thus, the preferred testing OD lengths are found as 45 μm to 70 μm, and the corresponding scratch depths on the Al pad are represented as 31.4% and 47.1% of Al pad thickness, respectively. The investigation approach demonstrated in this study contributed to analyzing the mechanical response of wafer probing test configuration under large strain conditions and assessed the geometric designs and material selections of probe needles to meet the requirement of high resolution and high-speed wafer-level probing test for thinned wafer application.

Keywords: wafer probing test, vertical probe, probe mark, mechanical response, FEA simulation

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84 Effect of Multi-Walled Carbon Nanotubes on Fuel Cell Membrane Performance

Authors: Rabindranath Jana, Biswajit Maity, Keka Rana

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The most promising clean energy source is the fuel cell, since it does not generate toxic gases and other hazardous compounds. Again the direct methanol fuel cell (DMFC) is more user-friendly as it is easy to be miniaturized and suited as energy source for automobiles as well as domestic applications and portable devices. And unlike the hydrogen used for some fuel cells, methanol is a liquid that is easy to store and transport in conventional tanks. The most important part of a fuel cell is its membrane. Till now, an overall efficiency for a methanol fuel cell is reported to be about 20 ~ 25%. The lower efficiency of the cell may be due to the critical factors, e.g. slow reaction kinetics at the anode and methanol crossover. The oxidation of methanol is composed of a series of successive reactions creating formaldehyde and formic acid as intermediates that contribute to slow reaction rates and decreased cell voltage. Currently, the investigation of new anode catalysts to improve oxidation reaction rates is an active area of research as it applies to the methanol fuel cell. Surprisingly, there are very limited reports on nanostructured membranes, which are rather simple to manufacture with different tuneable compositions and are expected to allow only the proton permeation but not the methanol due to their molecular sizing effects and affinity to the membrane surface. We have developed a nanostructured fuel cell membrane from polydimethyl siloxane rubber (PDMS), ethylene methyl co-acrylate (EMA) and multi-walled carbon nanotubes (MWNTs). The effect of incorporating different proportions of f-MWNTs in polymer membrane has been studied. The introduction of f-MWNTs in polymer matrix modified the polymer structure, and therefore the properties of the device. The proton conductivity, measured by an AC impedance technique using open-frame and two-electrode cell and methanol permeability of the membranes was found to be dependent on the f-MWNTs loading. The proton conductivity of the membranes increases with increase in concentration of f-MWNTs concentration due to increased content of conductive materials. Measured methanol permeabilities at 60oC were found to be dependant on loading of f-MWNTs. The methanol permeability decreased from 1.5 x 10-6 cm²/s for pure film to 0.8 x 10-7 cm²/s for a membrane containing 0.5wt % f-MWNTs. This is due to increasing proportion of f-MWNTs, the matrix becomes more compact. From DSC melting curves it is clear that the polymer matrix with f-MWNTs is thermally stable. FT-IR studies show good interaction between EMA and f-MWNTs. XRD analysis shows good crystalline behavior of the prepared membranes. Significant cost savings can be achieved when using the blended films which contain less expensive polymers.

Keywords: fuel cell membrane, polydimethyl siloxane rubber, carbon nanotubes, proton conductivity, methanol permeability

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83 Monsoon Controlled Mercury Transportation in Ganga Alluvial Plain, Northern India and Its Implication on Global Mercury Cycle

Authors: Anjali Singh, Ashwani Raju, Vandana Devi, Mohmad Mohsin Atique, Satyendra Singh, Munendra Singh

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India is the biggest consumer of mercury and, consequently, a major emitter too. The increasing mercury contamination in India’s water resources has gained widespread attention and, therefore, atmospheric deposition is of critical concern. However, little emphasis was placed on the role of precipitation in the aquatic mercury cycle of the Ganga Alluvial Plain which provides drinking water to nearly 7% of the world’s human population. A majority of the precipitation here occurs primarily in 10% duration of the year in the monsoon season. To evaluate the sources and transportation of mercury, water sample analysis has been conducted from two selected sites near Lucknow, which have a strong hydraulic gradient towards the river. 31 groundwater samples from Jehta village (26°55’15’’N; 80°50’21’’E; 119 m above mean sea level) and 31 river water samples from the Behta Nadi (a tributary of the Gomati River draining into the Ganga River) were collected during the monsoon season on every alternate day between 01 July to 30 August 2019. The total mercury analysis was performed by using Flow Injection Atomic Absorption Spectroscopy (AAS)-Mercury Hybride System, and daily rainfall data was collected from the India Meteorological Department, Amausi, Lucknow. The ambient groundwater and river-water concentrations were both 2-4 ng/L as there is no known geogenic source of mercury found in the area. Before the onset of the monsoon season, the groundwater and the river-water recorded mercury concentrations two orders of magnitude higher than the ambient concentrations, indicating the regional transportation of the mercury from the non-point source into the aquatic environment. Maximum mercury concentrations in groundwater and river-water were three orders of magnitude higher than the ambient concentrations after the onset of the monsoon season characterizing the considerable mobilization and redistribution of mercury by monsoonal precipitation. About 50% of both of the water samples were reported mercury below the detection limit, which can be mostly linked to the low intensity of precipitation in August and also with the dilution factor by precipitation. The highest concentration ( > 1200 ng/L) of mercury in groundwater was reported after 6-days lag from the first precipitation peak. Two high concentration peaks (>1000 ng/L) in river-water were separately correlated with the surface flow and groundwater outflow of mercury. We attribute the elevated mercury concentration in both of the water samples before the precipitation event to mercury originating from the extensive use of agrochemicals in mango farming in the plain. However, the elevated mercury concentration during the onset of monsoon appears to increase in area wetted with atmospherically deposited mercury, which migrated down from surface water to groundwater as downslope migration is a fundamental mechanism seen in rivers of the alluvial plain. The present study underscores the significance of monsoonal precipitation in the transportation of mercury to drinking water resources of the Ganga Alluvial Plain. This study also suggests that future research must be pursued for a better understand of the human health impact of mercury contamination and for quantification of the role of Ganga Alluvial Plain in the Global Mercury Cycle.

Keywords: drinking water resources, Ganga alluvial plain, india, mercury

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82 Electron Bernstein Wave Heating in the Toroidally Magnetized System

Authors: Johan Buermans, Kristel Crombé, Niek Desmet, Laura Dittrich, Andrei Goriaev, Yurii Kovtun, Daniel López-Rodriguez, Sören Möller, Per Petersson, Maja Verstraeten

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The International Thermonuclear Experimental Reactor (ITER) will rely on three sources of external heating to produce and sustain a plasma; Neutral Beam Injection (NBI), Ion Cyclotron Resonance Heating (ICRH), and Electron Cyclotron Resonance Heating (ECRH). ECRH is a way to heat the electrons in a plasma by resonant absorption of electromagnetic waves. The energy of the electrons is transferred indirectly to the ions by collisions. The electron cyclotron heating system can be directed to deposit heat in particular regions in the plasma (https://www.iter.org/mach/Heating). Electron Cyclotron Resonance Heating (ECRH) at the fundamental resonance in X-mode is limited by a low cut-off density. Electromagnetic waves cannot propagate in the region between this cut-off and the Upper Hybrid Resonance (UHR) and cannot reach the Electron Cyclotron Resonance (ECR) position. Higher harmonic heating is hence preferred in heating scenarios nowadays to overcome this problem. Additional power deposition mechanisms can occur above this threshold to increase the plasma density. This includes collisional losses in the evanescent region, resonant power coupling at the UHR, tunneling of the X-wave with resonant coupling at the ECR, and conversion to the Electron Bernstein Wave (EBW) with resonant coupling at the ECR. A more profound knowledge of these deposition mechanisms can help determine the optimal plasma production scenarios. Several ECRH experiments are performed on the TOroidally MAgnetized System (TOMAS) to identify the conditions for Electron Bernstein Wave (EBW) heating. Density and temperature profiles are measured with movable Triple Langmuir Probes in the horizontal and vertical directions. Measurements of the forwarded and reflected power allow evaluation of the coupling efficiency. Optical emission spectroscopy and camera images also contribute to plasma characterization. The influence of the injected power, magnetic field, gas pressure, and wave polarization on the different deposition mechanisms is studied, and the contribution of the Electron Bernstein Wave is evaluated. The TOMATOR 1D hydrogen-helium plasma simulator numerically describes the evolution of current less magnetized Radio Frequency plasmas in a tokamak based on Braginskii’s legal continuity and heat balance equations. This code was initially benchmarked with experimental data from TCV to determine the transport coefficients. The code is used to model the plasma parameters and the power deposition profiles. The modeling is compared with the data from the experiments.

Keywords: electron Bernstein wave, Langmuir probe, plasma characterization, TOMAS

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81 Thermal Ageing of a 316 Nb Stainless Steel: From Mechanical and Microstructural Analyses to Thermal Ageing Models for Long Time Prediction

Authors: Julien Monnier, Isabelle Mouton, Francois Buy, Adrien Michel, Sylvain Ringeval, Joel Malaplate, Caroline Toffolon, Bernard Marini, Audrey Lechartier

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Chosen to design and assemble massive components for nuclear industry, the 316 Nb austenitic stainless steel (also called 316 Nb) suits well this function thanks to its mechanical, heat and corrosion handling properties. However, these properties might change during steel’s life due to thermal ageing causing changes within its microstructure. Our main purpose is to determine if the 316 Nb will keep its mechanical properties after an exposition to industrial temperatures (around 300 °C) during a long period of time (< 10 years). The 316 Nb is composed by different phases, which are austenite as main phase, niobium-carbides, and ferrite remaining from the ferrite to austenite transformation during the process. Our purpose is to understand thermal ageing effects on the material microstructure and properties and to submit a model predicting the evolution of 316 Nb properties as a function of temperature and time. To do so, based on Fe-Cr and 316 Nb phase diagrams, we studied the thermal ageing of 316 Nb steel alloys (1%v of ferrite) and welds (10%v of ferrite) for various temperatures (350, 400, and 450 °C) and ageing time (from 1 to 10.000 hours). Higher temperatures have been chosen to reduce thermal treatment time by exploiting a kinetic effect of temperature on 316 Nb ageing without modifying reaction mechanisms. Our results from early times of ageing show no effect on steel’s global properties linked to austenite stability, but an increase of ferrite hardness during thermal ageing has been observed. It has been shown that austenite’s crystalline structure (cfc) grants it a thermal stability, however, ferrite crystalline structure (bcc) favours iron-chromium demixion and formation of iron-rich and chromium-rich phases within ferrite. Observations of thermal ageing effects on ferrite’s microstructure were necessary to understand the changes caused by the thermal treatment. Analyses have been performed by using different techniques like Atomic Probe Tomography (APT) and Differential Scanning Calorimetry (DSC). A demixion of alloy’s elements leading to formation of iron-rich (α phase, bcc structure), chromium-rich (α’ phase, bcc structure), and nickel-rich (fcc structure) phases within the ferrite have been observed and associated to the increase of ferrite’s hardness. APT results grant information about phases’ volume fraction and composition, allowing to associate hardness measurements to the volume fractions of the different phases and to set up a way to calculate α’ and nickel-rich particles’ growth rate depending on temperature. The same methodology has been applied to DSC results, which allowed us to measure the enthalpy of α’ phase dissolution between 500 and 600_°C. To resume, we started from mechanical and macroscopic measurements and explained the results through microstructural study. The data obtained has been match to CALPHAD models’ prediction and used to improve these calculations and employ them to predict 316 Nb properties’ change during the industrial process.

Keywords: stainless steel characterization, atom probe tomography APT, vickers hardness, differential scanning calorimetry DSC, thermal ageing

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80 Multiphase Equilibrium Characterization Model For Hydrate-Containing Systems Based On Trust-Region Method Non-Iterative Solving Approach

Authors: Zhuoran Li, Guan Qin

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A robust and efficient compositional equilibrium characterization model for hydrate-containing systems is required, especially for time-critical simulations such as subsea pipeline flow assurance analysis, compositional simulation in hydrate reservoirs etc. A multiphase flash calculation framework, which combines Gibbs energy minimization function and cubic plus association (CPA) EoS, is developed to describe the highly non-ideal phase behavior of hydrate-containing systems. A non-iterative eigenvalue problem-solving approach for the trust-region sub-problem is selected to guarantee efficiency. The developed flash model is based on the state-of-the-art objective function proposed by Michelsen to minimize the Gibbs energy of the multiphase system. It is conceivable that a hydrate-containing system always contains polar components (such as water and hydrate inhibitors), introducing hydrogen bonds to influence phase behavior. Thus, the cubic plus associating (CPA) EoS is utilized to compute the thermodynamic parameters. The solid solution theory proposed by van der Waals and Platteeuw is applied to represent hydrate phase parameters. The trust-region method combined with the trust-region sub-problem non-iterative eigenvalue problem-solving approach is utilized to ensure fast convergence. The developed multiphase flash model's accuracy performance is validated by three available models (one published and two commercial models). Hundreds of published hydrate-containing system equilibrium experimental data are collected to act as the standard group for the accuracy test. The accuracy comparing results show that our model has superior performances over two models and comparable calculation accuracy to CSMGem. Efficiency performance test also has been carried out. Because the trust-region method can determine the optimization step's direction and size simultaneously, fast solution progress can be obtained. The comparison results show that less iteration number is needed to optimize the objective function by utilizing trust-region methods than applying line search methods. The non-iterative eigenvalue problem approach also performs faster computation speed than the conventional iterative solving algorithm for the trust-region sub-problem, further improving the calculation efficiency. A new thermodynamic framework of the multiphase flash model for the hydrate-containing system has been constructed in this work. Sensitive analysis and numerical experiments have been carried out to prove the accuracy and efficiency of this model. Furthermore, based on the current thermodynamic model in the oil and gas industry, implementing this model is simple.

Keywords: equation of state, hydrates, multiphase equilibrium, trust-region method

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79 Mitochondrial DNA Defect and Mitochondrial Dysfunction in Diabetic Nephropathy: The Role of Hyperglycemia-Induced Reactive Oxygen Species

Authors: Ghada Al-Kafaji, Mohamed Sabry

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Mitochondria are the site of cellular respiration and produce energy in the form of adenosine triphosphate (ATP) via oxidative phosphorylation. They are the major source of intracellular reactive oxygen species (ROS) and are also direct target to ROS attack. Oxidative stress and ROS-mediated disruptions of mitochondrial function are major components involved in the pathogenicity of diabetic complications. In this work, the changes in mitochondrial DNA (mtDNA) copy number, biogenesis, gene expression of mtDNA-encoded subunits of electron transport chain (ETC) complexes, and mitochondrial function in response to hyperglycemia-induced ROS and the effect of direct inhibition of ROS on mitochondria were investigated in an in vitro model of diabetic nephropathy using human renal mesangial cells. The cells were exposed to normoglycemic and hyperglycemic conditions in the presence and absence of Mn(III)tetrakis(4-benzoic acid) porphyrin chloride (MnTBAP) or catalase for 1, 4 and 7 days. ROS production was assessed by the confocal microscope and flow cytometry. mtDNA copy number and PGC-1a, NRF-1, and TFAM, as well as ND2, CYTB, COI, and ATPase 6 transcripts, were all analyzed by real-time PCR. PGC-1a, NRF-1, and TFAM, as well as ND2, CYTB, COI, and ATPase 6 proteins, were analyzed by Western blotting. Mitochondrial function was determined by assessing mitochondrial membrane potential and adenosine triphosphate (ATP) levels. Hyperglycemia-induced a significant increase in the production of mitochondrial superoxide and hydrogen peroxide at day 1 (P < 0.05), and this increase remained significantly elevated at days 4 and 7 (P < 0.05). The copy number of mtDNA and expression of PGC-1a, NRF-1, and TFAM as well as ND2, CYTB, CO1 and ATPase 6 increased after one day of hyperglycemia (P < 0.05), with a significant reduction in all those parameters at 4 and 7 days (P < 0.05). The mitochondrial membrane potential decreased progressively at 1 to 7 days of hyperglycemia with the parallel progressive reduction in ATP levels over time (P < 0.05). MnTBAP and catalase treatment of cells cultured under hyperglycemic conditions attenuated ROS production reversed renal mitochondrial oxidative stress and improved mtDNA, mitochondrial biogenesis, and function. These results show that hyperglycemia-induced ROS caused an early increase in mtDNA copy number, mitochondrial biogenesis and mtDNA-encoded gene expression of the ETC subunits in human mesangial cells as a compensatory response to the decline in mitochondrial function, which precede the mtDNA defect and mitochondrial dysfunction with a progressive oxidative response. Protection from ROS-mediated damage to renal mitochondria induced by hyperglycemia may be a novel therapeutic approach for the prevention/treatment of DN.

Keywords: diabetic nephropathy, hyperglycemia, reactive oxygen species, oxidative stress, mtDNA, mitochondrial dysfunction, manganese superoxide dismutase, catalase

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78 Chiral Molecule Detection via Optical Rectification in Spin-Momentum Locking

Authors: Jessie Rapoza, Petr Moroshkin, Jimmy Xu

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Chirality is omnipresent, in nature, in life, and in the field of physics. One intriguing example is the homochirality that has remained a great secret of life. Another is the pairs of mirror-image molecules – enantiomers. They are identical in atomic composition and therefore indistinguishable in the scalar physical properties. Yet, they can be either therapeutic or toxic, depending on their chirality. Recent studies suggest a potential link between abnormal levels of certain D-amino acids and some serious health impairments, including schizophrenia, amyotrophic lateral sclerosis, and potentially cancer. Although indistinguishable in their scalar properties, the chirality of a molecule reveals itself in interaction with the surrounding of a certain chirality, or more generally, a broken mirror-symmetry. In this work, we report on a system for chiral molecule detection, in which the mirror-symmetry is doubly broken, first by asymmetric structuring a nanopatterned plasmonic surface than by the incidence of circularly polarized light (CPL). In this system, the incident circularly-polarized light induces a surface plasmon polariton (SPP) wave, propagating along the asymmetric plasmonic surface. This SPP field itself is chiral, evanescently bound to a near-field zone on the surface (~10nm thick), but with an amplitude greatly intensified (by up to 104) over that of the incident light. It hence probes just the molecules on the surface instead of those in the volume. In coupling to molecules along its path on the surface, the chiral SPP wave favors one chirality over the other, allowing for chirality detection via the change in an optical rectification current measured at the edges of the sample. The asymmetrically structured surface converts the high-frequency electron plasmonic-oscillations in the SPP wave into a net DC drift current that can be measured at the edge of the sample via the mechanism of optical rectification. The measured results validate these design concepts and principles. The observed optical rectification current exhibits a clear differentiation between a pair of enantiomers. Experiments were performed by focusing a 1064nm CW laser light at the sample - a gold grating microchip submerged in an approximately 1.82M solution of either L-arabinose or D-arabinose and water. A measurement of the current output was then recorded under both rights and left circularly polarized lights. Measurements were recorded at various angles of incidence to optimize the coupling between the spin-momentums of the incident light and that of the SPP, that is, spin-momentum locking. In order to suppress the background, the values of the photocurrent for the right CPL are subtracted from those for the left CPL. Comparison between the two arabinose enantiomers reveals a preferential signal response of one enantiomer to left CPL and the other enantiomer to right CPL. In sum, this work reports on the first experimental evidence of the feasibility of chiral molecule detection via optical rectification in a metal meta-grating. This nanoscale interfaced electrical detection technology is advantageous over other detection methods due to its size, cost, ease of use, and integration ability with read-out electronic circuits for data processing and interpretation.

Keywords: Chirality, detection, molecule, spin

Procedia PDF Downloads 74
77 Assessment of Environmental Mercury Contamination from an Old Mercury Processing Plant 'Thor Chemicals' in Cato Ridge, KwaZulu-Natal, South Africa

Authors: Yohana Fessehazion

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Mercury is a prominent example of a heavy metal contaminant in the environment, and it has been extensively investigated for its potential health risk in humans and other organisms. In South Africa, massive mercury contamination happened in1980s when the England-based mercury reclamation processing plant relocated to Cato Ridge, KwaZulu-Natal Province, and discharged mercury waste into the Mngceweni River. This mercury waste discharge resulted in high mercury concentration that exceeded the acceptable levels in Mngceweni River, Umgeni River, and human hair of the nearby villagers. This environmental issue raised the alarm, and over the years, several environmental assessments were reported the dire environmental crises resulting from the Thor Chemicals (now known as Metallica Chemicals) and urged the immediate removal of the around 3,000 tons of mercury waste stored in the factory storage facility over two decades. Recently theft of some containers with the toxic substance from the Thor Chemicals warehouse and the subsequent fire that ravaged the facility furtherly put the factory on the spot escalating the urgency of left behind deadly mercury waste removal. This project aims to investigate the mercury contamination leaking from an old Thor Chemicals mercury processing plant. The focus will be on sediments, water, terrestrial plants, and aquatic weeds such as the prominent water hyacinth weeds in the nearby water systems of Mngceweni River, Umgeni River, and Inanda Dam as a bio-indicator and phytoremediator for mercury pollution. Samples will be collected in spring around October when the condition is favourable for microbial activity to methylate mercury incorporated in sediments and blooming season for some aquatic weeds, particularly water hyacinth. Samples of soil, sediment, water, terrestrial plant, and aquatic weed will be collected per sample site from the point of source (Thor Chemicals), Mngceweni River, Umgeni River, and the Inanda Dam. One-way analysis of variance (ANOVA) tests will be conducted to determine any significant differences in the Hg concentration among all sampling sites, followed by Least Significant Difference post hoc test to determine if mercury contamination varies with the gradient distance from the source point of pollution. The flow injection atomic spectrometry (FIAS) analysis will also be used to compare the mercury sequestration between the different plant tissues (roots and stems). The principal component analysis is also envisaged for use to determine the relationship between the source of mercury pollution and any of the sampling points (Umgeni and Mngceweni Rivers and the Inanda Dam). All the Hg values will be expressed in µg/L or µg/g in order to compare the result with the previous studies and regulatory standards. Sediments are expected to have relatively higher levels of Hg compared to the soils, and aquatic macrophytes, water hyacinth weeds are expected to accumulate a higher concentration of mercury than terrestrial plants and crops.

Keywords: mercury, phytoremediation, Thor chemicals, water hyacinth

Procedia PDF Downloads 182
76 Dry Reforming of Methane Using Metal Supported and Core Shell Based Catalyst

Authors: Vinu Viswanath, Lawrence Dsouza, Ugo Ravon

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

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

Procedia PDF Downloads 142
75 The Role of Two Macrophyte Species in Mineral Nutrient Cycling in Human-Impacted Water Reservoirs

Authors: Ludmila Polechonska, Agnieszka Klink

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The biogeochemical studies of macrophytes shed light on elements bioavailability, transfer through the food webs and their possible effects on the biota, and provide a basis for their practical application in aquatic monitoring and remediation. Measuring the accumulation of elements in plants can provide time-integrated information about the presence of chemicals in aquatic ecosystems. The aim of the study was to determine and compare the contents of micro- and macroelements in two cosmopolitan macrophytes, submerged Ceratophyllum demersum (hornworth) and free-floating Hydrocharis morsus-ranae (European frog-bit), in order to assess their bioaccumulation potential, elements stock accumulated in each plant and their role in nutrients cycling in small water reservoirs. Sampling sites were designated in 25 oxbow lakes in urban areas in Lower Silesia (SW Poland). In each sampling site, fresh whole plants of C. demersum and H. morsus-ranae were collected from squares of 1x1 meters each where the species coexisted. European frog-bit was separated into leaves, stems and roots. For biomass measurement all plants growing on 1 square meter were collected, dried and weighed. At the same time, water samples were collected from each reservoir and their pH and EC were determined. Water samples were filtered and acidified and plant samples were digested in concentrated nitric acid. Next, the content of Ca, Cu, Fe, K, Mg, Mn, Ni and Zn was determined using atomic absorption method (AAS). Statistical analysis showed that C. demersum and organs of H. morsus-ranae differed significantly in respect of metals content (Kruskal-Wallis Anova, p<0.05). Contents of Cu, Mn, Ni and Zn were higher in hornwort, while European frog-bit contained more Ca, Fe, K, Mg. Bioaccumulation Factors (BCF=content in plant/concentration in water) showed similar pattern of metal bioaccumulation – microelements were more intensively accumulated by hornwort and macroelements by frog-bit. Based on BCF values both species may be positively evaluated as good accumulators of Cu, Fe, Mn, Ni and Zn. However, the distribution of metals in H. morsus-ranae was uneven – the majority of studied elements were retained in roots, which may indicate to existence of physiological barriers developed for dealing with toxicity. Some percent of Ca and K was actively transported to stems, but to leaves Mg only. Although the biomass of C. demersum was two times greater than biomass of H. morsus-ranae, the element off-take was greater only for Cu, Mn, Ni and Zn. Nevertheless, it can be stated that despite a relatively small biomass, compared to other macrophytes, both species may have an influence on the removal of trace elements from aquatic ecosystems and, as they serve as food for some animals, also on the incorporation of toxic elements into food chains. There was a significant positive correlation between content of Mn and Fe in water and roots of H. morus-ranae (R=0.51 and R=0.60, respectively) as well as between Cu concentration in water and in C. demersum (R=0.41) (Spearman rank correlation, p<0.05). High bioaccumulation rates and correlation between plants and water elements concentrations point to their possible use as passive biomonitors of aquatic pollution.

Keywords: aquatic plants, bioaccumulation, biomonitoring, macroelements, phytoremediation, trace metals

Procedia PDF Downloads 157
74 Solution Thermodynamics, Photophysical and Computational Studies of TACH2OX, a C-3 Symmetric 8-Hydroxyquinoline: Abiotic Siderophore Analogue of Enterobactin

Authors: B. K. Kanungo, Monika Thakur, Minati Baral

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8-hydroxyquinoline, (8HQ), experiences a renaissance due to its utility as a building block in metallosupramolecular chemistry and its versatile use of its derivatives in various fields of analytical chemistry, materials science, and pharmaceutics. It forms stable complexes with a variety of metal ions. Assembly of more than one such unit to form a polydentate chelator enhances its coordinating ability and the related properties due to the chelate effect resulting in high stability constant. Keeping in view the above, a nonadentate chelator N-[3,5-bis(8-hydroxyquinoline-2-amido)cyclohexyl]-8-hydroxyquinoline-2-carboxamide, (TACH2OX), containing a central cis,cis-1,3,5-triaminocyclohexane appended to three 8-hydroxyquinoline at 2-position through amide linkage is developed, and its solution thermodynamics, photophysical and Density Functional Theory (DFT) studies were undertaken. The synthesis of TACH2OX was carried out by condensation of cis,cis-1,3,5-triaminocyclohexane, (TACH) with 8‐hydroxyquinoline‐2‐carboxylic acid. The brown colored solid has been fully characterized through melting point, infrared, nuclear magnetic resonance, electrospray ionization mass and electronic spectroscopy. In solution, TACH2OX forms protonated complexes below pH 3.4, which consecutively deprotonates to generate trinegative ion with the rise of pH. Nine protonation constants for the ligand were obtained that ranges between 2.26 to 7.28. The interaction of the chelator with two trivalent metal ion Fe3+ and Al3+ were studied in aqueous solution at 298 K. The metal-ligand formation constants (ML) obtained by potentiometric and spectrophotometric method agree with each other. The protonated and hydrolyzed species were also detected in the system. The in-silico studies of the ligand, as well as the complexes including their protonated and deprotonated species assessed by density functional theory technique, gave an accurate correlation with each observed properties such as the protonation constants, stability constants, infra-red, nmr, electronic absorption and emission spectral bands. The nature of electronic and emission spectral bands in terms of number and type were ascertained from time-dependent density functional theory study and the natural transition orbitals (NTO). The global reactivity indices parameters were used for comparison of the reactivity of the ligand and the complex molecules. The natural bonding orbital (NBO) analysis could successfully describe the structure and bonding of the metal-ligand complexes specifying the percentage of contribution in atomic orbitals in the creation of molecular orbitals. The obtained high value of metal-ligand formation constants indicates that the newly synthesized chelator is a very powerful synthetic chelator. The minimum energy molecular modeling structure of the ligand suggests that the ligand, TACH2OX, in a tripodal fashion firmly coordinates to the metal ion as hexa-coordinated chelate displaying distorted octahedral geometry by binding through three sets of N, O- donor atoms, present in each pendant arm of the central tris-cyclohexaneamine tripod.

Keywords: complexes, DFT, formation constant, TACH2OX

Procedia PDF Downloads 120
73 Isolation and Characterization of Chromium Tolerant Staphylococcus aureus from Industrial Wastewater and Their Potential Use to Bioremediate Environmental Chromium

Authors: Muhammad Tariq, Muhammad Waseem, Muhammad Hidayat Rasool

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Isolation and characterization of chromium tolerant Staphylococcus aureus from industrial wastewater and their potential use to bioremediate environmental chromium. Objectives: Chromium with its great economic importance in industrial use is major metal pollutant of the environment. Chromium are used in different industries for various applications such as textile, dyeing and pigmentation, wood preservation, manufacturing pulp and paper, chrome plating, steel and tanning. The release of untreated chromium in industrial effluents causes serious threat to environment and human health, therefore, the current study designed to isolate chromium tolerant Staphylococcus aureus for removal of chromium prior to their final discharge into the environment due to its cost effective and beneficial advantage over physical and chemical methods. Methods: Wastewater samples were collected from discharge point of different industries. Heavy metal analysis by atomic absorption spectrophotometer and microbiological analysis such as total viable count, total coliform, fecal coliform and Escherichia coli were conducted. Staphylococcus aureus was identified through gram’s staining, biomeriux vitek 2 microbial identification system and 16S rRNA gene amplification by polymerase chain reaction. Optimum growth conditions with respect to temperature, pH, salt concentrations and effect of chromium on the growth of bacteria, resistance to other heavy metal ions, minimum inhibitory concentration and chromium uptake ability of Staphylococcus aureus strain K1 was determined by spectrophotometer. Antibiotic sensitivity pattern was also determined by disc diffusion method. Furthermore, chromium uptake ability was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope equipped with Oxford Energy Dipersive X-ray (EDX) micro analysis system. Results: The results presented that optimum temperature was 35ᵒC, pH was 8.0 and salt concentration was 0.5% for growth of Staphylococcus aureus K1. The maximum uptake ability of chromium by bacteria was 20mM than other heavy metal ions. The antibiotic sensitivity pattern revealed that Staphylococcus aureus was vancomycin and methicillin sensitive. Non hemolytic activity on blood agar and negative coagulase reaction showed that it was non-pathogenic. Furthermore, the growth of bacteria decreases in the presence of chromium and maximum chromium uptake by bacteria observed at optimum growth conditions. Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and Energy dispersive X-ray (EDX) analysis confirmed the presence of chromium uptake by Staphylococcus aureus K1. Conclusion: The study revealed that Staphylococcus aureus K1 have the potential to bio-remediate chromium toxicity from wastewater. Gradually, this biological treatment becomes more important due to its advantage over physical and chemical methods to protect environment and human health.

Keywords: wastewater, staphylococcus, chromium, bioremediation

Procedia PDF Downloads 145
72 Development of an Systematic Design in Evaluating Force-On-Force Security Exercise at Nuclear Power Plants

Authors: Seungsik Yu, Minho Kang

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As the threat of terrorism to nuclear facilities is increasing globally after the attacks of September 11, we are striving to recognize the physical protection system and strengthen the emergency response system. Since 2015, Korea has implemented physical protection security exercise for nuclear facilities. The exercise should be carried out with full cooperation between the operator and response forces. Performance testing of the physical protection system should include appropriate exercises, for example, force-on-force exercises, to determine if the response forces can provide an effective and timely response to prevent sabotage. Significant deficiencies and actions taken should be reported as stipulated by the competent authority. The IAEA(International Atomic Energy Agency) is also preparing force-on-force exercise program documents to support exercise of member states. Currently, ROK(Republic of Korea) is implementing exercise on the force-on-force exercise evaluation system which is developed by itself for the nuclear power plant, and it is necessary to establish the exercise procedure considering the use of the force-on-force exercise evaluation system. The purpose of this study is to establish the work procedures of the three major organizations related to the force-on-force exercise of nuclear power plants in ROK, which conduct exercise using force-on-force exercise evaluation system. The three major organizations are composed of licensee, KINAC (Korea Institute of Nuclear Nonproliferation and Control), and the NSSC(Nuclear Safety and Security Commission). Major activities are as follows. First, the licensee establishes and conducts an exercise plan, and when recommendations are derived from the result of the exercise, it prepares and carries out a force-on-force result report including a plan for implementation of the recommendations. Other detailed tasks include consultation with surrounding units for adversary, interviews with exercise participants, support for document evaluation, and self-training to improve the familiarity of the MILES (Multiple Integrated Laser Engagement System). Second, KINAC establishes a force-on-force exercise plan review report and reviews the force-on-force exercise plan report established by licensee. KINAC evaluate force-on-force exercise using exercise evaluation system and prepare training evaluation report. Other detailed tasks include MILES training, adversary consultation, management of exercise evaluation systems, and analysis of exercise evaluation results. Finally, the NSSC decides whether or not to approve the force-on-force exercise and makes a correction request to the nuclear facility based on the exercise results. The most important part of ROK's force-on-force exercise system is the analysis through the exercise evaluation system implemented by KINAC after the exercise. The analytical method proceeds in the order of collecting data from the exercise evaluation system and analyzing the collected data. The exercise application process of the exercise evaluation system introduced in ROK in 2016 will be concretely set up, and a system will be established to provide objective and consistent conclusions between exercise sessions. Based on the conclusions drawn up, the ultimate goal is to complement the physical protection system of licensee so that the system makes licensee respond effectively and timely against sabotage or unauthorized removal of nuclear materials.

Keywords: Force-on-Force exercise, nuclear power plant, physical protection, sabotage, unauthorized removal

Procedia PDF Downloads 119
71 Preliminary Design, Production and Characterization of a Coral and Alginate Composite for Bone Engineering

Authors: Sthephanie A. Colmenares, Fabio A. Rojas, Pablo A. Arbeláez, Johann F. Osma, Diana Narvaez

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The loss of functional tissue is a ubiquitous and expensive health care problem, with very limited treatment options for these patients. The golden standard for large bone damage is a cadaveric bone as an allograft with stainless steel support; however, this solution only applies to bones with simple morphologies (long bones), has a limited material supply and presents long term problems regarding mechanical strength, integration, differentiation and induction of native bone tissue. Therefore, the fabrication of a scaffold with biological, physical and chemical properties similar to the human bone with a fabrication method for morphology manipulation is the focus of this investigation. Towards this goal, an alginate and coral matrix was created using two production techniques; the coral was chosen because of its chemical composition and the alginate due to its compatibility and mechanical properties. In order to construct the coral alginate scaffold the following methodology was employed; cleaning of the coral, its pulverization, scaffold fabrication and finally the mechanical and biological characterization. The experimental design had: mill method and proportion of alginate and coral, as the two factors, with two and three levels each, using 5 replicates. The coral was cleaned with sodium hypochlorite and hydrogen peroxide in an ultrasonic bath. Then, it was milled with both a horizontal and a ball mill in order to evaluate the morphology of the particles obtained. After this, using a combination of alginate and coral powder and water as a binder, scaffolds of 1cm3 were printed with a SpectrumTM Z510 3D printer. This resulted in solid cubes that were resistant to small compression stress. Then, using a ESQUIM DP-143 silicon mold, constructs used for the mechanical and biological assays were made. An INSTRON 2267® was implemented for the compression tests; the density and porosity were calculated with an analytical balance and the biological tests were performed using cell cultures with VERO fibroblast, and Scanning Electron Microscope (SEM) as visualization tool. The Young’s moduli were dependent of the pulverization method, the proportion of coral and alginate and the interaction between these factors. The maximum value was 5,4MPa for the 50/50 proportion of alginate and horizontally milled coral. The biological assay showed more extracellular matrix in the scaffolds consisting of more alginate and less coral. The density and porosity were proportional to the amount of coral in the powder mix. These results showed that this composite has potential as a biomaterial, but its behavior is elastic with a small Young’s Modulus, which leads to the conclusion that the application may not be for long bones but for tissues similar to cartilage.

Keywords: alginate, biomaterial, bone engineering, coral, Porites asteroids, SEM

Procedia PDF Downloads 236
70 Developing Offshore Energy Grids in Norway as Capability Platforms

Authors: Vidar Hepsø

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The energy and oil companies on the Norwegian Continental shelf come from a situation where each asset control and manage their energy supply (island mode) and move towards a situation where the assets need to collaborate and coordinate energy use with others due to increased cost and scarcity of electric energy sharing the energy that is provided. Currently, several areas are electrified either with an onshore grid cable or are receiving intermittent energy from offshore wind-parks. While the onshore grid in Norway is well regulated, the offshore grid is still in the making, with several oil and gas electrification projects and offshore wind development just started. The paper will describe the shift in the mindset that comes with operating this new offshore grid. This transition process heralds an increase in collaboration across boundaries and integration of energy management across companies, businesses, technical disciplines, and engagement with stakeholders in the larger society. This transition will be described as a function of the new challenges with increased complexity of the energy mix (wind, oil/gas, hydrogen and others) coupled with increased technical and organization complexity in energy management. Organizational complexity denotes an increasing integration across boundaries, whether these boundaries are company, vendors, professional disciplines, regulatory regimes/bodies, businesses, and across numerous societal stakeholders. New practices must be developed, made legitimate and institutionalized across these boundaries. Only parts of this complexity can be mitigated technically, e.g.: by use of batteries, mixing energy systems and simulation/ forecasting tools. Many challenges must be mitigated with legitimated societal and institutionalized governance practices on many levels. Offshore electrification supports Norway’s 2030 climate targets but is also controversial since it is exploiting the larger society’s energy resources. This means that new systems and practices must also be transparent, not only for the industry and the authorities, but must also be acceptable and just for the larger society. The paper report from ongoing work in Norway, participant observation and interviews in projects and people working with offshore grid development in Norway. One case presented is the development of an offshore floating windfarm connected to two offshore installations and the second case is an offshore grid development initiative providing six installations electric energy via an onshore cable. The development of the offshore grid is analyzed using a capability platform framework, that describes the technical, competence, work process and governance capabilities that are under development in Norway. A capability platform is a ‘stack’ with the following layers: intelligent infrastructure, information and collaboration, knowledge sharing & analytics and finally business operations. The need for better collaboration and energy forecasting tools/capabilities in this stack will be given a special attention in the two use cases that are presented.

Keywords: capability platform, electrification, carbon footprint, control rooms, energy forecsting, operational model

Procedia PDF Downloads 44
69 Catalytic Alkylation of C2-C4 Hydrocarbons

Authors: Bolysbek Utelbayev, Tasmagambetova Aigerim, Toktasyn Raila, Markayev Yergali, Myrzakhanov Maxat

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Intensive development of secondary processes of destructive processing of crude oil has led to the occurrence of oil refining factories resources of C2-C4 hydrocarbons. Except for oil gases also contain basically C2-C4 hydrocarbon gases where some of the amounts are burned. All these data has induced interest to the study of producing alkylate from hydrocarbons С2-С4 which being as components of motor fuels. The purpose of this work was studying transformation propane-propene, butane-butene fractions at the presence of the ruthenium-chromic support catalyst whereas the carrier is served pillar - structural montmorillonite containing in native bentonite clay. In this work is considered condition and structure of the bentonite clay from the South-Kazakhstan area of the Republic Kazakhstan. For preparation rhodium support catalyst (0,5-1,0 mass. % Rh) was used chloride of rhodium-RhCl3∙3H2O, as a carrier was used modified bentonite clay. For modifying natural clay to pillar structural form were used polyhydroxy complexes of chromium. To aqueous solution of chloride chromium gradually flowed the solution of sodium hydroxide at gradual hashing up to pH~3-4. The concentration of chloride chromium was paid off proceeding from calculation 5-30 mmole Cr3+ per gram clay. Suspension bentonite (~1,0 mass. %) received by intensive washing it in water during 4 h, pH-water extract of clay makes -8-9. The acidity of environment supervised by means of digital pH meter OP-208/1. In order to prevent coagulation of a solution polyhydroxy complexes of chromium, it was slowly added to a suspension of clay. "Reserve of basicity" Cr3+:/OH-allowing to prevent coagulation chloride of rhodium made 1/3. After endurance processed suspensions of clay during 24 h, a deposit was washed by water and condensed. The sample, after separate from a liquid phase, dried at first at the room temperature, and then at 110°C (2h) with the subsequent rise the temperature up to 180°C (4h). After cooling the firm mass was pounded to a powder, it was shifted infractions with the certain sizes of particles. Fractions of particles modifying clay in the further were impregnated with an aqueous solution with rhodium-RhCl3∙3H2O (0,5-1,0 mаss % Rh ). Obtained pillar structural bentonite approaches heat resistance and its porous structure above the 773K. Pillar structural bentonite was used for preparation 1.0% Ru/Carrier (modifying bentonite) support catalysts where is realised alkylation of C2-C4 hydrocarbons. The process of alkylation is carried out at a partial pressure of hydrogen 0.5-1.0MPa. Outcome 2.2.4 three methyl pentane and 2.2.3 trimethylpentane achieved 40%. At alkylation butane-butene mixture outcome of the isooctane is achieved 60%. In this condition of studying the ethene is not undergoing to alkylation.

Keywords: alkylation, butene, pillar structure, ruthenium catalyst

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68 Real-Time Monitoring of Complex Multiphase Behavior in a High Pressure and High Temperature Microfluidic Chip

Authors: Renée M. Ripken, Johannes G. E. Gardeniers, Séverine Le Gac

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Controlling the multiphase behavior of aqueous biomass mixtures is essential when working in the biomass conversion industry. Here, the vapor/liquid equilibria (VLE) of ethylene glycol, glycerol, and xylitol were studied for temperatures between 25 and 200 °C and pressures of 1 to 10 bar. These experiments were performed in a microfluidic platform, which exhibits excellent heat transfer properties so that equilibrium is reached fast. Firstly, the saturated vapor pressure as a function of the temperature and the substrate mole fraction of the substrate was calculated using AspenPlus with a Redlich-Kwong-Soave Boston-Mathias (RKS-BM) model. Secondly, we developed a high-pressure and high-temperature microfluidic set-up for experimental validation. Furthermore, we have studied the multiphase flow pattern that occurs after the saturation temperature was achieved. A glass-silicon microfluidic device containing a 0.4 or 0.2 m long meandering channel with a depth of 250 μm and a width of 250 or 500 μm was fabricated using standard microfabrication techniques. This device was placed in a dedicated chip-holder, which includes a ceramic heater on the silicon side. The temperature was controlled and monitored by three K-type thermocouples: two were located between the heater and the silicon substrate, one to set the temperature and one to measure it, and the third one was placed in a 300 μm wide and 450 μm deep groove on the glass side to determine the heat loss over the silicon. An adjustable back pressure regulator and a pressure meter were added to control and evaluate the pressure during the experiment. Aqueous biomass solutions (10 wt%) were pumped at a flow rate of 10 μL/min using a syringe pump, and the temperature was slowly increased until the theoretical saturation temperature for the pre-set pressure was reached. First and surprisingly, a significant difference was observed between our theoretical saturation temperature and the experimental results. The experimental values were 10’s of degrees higher than the calculated ones and, in some cases, saturation could not be achieved. This discrepancy can be explained in different ways. Firstly, the pressure in the microchannel is locally higher due to both the thermal expansion of the liquid and the Laplace pressure that has to be overcome before a gas bubble can be formed. Secondly, superheating effects are likely to be present. Next, once saturation was reached, the flow pattern of the gas/liquid multiphase system was recorded. In our device, the point of nucleation can be controlled by taking advantage of the pressure drop across the channel and the accurate control of the temperature. Specifically, a higher temperature resulted in nucleation further upstream in the channel. As the void fraction increases downstream, the flow regime changes along the channel from bubbly flow to Taylor flow and later to annular flow. All three flow regimes were observed simultaneously. The findings of this study are key for the development and optimization of a microreactor for hydrogen production from biomass.

Keywords: biomass conversion, high pressure and high temperature microfluidics, multiphase, phase diagrams, superheating

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67 Inhibition of Mild Steel Corrosion in Hydrochloric Acid Medium Using an Aromatic Hydrazide Derivative

Authors: Preethi Kumari P., Shetty Prakasha, Rao Suma A.

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Mild steel has been widely employed as construction materials for pipe work in the oil and gas production such as down hole tubular, flow lines and transmission pipelines, in chemical and allied industries for handling acids, alkalis and salt solutions due to its excellent mechanical property and low cost. Acid solutions are widely used for removal of undesirable scale and rust in many industrial processes. Among the commercially available acids hydrochloric acid is widely used for pickling, cleaning, de-scaling and acidization of oil process. Mild steel exhibits poor corrosion resistance in presence of hydrochloric acid. The high reactivity of mild steel in presence of hydrochloric acid is due to the soluble nature of ferrous chloride formed and the cementite phase (Fe3C) normally present in the steel is also readily soluble in hydrochloric acid. Pitting attack is also reported to be a major form of corrosion in mild steel in the presence of high concentrations of acids and thereby causing the complete destruction of metal. Hydrogen from acid reacts with the metal surface and makes it brittle and causes cracks, which leads to pitting type of corrosion. The use of chemical inhibitor to minimize the rate of corrosion has been considered to be the first line of defense against corrosion. In spite of long history of corrosion inhibition, a highly efficient and durable inhibitor that can completely protect mild steel in aggressive environment is yet to be realized. It is clear from the literature review that there is ample scope for the development of new organic inhibitors, which can be conveniently synthesized from relatively cheap raw materials and provide good inhibition efficiency with least risk of environmental pollution. The aim of the present work is to evaluate the electrochemical parameters for the corrosion inhibition behavior of an aromatic hydrazide derivative, 4-hydroxy- N '-[(E)-1H-indole-2-ylmethylidene)] benzohydrazide (HIBH) on mild steel in 2M hydrochloric acid using Tafel polarization and electrochemical impedance spectroscopy (EIS) techniques at 30-60 °C. The results showed that inhibition efficiency increased with increase in inhibitor concentration and decreased marginally with increase in temperature. HIBH showed a maximum inhibition efficiency of 95 % at 8×10-4 M concentration at 30 °C. Polarization curves showed that HIBH act as a mixed-type inhibitor. The adsorption of HIBH on mild steel surface obeys the Langmuir adsorption isotherm. The adsorption process of HIBH at the mild steel/hydrochloric acid solution interface followed mixed adsorption with predominantly physisorption at lower temperature and chemisorption at higher temperature. Thermodynamic parameters for the adsorption process and kinetic parameters for the metal dissolution reaction were determined.

Keywords: electrochemical parameters, EIS, mild steel, tafel polarization

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66 Upgrading of Bio-Oil by Bio-Pd Catalyst

Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

Abstract:

This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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65 Recent Advances in Research on Carotenoids: From Agrofood Production to Health Outcomes

Authors: Antonio J. Melendez-Martinez

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Beyond their role as natural colorants, some carotenoids are provitamins A and may be involved in health-promoting biological actions and contribute to reducing the risk of developing non-communicable diseases, including several types of cancer, cardiovascular disease, eye conditions, skin disorders or metabolic disorders. Given the versatility of carotenoids, the COST-funded European network to advance carotenoid research and applications in agro-food and health (EUROCAROTEN) is aimed at promoting health through the diet and increasing well-being by means. Stakeholders from 38 countries participate in this network, and one of its main objectives is to promote research on little-studied carotenoids. In this contribution, recent advances of our research group and collaborators in the study of two such understudied carotenoids, namely phytoene and phytofluene, the colorless carotenoids, are outlined. The study of these carotenoids is important as they have been largely neglected despite they are present in our diets, fluids, and tissues, and evidence is accumulating that they may be involved in health-promoting actions. More specifically, studies on their levels in diverse tomato and orange varieties were carried out as well as on their potential bioavailability from different dietary sources. Furthermore, the potential effect of these carotenoids on an animal model subjected to oxidative stress was evaluated. The tomatoes were grown in research greenhouses, and some of them were subjected to regulated deficit irrigation, a sustainable agronomic practice. The citrus samples were obtained from an experimental field. The levels of carotenoids were assessed using HPLC according to routine methodologies followed in our lab. Regarding the potential bioavailability (bioaccessibility) studies, different products containing colorless carotenoids, like fruits, juices, were subjected to simulated in vitro digestions, and their incorporation into mixed micelles was assessed. The effect of the carotenoids on oxidative stress was evaluated on the Caenorhabditis elegans model. For that purpose, the worms were subjected to oxidative stress by means of a hydrogen peroxide challenge. In relation to the presence of colorless carotenoids in tomatoes and orange varieties, it was observed that they are widespread in such products and that there are mutants with very high quantities of them, for instance, the Cara Cara or Pinalate mutant oranges. The studies on their bioaccessibility revealed that, in general, phytoene and phytofluene are more bioaccessible than other common dietary carotenoids, probably due to their distinctive chemical structure. About the in vivo antioxidant capacity of phytoene and phytofluene, it was observed that they both exerted antioxidant effects at certain doses. In conclusion, evidence on the importance of phytoene and phytofluene as dietary easily bioavailable and antioxidant carotenoids has been obtained in recent studies from our group, which can be important shortly to innovate in health-promotion through the development of functional foods and related products.

Keywords: carotenoids, health, functional foods, nutrition, phytoene, phytofluene

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64 Nanoparticle Supported, Magnetically Separable Metalloporphyrin as an Efficient Retrievable Heterogeneous Nanocatalyst in Oxidation Reactions

Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

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Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

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63 Preparation, Solid State Characterization of Etraverine Co-Crystals with Improved Solubility for the Treatment of Human Immunodeficiency Virus

Authors: B. S. Muddukrishna, Karthik Aithal, Aravind Pai

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Introduction: Preparation of binary cocrystals of Etraverine (ETR) by using Tartaric Acid (TAR) as a conformer was the main focus of this study. Etravirine is a Class IV drug, as per the BCS classification system. Methods: Cocrystals were prepared by slow evaporation technique. A mixture of total 500mg of ETR: TAR was weighed in molar ratios of 1:1 (371.72mg of ETR and 128.27mg of TAR). Saturated solution of Etravirine was prepared in Acetone: Methanol (50:50) mixture in which tartaric acid is dissolved by sonication and then this solution was stirred using a magnetic stirrer until the solvent got evaporated. Shimadzu FTIR – 8300 system was used to acquire the FTIR spectra of the cocrystals prepared. Shimadzu thermal analyzer was used to achieve DSC measurements. X-ray diffractometer was used to obtain the X-ray powder diffraction pattern. Shake flask method was used to determine the equilibrium dynamic solubility of pure, physical mixture and cocrystals of ETR. USP buffer (pH 6.8) containing 1% of Tween 80 was used as the medium. The pure, physical mixture and the optimized cocrystal of ETR were accurately weighed sufficient to maintain the sink condition and were filled in hard gelatine capsules (size 4). Electrolab-Tablet Dissolution tester using basket apparatus at a rotational speed of 50 rpm and USP phosphate buffer (900 mL, pH = 6.8, 37 ˚C) + 1% Tween80 as a media, was used to carry out dissolution. Shimadzu LC-10 series chromatographic system was used to perform the analysis with PDA detector. An Hypersil BDS C18 (150mm ×4.6 mm ×5 µm) column was used for separation with mobile phase comprising of a mixture of ace¬tonitrile and phosphate buffer 20mM, pH 3.2 in the ratio 60:40 v/v. The flow rate was 1.0mL/min and column temperature was set to 30°C. The detection was carried out at 304 nm for ETR. Results and discussions: The cocrystals were subjected to various solid state characterization and the results confirmed the formation of cocrystals. The C=O stretching vibration (1741cm-1) in tartaric acid was disappeared in the cocrystal and the peak broadening of primary amine indicates hydrogen bond formation. The difference in the melting point of cocrystals when compared to pure Etravirine (265 °C) indicates interaction between the drug and the coformer which proves that first ordered transformation i.e. melting endotherm has disappeared. The difference in 2θ values of pure drug and cocrystals indicates the interaction between the drug and the coformer. Dynamic solubility and dissolution studies were also conducted by shake flask method and USP apparatus one respectively and 3.6 fold increase in the dynamic solubility were observed and in-vitro dissolution study shows four fold increase in the solubility for the ETR: TAR (1:1) cocrystals. The ETR: TAR (1:1) cocrystals shows improved solubility and dissolution as compared to the pure drug which was clearly showed by solid state characterization and dissolution studies.

Keywords: dynamic solubility, Etraverine, in vitro dissolution, slurry method

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62 Dietary Exposure Assessment of Potentially Toxic Trace Elements in Fruits and Vegetables Grown in Akhtala, Armenia

Authors: Davit Pipoyan, Meline Beglaryan, Nicolò Merendino

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Mining industry is one of the priority sectors of Armenian economy. Along with the solution of some socio-economic development, it brings about numerous environmental problems, especially toxic element pollution, which largely influences the safety of agricultural products. In addition, accumulation of toxic elements in agricultural products, mainly in edible parts of plants represents a direct pathway for their penetration into the human food chain. In Armenia, the share of plant origin food in overall diet is significantly high, so estimation of dietary intakes of toxic trace elements via consumption of selected fruits and vegetables are of great importance for observing the underlying health risks. Therefore, the present study was aimed to assess dietary exposure of potentially toxic trace elements through the intake of locally grown fruits and vegetables in Akhtala community (Armenia), where not only mining industry is developed, but also cultivation of fruits and vegetables. Moreover, this investigation represents one of the very first attempts to estimate human dietary exposure of potentially toxic trace elements in the study area. Samples of some commonly grown fruits and vegetables (fig, cornel, raspberry, grape, apple, plum, maize, bean, potato, cucumber, onion, greens) were randomly collected from several home gardens located near mining areas in Akhtala community. The concentration of Cu, Mo, Ni, Cr, Pb, Zn, Hg, As and Cd in samples were determined by using an atomic absorption spectrophotometer (AAS). Precision and accuracy of analyses were guaranteed by repeated analysis of samples against NIST Standard Reference Materials. For a diet study, individual-based approach was used, so the consumption of selected fruits and vegetables was investigated through food frequency questionnaire (FFQ). Combining concentration data with contamination data, the estimated daily intakes (EDI) and cumulative daily intakes were assessed and compared with health-based guidance values (HBGVs). According to the determined concentrations of the studied trace elements in fruits and vegetables, it can be stressed that some trace elements (Cu, Ni, Pb, Zn) among the majority of samples exceeded maximum allowable limits set by international organizations. Meanwhile, others (Cr, Hg, As, Cd, Mo) either did not exceed these limits or still do not have established allowable limits. The obtained results indicated that only for Cu the EDI values exceeded dietary reference intake (0.01 mg/kg/Bw/day) for some investigated fruits and vegetables in decreasing order of potato > grape > bean > raspberry > fig > greens. In contrast to this, for combined consumption of selected fruits and vegetables estimated cumulative daily intakes exceeded reference doses in the following sequence: Zn > Cu > Ni > Mo > Pb. It may be concluded that habitual and combined consumption of the above mentioned fruits and vegetables can pose a health risk to the local population. Hence, further detailed studies are needed for the overall assessment of potential health implications taking into consideration adverse health effects posed by more than one toxic trace element.

Keywords: daily intake, dietary exposure, fruits, trace elements, vegetables

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61 Thermo-Economic Evaluation of Sustainable Biogas Upgrading via Solid-Oxide Electrolysis

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

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

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

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