Search results for: Charge recombination

Authors: Jihuai Wu, Zeyu Song, Zhang Lan, Liuxue Sun

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Solar energy is clean, open, and infinite, but solar radiation on the earth is fluctuating, intermittent, and unstable. So, the sustainable utilization of solar energy requires a combination of high-efficient energy conversion and low-loss energy storage technologies. Hence, a photo capacitor integrated with photo-electrical conversion and electric-chemical storage functions in single device is a cost-effective, volume-effective and functional-effective optimal choice. However, owing to the multiple components, multi-dimensional structure and multiple functions in one device, especially the mismatch of the functional modules, the overall conversion and storage efficiency of the photocapacitors is less than 13%, which seriously limits the development of the integrated system of solar conversion and energy storage. To this end, two typical photocapacitors were studied. A three-terminal photocapacitor was integrated by using perovskite solar cell as solar conversion module and symmetrical supercapacitor as energy storage module. A function portfolio management concept was proposed the relationship among various efficiencies during photovoltaic conversion and energy storage process were clarified. By harmonizing the energy matching between conversion and storage modules and seeking the maximum power points coincide and the maximum efficiency points synchronize, the overall efficiency of the photocapacitor surpassed 18 %, and Joule efficiency was closed to 90%. A voltage adjustable hybrid supercapacitor (VAHSC) was designed as energy storage module, and two Si wafers in series as solar conversion module, a three-terminal photocapacitor was fabricated. The VAHSC effectively harmonizes the energy harvest and storage modules, resulting in the current, voltage, power, and energy match between both modules. The optimal photocapacitor achieved an overall efficiency of 15.49% and Joule efficiency of 86.01%, along with excellent charge/discharge cycle stability. In addition, the Joule efficiency (ηJoule) was defined as the energy ratio of discharge/charge of the devices for the first time.

Keywords: joule efficiency, perovskite solar cell, photocapacitor, silicon solar cell, supercapacitor

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Authors: Keltoum Bouherine, Olivier Leroy

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The present work is dedicated to study a three–dimensional (3D) self-consistent fluid simulation of microwave discharges of argon plasma in PECVD reactor. The model solves the Maxwell’s equations, continuity equations for charged species and the electron energy balance equation, coupled with Poisson’s equation, and Navier-Stokes equations by finite element method, using COMSOL Multiphysics software. In this study, the simulations yield the profiles of plasma components as well as the charge densities and electron temperature, the electric field, the gas velocity, and gas temperature. The results show that the microwave plasma reactor is outside of local thermodynamic equilibrium.The present work is dedicated to study a three–dimensional (3D) self-consistent fluid simulation of microwave discharges of argon plasma in PECVD reactor. The model solves the Maxwell’s equations, continuity equations for charged species and the electron energy balance equation, coupled with Poisson’s equation, and Navier-Stokes equations by finite element method, using COMSOL Multiphysics software. In this study, the simulations yield the profiles of plasma components as well as the charge densities and electron temperature, the electric field, the gas velocity, and gas temperature. The results show that the microwave plasma reactor is outside of local thermodynamic equilibrium.

Keywords: electron density, electric field, microwave plasma reactor, gas velocity, non-equilibrium plasma

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Authors: Kok Hong Tan, Hing Wah Lee, Jhih-Wei Chen, Chang Fu Dee, Chung-Lin Wu, Siang-Piao Chai, Wei Sea Chang

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Semiconductor photocatalyst is known as one of the key roles in developing clean and sustainable energy. However, most of the semiconductor only possesses photoactivity within the UV light region, and hence, decreases the overall photocatalyst efficiency. Generally, the overall effectiveness of the photocatalyst activity is determined by three critical steps: (i) light absorption efficiency and photoexcitation electron-hole pair generation, (ii) separation and migration of charge carriers to the surface of the photocatalyst, and (iii) surface reaction of the carriers with its environment. Much effort has been invested on optimizing hierarchical nanostructures of semiconductors for efficient photoactivity due to the fact that the visible light absorption capability and occurrence of the chemical reactions mostly depend on the dimension of photocatalysts. In this work, we incorporated zero-dimensional (0D) gold nanoparticles (AuNPs) and one dimensional (1D) Zinc Oxide (ZnO) nanorods (NRs) onto strontium titanate (STO) for efficient visible light absorption, charge transfer, and separation. We demonstrate that the electrical and optical properties of the photocatalyst can be tuned by controlling the dimensional structures of AuNPs and ZnO NRs. We found that smaller AuNPs sizes exhibited higher photoactivity because of Fermi level shifting toward the conductive band of STO, STO band gap narrowing and broadening of absorption spectrum to the visible light region. For ZnO NRs, it was found that the average ZnO NRs c-axis length must achieve of certain length to induce multiphoton absorption as a result of light reflection and trapping behavior in the free space between adjacent ZnO NRs hence broadening the absorption spectrum of ZnO from UV to visible light region. This work opens up a new way of broadening the absorption spectrum by incorporating controllable nanostructures of semiconductors, which is important in optimizing the solar water splitting process.

Keywords: gold nanoparticles, photoelectrochemical, PEC, semiconductor photocatalyst, zinc oxide nanorods

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Authors: Mahfuzur Rahman

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Back-contact solar cells improve optical properties by moving all electrically conducting parts to the back of the cell. The cell's structure allows silicon solar cells to surpass the 25% efficiency barrier and interdigitated solar cells are now the most efficient. In this work, the fabrication of a light, efficient and temperature resistant interdigitated back contact (IBC) solar cell is investigated. This form of solar cell differs from a conventional solar cell in that the electrodes are located at the back of the cell, eliminating the need for grids on the top, allowing the full surface area of the cell to receive sunlight, resulting in increased efficiency. In this project, we will use SILVACO TCAD, an optoelectronic device simulator, to construct a very thin solar cell with dimensions of 100x250um in 2D Luminous. The influence of sunlight intensity and atmospheric temperature on solar cell output power is highly essential and it has been explored in this work. The cell's optimum performance with 150um bulk thickness provides 28.81% efficiency with an 87.68% fill factor rate making it very thin, flexible and resilient, providing diverse operational capabilities.

Keywords: interdigitated, shading, recombination loss, incident-plane, drift-diffusion, luminous, SILVACO

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Authors: Sara Mosallanejad, Bogdan Z. Dlugogorski, Jeff Gore, Mohammednoor Altarawneh

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Ammonium nitrate (NH­₄NO₃, AN) is commonly used as the main component of AN emulsion and fuel oil (ANFO) explosives, that use extensively in civilian and mining operations for underground development and tunneling applications. The emulsion formulation and wettability of AN prills, which affect the physical stability and detonation of ANFO, highly depend on the surface tension, density, viscosity of the used liquid. Therefore, for engineering applications of this material, the determination of density and surface tension of concentrated aqueous solutions of AN is essential. The molecular dynamics (MD) simulation method have been used to investigate the density and the surface tension of high concentrated ammonium nitrate solutions; up to its solubility limit in water. Non-polarisable models for water and ions have carried out the simulations, and the electronic continuum correction model (ECC) uses a scaling of the charges of the ions to apply the polarisation implicitly into the non-polarisable model. The results of calculated density and the surface tension of the solutions have been compared to available experimental values. Our MD simulations show that the non-polarisable model with full-charge ions overestimates the experimental results while the reduce-charge model for the ions fits very well with the experimental data. Ions in the solutions show repulsion from the interface using the non-polarisable force fields. However, when charges of the ions in the original model are scaled in line with the scaling factor of the ECC model, the ions create a double ionic layer near the interface by the migration of anions toward the interface while cations stay in the bulk of the solutions. Similar ions orientations near the interface were observed when polarisable models were used in simulations. In conclusion, applying the ECC model to the non-polarisable force field yields the density and surface tension of the AN solutions with high accuracy in comparison to the experimental measurements.

Keywords: ammonium nitrate, electronic continuum correction, non-polarisable force field, surface tension

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Authors: Daniel F. Sava, Anton Ficai, Bogdan S. Vasile, Georgeta Voicu, Ecaterina Andronescu

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The energy crisis and environmental contamination are very serious problems, therefore searching for better and sustainable renewable energy is a must. It is predicted that the global energy demand will double until 2050. Solar water splitting and photocatalysis are considered as one of the solutions to these issues. The use of oxide semiconductors for solar water splitting and photocatalysis started in 1972 with the experiments of Fujishima and Honda on TiO2 electrodes. Since then, the evolution of nanoscience and characterization methods leads to a better control of size, shape and properties of materials. Although the past decade advancements are astonishing, for these applications the properties have to be controlled at a much finer level, allowing the control of charge-carrier lives, energy level positions, charge trapping centers, etc. Graphene has attracted a lot of attention, since its discovery in 2004, due to the excellent electrical, optical, mechanical and thermal properties that it possesses. These properties make it an ideal support for photocatalysts, thus graphene composites with oxide semiconductors are of great interest. We present in this work the synthesis and characterization of graphene-related materials and oxide semiconductors and their different composites. These materials can be used in constructing devices for different applications (batteries, water splitting devices, solar cells, etc), thus showing their application flexibility. The synthesized materials are different morphologies and sizes of TiO2, ZnO and Fe2O3 that are obtained through hydrothermal, sol-gel methods and graphene oxide which is synthesized through a modified Hummer method and reduced with different agents. Graphene oxide and the reduced form could also be used as a single material for transparent conductive films. The obtained single materials and composites were characterized through several methods: XRD, SEM, TEM, IR spectroscopy, RAMAN, XPS and BET adsorption/desorption isotherms. From the results, we see the variation of the properties with the variation of synthesis parameters, size and morphology of the particles.

Keywords: composites, graphene, hydrothermal, renewable energy

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Authors: Jyh-Cheng Chen, Tai-Jing Wang, Yun-Wei Lin

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Astaxanthin has been demonstrated to exhibit a wide range of beneficial effects including anti-inflammatory and anti-cancer properties. However, the molecular mechanism of astaxanthin-induced cytotoxicity in non-small cell lung cancer (NSCLC) cells has not been identified. Rad51 plays a central role in homologous recombination and high levels of Rad51 expression are observed in chemo- or radioresistant carcinomas. In this study, astaxanthin treatment inhibited cell viability and proliferation of two NSCLC cells, A549 and H1703. Treatment with astaxanthin decreased Rad51 expression and phospho-AKT protein level in a time and dose-dependent manner. Furthermore, expression of constitutively active AKT (AKT-CA) vector significantly rescued the decreased Rad51 protein and mRNA levels in astaxanthin-treated NSCLC cells. Combined treatment with PI3K inhibitors (LY294002 or wortmannin) and astaxanthin further decreased the Rad51 expression in NSCLC cells. Knockdown of Rad51 enhanced astaxanthin-induced cytotoxicity and growth inhibition in NSCLC cells. These findings may have implications for the rational design of future drug regimens incorporating astaxanthin for the treatment of NSCLC.

Keywords: astaxanthin, cytotoxicity, AKT, non-small cell lung cancer, PI3K

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Authors: Corentin Jankowiak, Aggelos Zacharopoulos, Caterina Brandoni

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In a context of increasing stress put on the electricity network by the decarbonization of many sectors, energy storage is likely to be the key mitigating element, by acting as a buffer between production and demand. In particular, the highest potential for storage is when connected closer to the loads. Yet, low voltage storage struggles to penetrate the market at a large scale due to the novelty and complexity of the solution, and the competitive advantage of fossil fuel-based technologies regarding regulations. Strong and reliable numerical simulations are required to show the benefits of storage located near loads and promote its development. The present study was restrained from excluding aggregated control of storage: it is assumed that the storage units operate independently to one another without exchanging information – as is currently mostly the case. A computationally light battery model is presented in detail and validated by direct comparison with a domestic battery operating in real conditions. This model is then used to develop Peak-Shaving (PS) control strategies as it is the decentralized service from which beneficial impacts are most likely to emerge. The aggregation of flatter, peak- shaved consumption profiles is likely to lead to flatter and arbitraged profile at higher voltage layers. Furthermore, voltage fluctuations can be expected to decrease if spikes of individual consumption are reduced. The crucial part to achieve PS lies in the charging pattern: peaks depend on the switching on and off of appliances in the dwelling by the occupants and are therefore impossible to predict accurately. A performant PS strategy must, therefore, include a smart charge recovery algorithm that can ensure enough energy is present in the battery in case it is needed without generating new peaks by charging the unit. Three categories of PS algorithms are introduced in detail. First, using a constant threshold or power rate for charge recovery, followed by algorithms using the State Of Charge (SOC) as a decision variable. Finally, using a load forecast – of which the impact of the accuracy is discussed – to generate PS. A performance metrics was defined in order to quantitatively evaluate their operating regarding peak reduction, total energy consumption, and self-consumption of domestic photovoltaic generation. The algorithms were tested on load profiles with a 1-minute granularity over a 1-year period, and their performance was assessed regarding these metrics. The results show that constant charging threshold or power are far from optimal: a certain value is not likely to fit the variability of a residential profile. As could be expected, forecast-based algorithms show the highest performance. However, these depend on the accuracy of the forecast. On the other hand, SOC based algorithms also present satisfying performance, making them a strong alternative when the reliable forecast is not available.

Keywords: decentralised control, domestic integrated batteries, electricity network performance, peak-shaving algorithm

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Authors: Thirupathi Thippani, Kothandaraman Ramanujam

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Current research on energy storage has been paid to metal-air batteries, because of attractive alternate energy source for the future. Metal – air batteries have the probability to significantly increase the power density, decrease the cost of energy storage and also used for a long time due to its high energy density, low-level pollution, light weight. The performance of these batteries mostly restricted by the slow kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on cathode during battery discharge and charge. The ORR and OER are conventionally carried out with precious metals (such as Pt) and metal oxides (such as RuO₂ and IrO₂) as catalysts separately. However, these metal-based catalysts are regularly undergoing some difficulties, including high cost, low selectivity, poor stability and unfavorable to environmental effects. So, in order to develop the active, stable, corrosion resistance and inexpensive bi-functional catalyst material is mandatory for the commercialization of zinc-air rechargeable battery technology. We have attempted and synthesized non-precious metal (NPM) catalysts comprising cobalt and N-doped multiwalled carbon nanotubes (N-MWCNTs-Co) were synthesized by the solid-state pyrolysis (SSP) of melamine with Co₃O₄. N-MWCNTs-Co acts as an excellent electrocatalyst for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), and hence can be used in secondary metal-air batteries and in unitized regenerative fuel cells. It is important to study the OER and ORR at high concentrations of KOH as most of the metal-air batteries employ KOH concentrations > 4M. In the first 16 cycles of the zinc-air battery while using N-MWCNTs-Co, 20 wt.% Pt/C or 20 wt.% IrO₂/C as air electrodes. In the ORR regime (the discharge profile of the zinc-air battery), the cell voltage exhibited by N-MWCNTs-Co was 44 and 83 mV higher (based on 5th cycle) in comparison to of 20 wt.% Pt/C and 20 wt.% IrO₂/C respectively. To demonstrate this promise, a zinc-air battery was assembled and tested at a current density of 0.5 Ag⁻¹ for charge-discharge 100 cycles.

Keywords: oxygen reduction reaction (ORR), oxygen evolution reaction(OER), non-platinum, zinc air battery

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Authors: Tomas Vincze, Michal Micjan, Milan Pavuk, Martin Weis

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In recent years, alternative materials are gaining attention to replace polycrystalline and amorphous silicon, which are a standard for low requirement devices, where silicon is unnecessarily and high cost. For that reason, metal oxides are envisioned as the new materials for these low-requirement applications such as sensors, solar cells, energy storage devices, or field-effect transistors. Their most common way of layer growth is sputtering; however, this is a high-cost fabrication method, and a more industry-suitable alternative is the sol-gel method. In this group of materials, many oxides exhibit a semiconductor-like behavior with sufficiently high mobility to be applied as transistors. The sol-gel method is a cost-effective deposition technique for semiconductor-based devices. Copper oxides, as p-type semiconductors with free charge mobility up to 1 cm2/Vs., are suitable replacements for poly-Si or a-Si:H devices. However, to reach the potential of silicon devices, a fine-tuning of material properties is needed. Here we focus on the optimization of the electrical parameters of copper oxide-based field-effect transistors by modification of precursor solvent (usually 2-methoxy ethanol). However, to achieve solubility and high-quality films, a better solvent is required. Since almost no solvents have both high dielectric constant and high boiling point, an alternative approach was proposed with blend solvents. By mixing isopropyl alcohol (IPA) and 2-methoxy ethanol (2ME) the precursor reached better solubility. The quality of the layers fabricated using mixed solutions was evaluated in accordance with the surface morphology and electrical properties. The IPA:2ME solution mixture reached optimum results for the weight ratio of 1:3. The cupric oxide layers for optimal mixture had the highest crystallinity and highest effective charge mobility.

Keywords: copper oxide, field-effect transistor, semiconductor, sol-gel method

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

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

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

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Authors: Yasar N. Kavil, Yasser A. Shaban, Radwan K. Al Farawati, Mohamed I. Orif, Shahed U. M. Khanc

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Photocatalytic way of reduction of CO₂ in polluted seawater into chemical fuel, methanol, was successfully gained over Cu/C-co-doped TiO₂ nanoparticles under UV and natural sunlight. A homemade stirred batch annular reactor was used to carry out the photocatalytic reduction experiments. Photocatalysts with various Cu loadings (0, 0.5, 1, 3, 5 and 7 wt.%) were synthesized by the sol-gel procedure and were characterized by XRD, SEM, UV–Vis, FTIR, and XPS. The photocatalytic production of methanol was promoted by the co-doping with C and Cu into TiO₂. This improvement was attributed to the modification of bandgap energy and the hindrance of the charges recombination. The polluted seawater showing the yield depended on its background hydrographic parameters. We assessed two types of polluted seawater system, the observed yield was 2910 and 990 µmol g⁻¹ after 5 h of illumination under UV and natural sunlight respectively in system 1 and the corresponding yield in system 2 was 2250 and 910 µmol g⁻¹ after 5 h of illumination. The production of methanol in the case of oxygen-depleted water was low, this is mainly attributed to the competition of methanogenic bacteria over methanol production. The results indicated that the methanol yield produced by Cu-C/TiO₂ was much higher than those of carbon-modified titanium oxide (C/TiO₂) and Degussa (P25-TiO₂). Under the current experimental condition, the optimum loading was achieved by the doping of 3 wt % of Cu. The highest methanol yield was obtained over 1 g L-1 of 3wt% Cu/C-TiO₂.

Keywords: CO₂ photoreduction, copper, Cu/C-co-doped TiO₂, methanol, seawater

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Authors: Khamael M. Abualnaja, Lidija Šiller, Ben R. Horrocks

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The structural characterization of silicon nano crystals (SiNCs) have been carried out using transmission electron microscope (TEM) and atomic force microscopy (AFM). SiNCs are crystalline with an average diameter of 65 nm. Erbium trichloride was added to silicon nano crystals using a simple chemical procedure. Erbium is useful in this context because it has a narrow emission band at ⋍1536 nm which corresponds to a standard optical telecommunication wavelength. The optical properties of SiNCs and erbium-mixed SiNCs samples have been characterized using UV-vis spectroscopy, confocal Raman spectroscopy and photoluminescence spectroscopy (PL). SiNCs and erbium-mixed SiNCs samples exhibit an orange PL emission peak at around 595 nm that arise from radiative recombination of Si. Erbium-mixed SiNCs also shows a weak PL emission peak at ⋍1536 nm that attributed to the intra-4f transition in erbium ions. The intensity of the PL peak of Si in erbium-mixed SiNCs is increased in the intensity up to ×3 as compared to pure SiNCs. It was observed that intensity of 1536 nm peak decreased dramatically in the presence of silicon nano crystals and the PL emission peak of silicon nano crystals is increased. Therefore, the resulted data present that the energy transfer from erbium ions to SiNCs due to the chemical mixing method which used in this work.

Keywords: Silicon Nanocrystals (SiNCs), Erbium Ion, photoluminescence, energy transfer

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Authors: Julia Langen

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This article describes the challenges of a wireless charging system for a cab waiting lane in a public space and presents a concept for solving them. In this concept, multiple cabs can be charged simultaneously and during stopping and rolling. Particular technical challenges are a coil topology that meets the EMF requirements and an intelligent control concept that allows the individual coil segments to be switched on and off. The charging concept explained here is currently being implemented as a pilot project, so that initial results on the operation can be presented.

Keywords: charge lane, inductive charging solution, smart city, wireless power transfer

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Authors: Xiaowei Zhang, Min Xu, Saeid Habibi, Fengjun Yan, Ryan Ahmed

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Recently, Electric Vehicles (EVs) have received extensive consideration since they offer a more sustainable and greener transportation alternative compared to fossil-fuel propelled vehicles. Lithium-Ion (Li-ion) batteries are increasingly being deployed in EVs because of their high energy density, high cell-level voltage, and low rate of self-discharge. Since Li-ion batteries represent the most expensive component in the EV powertrain, accurate monitoring and control strategies must be executed to ensure their prolonged lifespan. The Battery Management System (BMS) has to accurately estimate parameters such as the battery State-of-Charge (SOC), State-of-Health (SOH), and Remaining Useful Life (RUL). In order for the BMS to estimate these parameters, an accurate and control-oriented battery model has to work collaboratively with a robust state and parameter estimation strategy. Since battery physical parameters, such as the internal resistance and diffusion coefficient change depending on the battery state-of-life (SOL), the BMS has to be adaptive to accommodate for this change. In this paper, an extensive battery aging study has been conducted over 12-months period on 5.4 Ah, 3.7 V Lithium polymer cells. Instead of using fixed charging/discharging aging cycles at fixed C-rate, a set of real-world driving scenarios have been used to age the cells. The test has been interrupted every 5% capacity degradation by a set of reference performance tests to assess the battery degradation and track model parameters. As battery ages, the combined model parameters are optimized and tracked in an offline mode over the entire batteries lifespan. Based on the optimized model, a state and parameter estimation strategy based on the Extended Kalman Filter (EKF) and the relatively new Smooth Variable Structure Filter (SVSF) have been applied to estimate the SOC at various states of life.

Keywords: lithium-ion batteries, genetic algorithm optimization, battery aging test, parameter identification

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Authors: J. Martin, A. Nominé, T. Czerwiec, G. Henrion, T. Belmonte

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The plasma electrolytic oxidation (PEO) is a particular electrochemical process to produce protective oxide ceramic coatings on light-weight metals (Al, Mg, Ti). When applied to aluminum alloys, the resulting PEO coating exhibit improved wear and corrosion resistance because thick, hard, compact and adherent crystalline alumina layers can be achieved. Several investigations have been carried out to improve the efficiency of the PEO process and one particular way consists in tuning the suitable electrical regime. Despite the considerable interest in this process, there is still no clear understanding of the underlying discharge mechanisms that make possible metal oxidation up to hundreds of µm through the ceramic layer. A key parameter that governs the PEO process is the numerous short-lived micro-discharges (micro-plasma in liquid) that occur continuously over the processed surface when the high applied voltage exceeds the critical dielectric breakdown value of the growing ceramic layer. By using a bipolar pulsed current to supply the electrodes, we previously observed that micro-discharges are delayed with respect to the rising edge of the anodic current. Nevertheless, explanation of the origin of such phenomena is still not clear and needs more systematic investigations. The aim of the present communication is to identify the relationship that exists between this delay and the mechanisms responsible of the oxide growth. For this purpose, the delay of micro-discharges ignition is investigated as the function of various electrical parameters such as the current density (J), the current pulse frequency (F) and the anodic to cathodic charge quantity ratio (R = Qp/Qn) delivered to the electrodes. The PEO process was conducted on Al2214 aluminum alloy substrates in a solution containing potassium hydroxide [KOH] and sodium silicate diluted in deionized water. The light emitted from micro-discharges was detected by a photomultiplier and the micro-discharge parameters (number, size, life-time) were measured during the process by means of ultra-fast video imaging (125 kfr./s). SEM observations and roughness measurements were performed to characterize the morphology of the elaborated oxide coatings while XRD was carried out to evaluate the amount of corundum -Al203 phase. Results show that whatever the applied current waveform, the delay of micro-discharge appearance increases as the process goes on. Moreover, the delay is shorter when the current density J (A/dm2), the current pulse frequency F (Hz) and the ratio of charge quantity R are high. It also appears that shorter delays are associated to stronger micro-discharges (localized, long and large micro-discharges) which have a detrimental effect on the elaborated oxide layers (thin and porous). On the basis of the results, a model for the growth of the PEO oxide layers will be presented and discussed. Experimental results support that a mechanism of electrical charge accumulation at the oxide surface / electrolyte interface takes place until the dielectric breakdown occurs and thus until micro-discharges appear.

Keywords: aluminium, micro-discharges, oxidation mechanisms, plasma electrolytic oxidation

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Authors: Qianying Sun, Abdelhadi Kassiba, Guorong Li

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ZnO with wurtzite structure is a well-known semiconducting oxide (SCO), being applied in thermoelectric devices, varistors, gas sensors, transparent electrodes, solar cells, liquid crystal displays, piezoelectric and electro-optical devices. Intrinsically, ZnO is weakly n-type SCO due to native defects (Znⱼ, Vₒ). However, the substitutional doping by metallic elements as (Al, Ti) gives rise to a high n-type conductivity ensured by donor centers. Under CO+N₂ sintering atmosphere, Schottky barriers of ZnO ceramics will be suppressed by lowering the concentration of acceptors at grain boundaries and then inducing a large increase in the Hall mobility, thereby increasing the conductivity. The presented work concerns ZnO based ceramics, which are fabricated with doping by TiO₂ (0.50mol%), Al₂O₃ (0.25mol%) and MgO (1.00mol%) and sintering in different atmospheres (Air (A), N₂ (N), CO+N₂(C)). We obtained uniform, dense ceramics with ZnO as the main phase and Zn₂TiO₄ spinel as a secondary and minor phase. An important increase of the conductivity was shown for the samples A, N, and C which were sintered under different atmospheres. The highest conductivity (σ = 1.52×10⁵ S·m⁻¹) was obtained under the reducing atmosphere (CO). The role of doping was investigated with the aim to identify the local environment and valence states of the doping elements. Thus, Electron paramagnetic spectroscopy (EPR) determines the concentration of defects and the effects of charge carriers in ZnO ceramics as a function of the sintering atmospheres. The relation between conductivity and defects concentration shows the opposite behavior between these parameters suggesting that defects act as traps for charge carriers. For Al ions, nuclear magnetic resonance (NMR) technique was used to identify the involved local coordination of these ions. Beyond the six and forth coordinated Al, an additional NMR signature of ZnO based TCO requires analysis taking into account the grain boundaries and the conductivity through the Knight shift effects. From the thermal evolution of the conductivity as a function of the sintering atmosphere, we succeed in defining the conditions to realize ZnO based TCO ceramics with an important thermal coefficient of resistance (TCR) which is promising for electrical safety of devices.

Keywords: ceramics, conductivity, defects, TCO, ZnO

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Authors: I. Ben Kaddour, S. Larbaoui

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Since their first synthesis, the Silicoaluminophosphates materials have proved their efficiency as a good adsorbent and catalyst in several environmental and energetic applications. In this work, the photocatalytic hydrogen production from water splitting reactions has been conducted under visible radiations in the presence of a series of iron and/or titanium-containing microporous silico-alumino-phosphates materials synthesized by hydrothermal method, using triethylamine as an organic structuring agent to obtain the AFI structure type. These photo-catalysts were then characterized by various physicochemical methods to determine their structural, textural and morphological properties such as X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) coupled with X rays microanalysis, nitrogen adsorption measurements, UV-visible diffuse reflectance spectroscopy (UV-Vis-DRS), and X-rays photoelectron spectroscopy (XPS) and the analysis revealed that these materials have significant photocatalytic properties. The hydrogen production process has been followed by photoelectrochemical characterization (PEC). The results showed that hydrogen is the only gas produced, and the reaction takes place in the conduction band where water is reduced to hydrogen. The electron recombination has also been avoided, as holes are entrapped using hole scavengers. In addition, these catalysts have been shown to remain stable during reuse for up to five cycles.

Keywords: photocatalysis, SAPO-5, hydrothermal synthesis, hydrogen production

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Authors: Istvan Szilagyi, Marko Pavlovic, Paul Rouster

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Antioxidant enzymes are the most efficient defense systems against reactive oxygen species, which cause severe damage in living organisms and industrial products. However, their supplementation is problematic due to their high sensitivity to the environmental conditions. Immobilization on carrier nanoparticles is a promising research direction towards the improvement of their functional and colloidal stability. In that way, their applications in biomedical treatments and manufacturing processes in the food, textile and cosmetic industry can be extended. The main goal of the present research was to prepare and formulate antioxidant bionanocomposites composed of superoxide dismutase (SOD) enzyme, anionic clay (layered double hydroxide, LDH) nanoparticle and heparin (HEP) polyelectrolyte. To characterize the structure and the colloidal stability of the obtained compounds in suspension and solid state, electrophoresis, dynamic light scattering, transmission electron microscopy, spectrophotometry, thermogravimetry, X-ray diffraction, infrared and fluorescence spectroscopy were used as experimental techniques. LDH-SOD composite was synthesized by enzyme immobilization on the clay particles via electrostatic and hydrophobic interactions, which resulted in a strong adsorption of the SOD on the LDH surface, i.e., no enzyme leakage was observed once the material was suspended in aqueous solutions. However, the LDH-SOD showed only limited resistance against salt-induced aggregation and large irregularly shaped clusters formed during short term interval even at lower ionic strengths. Since sufficiently high colloidal stability is a key requirement in most of the applications mentioned above, the nanocomposite was coated with HEP polyelectrolyte to develop highly stable suspensions of primary LDH-SOD-HEP particles. HEP is a natural anticoagulant with one of the highest negative line charge density among the known macromolecules. The experimental results indicated that it strongly adsorbed on the oppositely charged LDH-SOD surface leading to charge inversion and to the formation of negatively charged LDH-SOD-HEP. The obtained hybrid materials formed stable suspension even under extreme conditions, where classical colloid chemistry theories predict rapid aggregation of the particles and unstable suspensions. Such a stabilization effect originated from electrostatic repulsion between the particles of the same sign of charge as well as from steric repulsion due to the osmotic pressure raised during the overlap of the polyelectrolyte chains adsorbed on the surface. In addition, the SOD enzyme kept its structural and functional integrity during the immobilization and coating processes and hence, the LDH-SOD-HEP bionanocomposite possessed excellent activity in decomposition of superoxide radical anions, as revealed in biochemical test reactions. In conclusion, due to the improved colloidal stability and the good efficiency in scavenging superoxide radical ions, the developed enzymatic system is a promising antioxidant candidate for biomedical or other manufacturing processes, wherever the aim is to decompose reactive oxygen species in suspensions.

Keywords: clay, enzyme, polyelectrolyte, formulation

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Authors: C. D’Urso, L. Frusteri, M. Samperi, G. Leonardi

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Solid metal halides are used as active cathode ingredients in the case of Na-NiCl2 batteries that require a fused secondary electrolyte, sodium tetrachloraluminate (NaAlCl4), to facilitate the movement of the Na+ ion into the cathode. The sodium-nickel chloride (Na - NiCl2) battery has been extensively investigated as a promising system for large-scale energy storage applications. The growth of Ni and NaCl particles in the cathodes is one of the most important factors that degrade the performance of the Na-NiCl2 battery. The larger the particles of active ingredients contained in the cathode, the smaller the active surface available for the electrochemical reaction. Therefore, the growth of Ni and NaCl particles can lead to an increase in cell polarization resulting from the reduced active area. A higher current density, a higher state of charge (SOC) at the end of the charge (EOC) and a lower Ni / NaCl ratio are the main parameters that result in the rapid growth of Ni particles. In light of these problems, cathode and chemistry Nano-materials with recognized and well-documented electrochemical functions have been studied and manufactured to simultaneously improve battery performance and develop less expensive and more performing, sustainable and environmentally friendly materials. Starting from the well-known cathodic material (Na-NiCl2), the new electrolytic materials have been prepared on the replacement of nickel with iron (10-90%substitution of Nichel with Iron), to obtain a new material with potential advantages compared to current battery technologies; for example,, (1) lower cost of cathode material compared to state of the art as well as (2) choices of cheaper materials (stainless steels could be used for cell components, including cathode current collectors and cell housings). The study on the particle size of the cathode and the physicochemical characterization of the cathode was carried out in the test cell using, where possible, the GITT method (galvanostatic technique of intermittent titration). Furthermore, the impact of temperature on the different cathode compositions of the positive electrode was studied. Especially the optimum operating temperature is an important parameter of the active material.

Keywords: critical raw materials, energy storage, sodium metal halide, battery

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Authors: Rudolf Hrach, Stanislav Novak, Vera Hrachova

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Composite and nanocomposite films represent the class of promising materials and are often objects of the study due to their mechanical, electrical and other properties. The most interesting ones are probably the composite metal/dielectric structures consisting of a metal component embedded in an oxide or polymer matrix. Behaviour of composite films varies with the amount of the metal component inside what is called filling factor. The structures contain individual metal particles or nanoparticles completely insulated by the dielectric matrix for small filling factors and the films have more or less dielectric properties. The conductivity of the films increases with increasing filling factor and finally a transition into metallic state occurs. The behaviour of composite films near a percolation threshold, where the change of charge transport mechanism from a thermally-activated tunnelling between individual metal objects to an ohmic conductivity is observed, is especially important. Physical properties of composite films are given not only by the concentration of metal component but also by the spatial and size distributions of metal objects which are influenced by a technology used. In our contribution, a study of composite structures with the help of methods of computational physics was performed. The study consists of two parts: -Generation of simulated composite and nanocomposite films. The techniques based on hard-sphere or soft-sphere models as well as on atomic modelling are used here. Characterizations of prepared composite structures by image analysis of their sections or projections follow then. However, the analysis of various morphological methods must be performed as the standard algorithms based on the theory of mathematical morphology lose their sensitivity when applied to composite films. -The charge transport in the composites was studied by the kinetic Monte Carlo method as there is a close connection between structural and electric properties of composite and nanocomposite films. It was found that near the percolation threshold the paths of tunnel current forms so-called fuzzy clusters. The main aim of the present study was to establish the correlation between morphological properties of composites/nanocomposites and structures of conducting paths in them in the dependence on the technology of composite films.

Keywords: composite films, computer modelling, image analysis, nanocomposite films

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Authors: Endris Yibru Hanurry, Wei-Hsin Hsu, Hsieh-Chih Tsai

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In recent years, the discovery of small interfering RNAs (siRNAs) has got great attention for the treatment of cancer and other diseases. However, the therapeutic efficacy of siRNAs has been faced with many drawbacks because of short half-life in blood circulation, poor membrane penetration, weak endosomal escape and inadequate release into the cytosol. To overcome these drawbacks, we designed a non-viral vector by conjugating polyamidoamine generation 4.5 dendrimer (PDG4.5) with diethylenetriamine (DETA)- and tetraethylenepentamine (TEPA) followed by binding with siRNA to form polyplexes through electrostatic interaction. The result of 1H nuclear magnetic resonance (NMR), 13C NMR, correlation spectroscopy, heteronuclear single–quantum correlation spectroscopy, and Fourier transform infrared spectroscopy confirmed the successful conjugation of DETA and TEPA with PDG4.5. Then, the size, surface charge, morphology, binding ability, stability, release assay, toxicity and cellular internalization were analyzed to explore the physicochemical and biological properties of PDG4.5-DETA and PDG4.5-TEPA polyplexes at specific N/P ratios. The polyplexes (N/P = 8) exhibited spherical nanosized (125 and 85 nm) particles with optimum surface charge (13 and 26 mV), showed strong siRNA binding ability, protected the siRNA against enzyme digestion and accepted biocompatibility to the HeLa cells. Qualitatively, the fluorescence microscopy image revealed the delocalization (Manders’ coefficient 0.63 and 0.53 for PDG4.5-DETA and PDG4.5-TEPA, respectively) of polyplexes and the translocation of the siRNA throughout the cytosol to show a decent cellular internalization and intracellular biodistribution of polyplexes in HeLa cells. Quantitatively, the flow cytometry result indicated that a significant (P < 0.05) amount of siRNA was internalized by cells treated with PDG4.5-DETA (68.5%) and PDG4.5-TEPA (73%) polyplexes. Generally, PDG4.5-DETA and PDG4.5-TEPA were ideal nanocarriers of siRNA in vitro and might be used as promising candidates for in vivo study and future pharmaceutical applications.

Keywords: non-viral carrier, oligoalkylamine, poly(amidoamine) dendrimer, polyplexes, siRNA

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Authors: Archana Gupta, Rajesh Kumar

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The chemistry of chalcones has generated intensive scientific studies throughout the world. Especially, interest has been focused on the synthesis and biodynamic activities of chalcones. The blue light transmittance, excellent crystallizability and the two planar rings connected through a conjugated double bond show that chalcone derivatives are superior nonlinear organic compounds. 3-(2-Chloro-6-fluoro¬phen¬yl)-1-(2-thien¬yl) prop-2-en-1-one, 3-(2, 4- Dichlorophenyl) – 1 - (4-methylphenyl) – prop -2-en-1-one, (2E)-3-[4-(methylsulfanyl) phenyl]-1-(4-nitrophenyl) prop-2-en-1-one are some chalcone derivatives exhibiting non linear optical (NLO) properties. NLO materials have been extensively investigated in recent years as they are the key elements for photonic technologies of optical communication, optical interconnect oscillator, amplifier, frequency converter etc. Due to their high molecular hyperpolarizabilities, organic materials display a number of significant NLO properties. Experimental measurements and theoretical calculations on molecular hyperpolarizability β have become one of the key factors in the design of second order NLO materials. Theoretical determination of hyperpolarizability is quite useful both in understanding the relationship between the molecular structure and NLO properties. It also provides a guideline to experimentalists for the design and synthesis of organic NLO materials. Quantum-chemical calculations have made an important contribution to the understanding of the electronic polarization underlying the molecular NLO processes and the establishment of structure–property relationships. In the present investigation, the detailed vibrational analysis of some chalcone derivatives is taken up to understand the correlation of the charge transfer interaction and the NLO activity of the molecules based on density functional theory calculations. The vibrational modes contributing toward the NLO activity have been identified and analyzed. Rather large hyperpolarizability derived by theoretical calculations suggests the possible future use of these compounds for non-linear optical applications. The study suggests the importance of π - conjugated systems for non-linear optical properties and the possibility of charge transfer interactions. We hope that the results of the present study of chalcone derivatives are of assistance in development of new efficient materials for technological applications.

Keywords: hyperpolarizability, molecular structure, NLO material, quantum chemical calculations

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Authors: Włodzimierz Lewandowski, Renata Świsłocka, Aleksandra Golonko, Grzegorz Świderski, Monika Kalinowska

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Caffeic acid (3,4-dihydroxycinnamic) is distributed in a free form or as ester conjugates in many fruits, vegetables and seasonings including plants used for medical purpose. Caffeic acid is present in propolis – a substance with exceptional healing properties used in natural medicine since ancient times. The antioxidant, antibacterial, antiinflammatory and anticarcinogenic properties of caffeic acid are widely described in the literature. The biological activity of chemical compounds can be modified by the synthesis of their derivatives or metal complexes. The structure of the compounds determines their biological properties. This work is a continuation of the broader topic concerning the investigation of the correlation between the electronic charge distribution and biological (anticancer and antioxidant) activity of the chosen phenolic acids and their metal complexes. In the framework of this study the synthesis of new metal complexes of sodium, magnesium, aluminium, iron (III) ruthenium (III) and osmium (III) with caffeic acid was performed. The spectroscopic properties of these compounds were studied by means of FT-IR, FT-Raman, UV-Vis, ¹H and ¹³C NMR. The quantum-chemical calculations (at B3LYP/LAN L2DZ level) of caffeic acid and selected complexes were done. Moreover the antioxidant properties of synthesized complexes were studied in relation to selected stable radicals (method of reduction of DPPH and method of reduction of ABTS). On the basis of the differences in the number, intensity and locations of the bands from the IR, Raman, UV/Vis and NMR spectra of caffeic acid and its metal complexes the effect of metal cations on the electronic system of ligand was discussed. The geometry, theoretical spectra and electronic charge distribution were calculated by the use of Gaussian 09 programme. The geometric aromaticity indices (Aj – normalized function of the variance in bond lengths; BAC - bond alternation coefficient; HOMA – harmonic oscillator model of aromaticity and I₆ – Bird’s index) were calculated and the changes in the aromaticity of caffeic acid and its complexes was discussed. This work was financially supported by National Science Centre, Poland, under the research project number 2014/13/B/NZ7/02-352.

Keywords: antioxidant properties, caffeic acid, metal complexes, spectroscopic methods

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Authors: Arafa A. Alholaisi, Jamal H. Madani, M. A. Alvi

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The radial form of nuclear matter distribution, charge and the shape of nuclei are essential properties of nuclei, and hence, are of great attention for several areas of research in nuclear physics. More than last three decades have witnessed a range of experimental means employing leptonic probes (such as muons, electrons etc.) for exploring nuclear charge distributions, whereas the hadronic probes (for example alpha particles, protons, etc.) have been used to investigate the nuclear matter distributions. In this paper, p-^9,11Li elastic scattering differential cross sections in the energy range  to  MeV have been studied by means of Coulomb modified Glauber scattering formalism. By applying the semi-phenomenological Bhagwat-Gambhir-Patil [BGP] nuclear density for loosely bound neutron rich ¹¹Li nucleus, the estimated matter radius is found to be 3.446 fm which is quite large as compared to so known experimental value 3.12 fm. The results of microscopic optical model based calculation by applying Bethe-Brueckner–Hartree–Fock formalism (BHF) have also been compared. It should be noted that in most of phenomenological density model used to reproduce the p-¹¹Li differential elastic scattering cross sections data, the calculated matter radius lies between 2.964 and 3.55 fm. The calculated results with phenomenological BGP model density and with nucleon density calculated in the relativistic mean-field (RMF) reproduces p-⁹Li and p-¹¹Li experimental data quite nicely as compared to Gaussian- Gaussian or Gaussian-Oscillator densities at all energies under consideration. In the approach described here, no free/adjustable parameter has been employed to reproduce the elastic scattering data as against the well-known optical model based studies that involve at least four to six adjustable parameters to match the experimental data. Calculated reaction cross sections σ_R for p-¹¹Li at these energies are quite large as compared to estimated values reported by earlier works though so far no experimental studies have been performed to measure it.

Keywords: Bhagwat-Gambhir-Patil density, Coulomb modified Glauber model, halo nucleus, optical limit approximation

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Authors: Jae-Hyung Jin, Kyung-Tae Lee, Yee-Seul So, Eunji Jeong, Yeonseon Lee, Dongpil Lee, Dong-Gi Lee, Yong-Sun Bahn

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Cryptococcus neoformans causes cryptococcal meningoencephalitis mainly in immunocompromised patients as well as immunocompetent people. But therapeutic options are limited to treat cryptococcosis. Some signaling pathways including cyclic AMP pathway, MAPK pathway, and calcineurin pathway play a central role in the regulation of the growth, differentiation, and virulence of C. neoformans. To understand signaling networks regulating the virulence of C. neoformans, we selected the 114 putative phosphatase genes, one of the major components of signaling networks, in the genome of C. neoformans. We identified putative phosphatases based on annotation in C. neoformans var. grubii genome database provided by the Broad Institute and National Center for Biotechnology Information (NCBI) and performed a BLAST search of phosphatases of Saccharomyces cerevisiae, Aspergillus nidulans, Candida albicans and Fusarium graminearum to Cryptococcus neoformans. We classified putative phosphatases into 14 groups based on InterPro phosphatase domain annotation. Here, we constructed 170 signature-tagged gene-deletion strains through homologous recombination methods for 91 putative phosphatases. We examined their phenotypic traits under 30 different in vitro conditions, including growth, differentiation, stress response, antifungal resistance and virulence-factor production.

Keywords: human fungal pathogen, phosphatase, deletion library, functional genomics

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Authors: M. Abdoul-Hakim, A. Zeroual, H. Garmes

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In this work, the reaction of 2-chlorobenzimidazole with two distinct 1,3-dipoles such as benzonitrile N-oxide and an azomethine imine was carried out by DFT at the B3LYP/6-311+G(d, p) level to understand the effect of solvent (MeOH). The results show that MeOH has a significant effect on the evolution of the reaction. The charge transfer interactions n(O) → σ*(C-Cl), n(N)→σ*(C-Cl) and σ(N-C) →σ*(C-Cl) stabilize the transition states in an intramolecular nucleophilic substitution (SNi) step of the imidoyl group. Finally, this study provides a theoretical basis for the design of different polycyclic benzimidazole.

Keywords: azomethine imine, benzonitrile N-oxide, DFT, intramolecular nucleophilic substitution (SNi), polycyclic benzimidazole

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Authors: Azhan Azhar, Mohammed Sakib, Zaurez Ahmad

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The energy we receive from the sun is known as solar energy, and it is a reliable, long-lasting, eco-friendly and the most widely used energy source in the 21st century. It is. There are several techniques for harnessing solar energy, and we are all seeing large utility-scale projects to collect maximum amperes from the sun using current technologies. Solar PV is now on the rise as a means of harvesting energy from the sun. Moving a step further, our project is focused on designing an All-in-one portable Solar Energy based solution. We considered the minimum load conditions and evaluated the requirements of various devices utilized in this study to resolve the power requirements of small stores, hawkers, or travelers.

Keywords: DOD-depth of discharge, pulse width modulation charge controller, renewable energy, solar PV- solar photovoltaic

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Authors: Rowan Moore, Kai Scheffler, Eugen Damoc, Jennifer Sutton, Aaron Bailey, Stephane Houel, Simon Cubbon, Jonathan Josephs

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Purpose: MS analysis of monoclonal antibodies (mAbs) at the protein and peptide levels is critical during development and production of biopharmaceuticals. The compositions of current generation therapeutic proteins are often complex due to various modifications which may affect efficacy. Intact proteins analyzed by MS are detected in higher charge states that also provide more complexity in mass spectra. Protein analysis in native or native-like conditions with zero or minimal organic solvent and neutral or weakly acidic pH decreases charge state value resulting in mAb detection at higher m/z ranges with more spatial resolution. Methods: Three commercially available mAbs were used for all experiments. Intact proteins were desalted online using size exclusion chromatography (SEC) or reversed phase chromatography coupled on-line with a mass spectrometer. For streamlined use of the LC- MS platform we used a single SEC column and alternately selected specific mobile phases to perform separations in either denaturing or native-like conditions: buffer A (20 % ACN, 0.1 % FA) with Buffer B (100 mM ammonium acetate). For peptide analysis mAbs were proteolytically digested with and without prior reduction and alkylation. The mass spectrometer used for all experiments was a commercially available Thermo Scientific™ hybrid Quadrupole-Orbitrap™ mass spectrometer, equipped with the new BioPharma option which includes a new High Mass Range (HMR) mode that allows for improved high mass transmission and mass detection up to 8000 m/z. Results: We have analyzed the profiles of three mAbs under reducing and native conditions by direct infusion with offline desalting and with on-line desalting via size exclusion and reversed phase type columns. The presence of high salt under denaturing conditions was found to influence the observed charge state envelope and impact mass accuracy after spectral deconvolution. The significantly lower charge states observed under native conditions improves the spatial resolution of protein signals and has significant benefits for the analysis of antibody mixtures, e.g. lysine variants, degradants or sequence variants. This type of analysis requires the detection of masses beyond the standard mass range ranging up to 6000 m/z requiring the extended capabilities available in the new HMR mode. We have compared each antibody sample that was analyzed individually with mixtures in various relative concentrations. For this type of analysis, we observed that apparent native structures persist and ESI is benefited by the addition of low amounts of acetonitrile and formic acid in combination with the ammonium acetate-buffered mobile phase. For analyses on the peptide level we analyzed reduced/alkylated, and non-reduced proteolytic digests of the individual antibodies separated via reversed phase chromatography aiming to retrieve as much information as possible regarding sequence coverage, disulfide bridges, post-translational modifications such as various glycans, sequence variants, and their relative quantification. All data acquired were submitted to a single software package for analysis aiming to obtain a complete picture of the molecules analyzed. Here we demonstrate the capabilities of the mass spectrometer to fully characterize homogeneous and heterogeneous therapeutic proteins on one single platform. Conclusion: Full characterization of heterogeneous intact protein mixtures by improved mass separation on a quadrupole-Orbitrap™ mass spectrometer with extended capabilities has been demonstrated.

Keywords: disulfide bond analysis, intact analysis, native analysis, mass spectrometry, monoclonal antibodies, peptide mapping, post-translational modifications, sequence variants, size exclusion chromatography, therapeutic protein analysis, UHPLC

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Authors: Xiaoyu Shen, Fang Fang, Chujun Qiu

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Herewith we present a Fourier method for credit risk quantification and allocation in the factor-copula model framework. The key insight is that, compared to directly computing the cumulative distribution function of the portfolio loss via Monte Carlo simulation, it is, in fact, more efficient to calculate the transformation of the distribution function in the Fourier domain instead and inverting back to the real domain can be done in just one step and semi-analytically, thanks to the popular COS method (with some adjustments). We also show that the Euler risk allocation problem can be solved in the same way since it can be transformed into the problem of evaluating a conditional cumulative distribution function. Once the conditional or unconditional cumulative distribution function is known, one can easily calculate various risk metrics. The proposed method not only fills the niche in literature, to the best of our knowledge, of accurate numerical methods for risk allocation but may also serve as a much faster alternative to the Monte Carlo simulation method for risk quantification in general. It can cope with various factor-copula model choices, which we demonstrate via examples of a two-factor Gaussian copula and a two-factor Gaussian-t hybrid copula. The fast error convergence is proved mathematically and then verified by numerical experiments, in which Value-at-Risk, Expected Shortfall, and conditional Expected Shortfall are taken as examples of commonly used risk metrics. The calculation speed and accuracy are tested to be significantly superior to the MC simulation for real-sized portfolios. The computational complexity is, by design, primarily driven by the number of factors instead of the number of obligors, as in the case of Monte Carlo simulation. The limitation of this method lies in the "curse of dimension" that is intrinsic to multi-dimensional numerical integration, which, however, can be relaxed with the help of dimension reduction techniques and/or parallel computing, as we will demonstrate in a separate paper. The potential application of this method has a wide range: from credit derivatives pricing to economic capital calculation of the banking book, default risk charge and incremental risk charge computation of the trading book, and even to other risk types than credit risk.

Keywords: credit portfolio, risk allocation, factor copula model, the COS method, Fourier method

Procedia PDF Downloads 118