Search results for: equilibrium and kinetics

Authors: Hristina Šalipur, Jasmina Dostanić, Davor Lončarević, Matej Huš

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Photocatalytic water splitting/alcohol photoreforming has been used for the conversion of sunlight energy in the process of hydrogen production due to its sustainability, environmental safety, effectiveness and simplicity. Titanate nanotubes are frequently studied materials since they combine the properties of photo-active semiconductors with the properties of layered titanates, such as the ion-exchange ability. Platinum (Pt) doping into titanate structure has been considered an effective strategy in better separation efficiency of electron-hole pairs and lowering the overpotential for hydrogen production, which results in higher photocatalytic activity. In our work, Pt doped titanate catalysts were synthesized via simple alkaline hydrothermal treatment, incipient wetness impregnation method and temperature-programmed reduction. The structural, morphological and optical properties of the prepared catalysts were investigated using various characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, and diffuse reflectance spectroscopy (DRS). The activities of the prepared Pt-doped titanate photocatalysts were tested for hydrogen production via photocatalytic water splitting/alcohol photoreforming process under simulated solar light irradiation. Characterization of synthesized Pt doped titanate catalysts showed crystalline anatase phase, preserved nanotubular structure and high specific surface area. The result showed enhancement of activity in photocatalytic water splitting/alcohol photoreforming in the following order 2-butanol>1-butanol>tert-butanol, with obtained maximal hydrogen production rate of 7.5, 5.3 and 2 mmol g-1 h-1, respectively. Different possible factors influencing the hole scavenging ability, such as hole scavenger redox potential and diffusivity, adsorption and desorption rate of the hole scavenger on the surface and stability of the alcohol radical species generated via hole scavenging, were investigated. The theoretical evaluation using density functional theory (DFT) further elucidated the reaction kinetics and detailed mechanism of photocatalytic water splitting/alcohol photoreforming.

Keywords: hydrogen production, platinum, semiconductor, water splitting, density functional theory

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Authors: Sellidj Abdelaziz, Lebaili Soltane

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A cobalt-based alloy type Co-Cr-Ni-WC was deposited by plasma transferred arc projection (PTA) on a stainless steel valve. The alloy is characterized at the equilibrium by a solid solution Co (γ) mainly dendritic, and eutectic carbides M₇C₃ and ηM₆C. At the deposit/substrate interface, this microstructure is modified by the fast cooling mode of the alloy when applied in the liquid state on the relatively cold steel substrate. The structure formed in this case is heterogeneous and metastable phases can occur and evolve over temperature service. Coating properties and reliability are directly related to microstructures formed during deposition. We were interested more particularly in this microstructure formed during the solidification of the deposit in the region of the interface joining the soldered couple and its evolution during cyclic heat treatments at temperatures similar to those of the thermal environment of the valve. The characterization was carried out by SEM-EDS microprobe CAMECA, XRD, and micro hardness profiles. The deposit obtained has a linear and regular appearance that is free of cracks and with little porosity. The morphology of the microstructure represents solidification stages that are relatively fast with a temperature gradient high at the beginning of the interface by forming a plane front solid solution Co (γ). It gradually changes with the decreasing temperature gradient by getting farther from the junction towards the outer limit of the deposit. The matrix takes the forms: cellular, mixed (cells and dendrites) and dendritic. Dendritic growth is done according to primary ramifications in the direction of the heat removal which takes place in the direction perpendicular to the interface, towards the external surface of the deposit, following secondary and tertiary undeveloped arms. The eutectic carbides M₇C₃ and ηM₆C formed are very thin and are located in the intercellular and interdendritic spaces of the solid solution Co (γ).

Keywords: Co-Ni-Cr-W-C alloy, solid deposit, microstructure, carbides, cyclic heat treatment

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Authors: Jiahui Song

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The use of electric fields with high intensity (~ 100kV/cm or higher) and ultra short pulse durations (nanosecond range) has been a recent development. Most of the studies of electroporation have ignored possible thermal effects because of the small duration of the applied voltage pulses. However, it has been predicted membrane temperature gradients ranging from 0.2×109 to 109 K/m. This research focuses on thermal effects that drive for electroporative enhancements, even though the actual temperature values might not have changed appreciably from their equilibrium levels. The dynamics of pore formation with the application of an externally applied electric field is studied on the basis of molecular dynamics (MD) simulations using the GROMACS package. MD simulations of a lipid layer with constant electric field strength of 0.5 V/nm at 25 °C and 47 °C are implemented to simulate the appropriate thermal effects. The GROMACS provides the force fields for the lipid membranes, which is taken to comprise of dipalmitoyl-phosphatidyl-choline (DPPC) molecules. The water model mimicks the aqueous environment surrounding the membrane. Velocities of water and membrane molecules are generated randomly at each simulation run according to a Maxwellian distribution. The high background electric field is typically used in MD simulations to probe electroporation. It serves as an accelerated test of the pore formation process since low electric fields would take inordinately long simulation time. MD simulation shows no pore is formed in a 1-ns snapshot for a DPPC membrane set at a temperature of 25°C after a 0.5 V/nm electric field is applied. A nano-sized pore is clearly seen in a 0.75-ns snapshot on the same geometry, but with the membrane surfaces kept at temperatures of 47°C. And the pore increases at 1 ns. The MD simulation results suggest the possibility that the increase in temperature can result in different degrees of electrically stimulated bio-effects. The results points to the role of thermal effects in facilitating and accelerating the electroporation process.

Keywords: high-intensity, ultra-short, electroporation, thermal effects, molecular dynamics

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Authors: Navpreet Kaur, Himkusha Thakur, Nirmal Prabhakar

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One of the most publicized and controversial issue in crop production is the use of agrichemicals- also known as pesticides. This is evident in many reports that Organophosphate (OP) insecticides, among the broad range of pesticides are mainly involved in acute and chronic poisoning cases. Therefore, detection of OPs is very necessary for health protection, food and environmental safety. In our study, a nanocomposite of poly (3,4 ethylenedioxythiophene) (PEDOT) and multi-walled carbon nanotubes (MWCNTs) has been deposited electrochemically onto the surface of fluorine doped tin oxide sheets (FTO) for the analysis of malathion OP. The -COOH functionalization of MWCNTs has been done for the covalent binding with amino groups of AChE enzyme. The use of PEDOT-MWCNT films exhibited an excellent conductivity, enables fast transfer kinetics and provided a favourable biocompatible microenvironment for AChE, for the significant malathion OP detection. The prepared PEDOT-MWCNT/FTO and AChE/PEDOT-MWCNT/FTO nano-biosensors were characterized by Fourier transform infrared spectrometry (FTIR), Field emission-scanning electron microscopy (FE-SEM) and electrochemical studies. Electrochemical studies were done using Cyclic Voltammetry (CV) or Differential Pulse Voltammetry (DPV) and Electrochemical Impedance Spectroscopy (EIS). Various optimization studies were done for different parameters including pH (7.5), AChE concentration (50 mU), substrate concentration (0.3 mM) and inhibition time (10 min). The detection limit for malathion OP was calculated to be 1 fM within the linear range 1 fM to 1 µM. The activity of inhibited AChE enzyme was restored to 98% of its original value by 2-pyridine aldoxime methiodide (2-PAM) (5 mM) treatment for 11 min. The oxime 2-PAM is able to remove malathion from the active site of AChE by means of trans-esterification reaction. The storage stability and reusability of the prepared nano-biosensor is observed to be 30 days and seven times, respectively. The application of the developed nano-biosensor has also been evaluated for spiked lettuce sample. Recoveries of malathion from the spiked lettuce sample ranged between 96-98%. The low detection limit obtained by the developed nano-biosensor made them reliable, sensitive and a low cost process.

Keywords: PEDOT-MWCNT, malathion, organophosphates, acetylcholinesterase, nano-biosensor, oxime (2-PAM)

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Authors: Mateen A Khan, Taj Mohammad, Md. Imtaiyaz Hassan

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Alzheimer’s disease is characterized by the accumulation of the processing products of the amyloid beta peptide cleaved by amyloid precursor protein (APP). Iron increases the synthesis of amyloid beta peptides, which is why iron is present in Alzheimer's disease patients' amyloid plaques. Iron misregulation in the brain is linked to the overexpression of APP protein, which is directly related to amyloid-β aggregation in Alzheimer’s disease. The APP 5'-UTR region encodes a functional iron-responsive element (IRE) stem-loop that represents a potential target for modulating amyloid production. Targeted regulation of APP gene expression through the modulation of 5’-UTR sequence function represents a novel approach for the potential treatment of AD because altering APP translation can be used to improve both the protective brain iron balance and provide anti-amyloid efficacy. The molecular docking analysis of APP IRE RNA with eukaryotic translation initiation factors yields several models exhibiting substantial binding affinity. The finding revealed that the interaction involved a set of functionally active residues within the binding sites of eIF4F. Notably, APP IRE RNA and eIF4F interaction were stabilized by multiple hydrogen bonds with residues of APP IRE RNA and eIF4F. It was evident that APP IRE RNA exhibited a structural complementarity that tightly fit within binding pockets of eIF4F. The simulation studies further revealed the stability of the complexes formed between RNA and eIF4F, which is crucial for assessing the strength of these interactions and subsequent roles in the pathophysiology of Alzheimer’s disease. In addition, MD simulations would capture conformational changes in the IRE RNA and protein molecules during their interactions, illustrating the mechanism of interaction, conformational change, and unbinding events and how it may affect aggregation propensity and subsequent therapeutic implications. Our binding studies correlated well with the translation efficiency of APP mRNA. Overall, the outcome of this study suggests that the genomic modification and/or inhibiting the expression of amyloid protein by targeting APP IRE RNA can be a viable strategy to identify potential therapeutic targets for AD and subsequently be exploited for developing novel therapeutic approaches.

Keywords: Alzheimer's disease, Protein-RNA interaction analysis, molecular docking simulations, conformational dynamics, binding stability, binding kinetics, protein synthesis.

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Authors: Pardeep, Yugandhar Bitla, A. K. Patra, G. A. Basheed

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The topological protected nanosized particle-like swirling spin textures, “skyrmion,” has been observed in various ferromagnets with chiral crystal structures like MnSi, FeGe, Cu₂OSeO₃ alloys, however the magnetic ordering in these systems takes place at very low temperatures. For skyrmion-based spintronics devices, the skyrmion phase is required to stabilize in a wide temperature – field (T - H) region. The equilibrium skyrmion phase (SkX) in Co₇Zn₇Mn₆ alloy exists in a narrow T – H region just below transition temperature (TC ~ 215 K) and can be quenched by field cooling as a metastable skyrmion phase (MSkX) below SkX region. To realize robust MSkX at 110 K, field sweep ac susceptibility χ(H) measurements were performed after the zero field cooling (ZFC) and field cooling (FC) process. In ZFC process, the sample was cooled from 320 K to 110 K in zero applied magnetic field and then field sweep measurement was performed (up to 2 T) in positive direction (black curve). The real part of ac susceptibility (χ′(H)) at 110 K in positive field direction after ZFC confirms helical to conical phase transition at low field HC₁ (= 42 mT) and conical to ferromagnetic (FM) transition at higher field HC₂ (= 300 mT). After ZFC, FC measurements were performed i.e., sample was initially cooled in zero fields from 320 to 206 K and then a sample was field cooled in the presence of 15 mT field down to the temperature 110 K. After FC process, isothermal χ(H) was measured in positive (+H, red curve) and negative (-H, blue curve) field direction with increasing and decreasing field upto 2 T. Hysteresis behavior in χ′(H), measured after ZFC and FC process, indicates the stabilization of MSkX at 110 K which is in close agreement with literature. Also, the asymmetry between field-increasing curves measured after FC process in both sides confirm the stabilization of MSkX. In the returning process from the high field polarized FM state, helical state below HC₁ is destroyed and only the conical state is observed. Thus, the robust MSkX state is stabilized below its SkX phase over a much wider T - H region by FC in polycrystalline Co₇Zn₇Mn₆ alloy.

Keywords: skyrmions, magnetic susceptibility, metastable phases, topological phases

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Authors: Stefan Andersson, Balram Panjwani, Bernd Wittgens, Jan Erik Olsen

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Polycyclic Aromatic hydrocarbons are organic compounds consisting of only hydrogen and carbon aromatic rings. PAH are neutral, non-polar molecules that are produced due to incomplete combustion of organic matter. These compounds are carcinogenic and interact with biological nucleophiles to inhibit the normal metabolic functions of the cells. Norways, the most important sources of PAH pollution is considered to be aluminum plants, the metallurgical industry, offshore oil activity, transport, and wood burning. Stricter governmental regulations regarding emissions to the outer and internal environment combined with increased awareness of the potential health effects have motivated Norwegian metal industries to increase their efforts to reduce emissions considerably. One of the objective of the ongoing industry and Norwegian research council supported "SCORE" project is to reduce potential PAH emissions from an off gas stream of a ferroalloy furnace through controlled combustion. In a dedicated combustion chamber. The sizing and configuration of the combustion chamber depends on the combined properties of the bulk gas stream and the properties of the PAH itself. In order to achieve efficient and complete combustion the residence time and minimum temperature need to be optimized. For this design approach reliable kinetic data of the individual PAH-species and/or groups thereof are necessary. However, kinetic data on the combustion of PAH are difficult to obtain and there is only a limited number of studies. The paper presents an evaluation of the kinetic data for some of the PAH obtained from literature. In the present study, the oxidation is modelled for pure PAH and also for PAH mixed with process gas. Using a perfectly stirred reactor modelling approach the oxidation is modelled including advanced reaction kinetics to study influence of residence time and temperature on the conversion of PAH to CO2 and water. A Chemical Reactor Network (CRN) approach is developed to understand the oxidation of PAH inside the combustion chamber. Chemical reactor network modeling has been found to be a valuable tool in the evaluation of oxidation behavior of PAH under various conditions.

Keywords: PAH, PSR, energy recovery, ferro alloy furnace

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Authors: Renzhi Qi, Zhaoping Zhong

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Under the dual pressure of the global energy crisis and environmental pollution, avoiding the consumption of non-renewable fossil fuels based on carbon as the energy carrier and developing and utilizing non-carbon energy carriers are the basic requirements for the future new energy economy. Electrocatalyst for water splitting plays an important role in building sustainable and environmentally friendly energy conversion. The oxygen evolution reaction (OER) is essentially limited by the slow kinetics of multi-step proton-electron transfer, which limits the efficiency and cost of water splitting. In this work, CeO₂@NiCo-NRGO/NF hybrid materials were prepared using nickel foam (NF) and nitrogen-doped reduced graphene oxide (NRGO) as conductive substrates by multi-step hydrothermal method and were used as highly efficient catalysts for OER. The well-connected nanosheet array forms a three-dimensional (3D) network on the substrate, providing a large electrochemical surface area with abundant catalytic active sites. The doping of CeO₂ in NiCo-NRGO/NF electrocatalysts promotes the dispersion of substances and its synergistic effect in promoting the activation of reactants, which is crucial for improving its catalytic performance against OER. The results indicate that CeO₂@NiCo-NRGO/NF only requires a lower overpotential of 250 mV to drive the current density of 10 mA cm-2 for an OER reaction of 1 M KOH, and exhibits excellent stability at this current density for more than 10 hours. The double layer capacitance (Cdl) values show that CeO₂@NiCo-NRGO/NF significantly affects the interfacial conductivity and electrochemically active surface area. The hybrid structure could promote the catalytic performance of oxygen evolution reaction, such as low initial potential, high electrical activity, and excellent long-term durability. The strategy for improving the catalytic activity of NiCo-LDH can be used to develop a variety of other electrocatalysts for water splitting.

Keywords: CeO₂, reduced graphene oxide, NiCo-layered double hydroxide, oxygen evolution reaction

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Authors: Diogo Pereira, Maria Moura, Joana Campos, João Nunes

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As the Ukraine war highlights the European Economic Area’s vulnerability and external dependence on feed and food, agriculture gains significant importance. Transformative change is necessary to reach a sustainable and resilient agricultural sector. Agriculture is an important drive for bioeconomy and the equilibrium and survival of society and rural fires resilience. The pressure of (1) water stress, (2) nutrient cycle, and (3) social demographic evolution towards 70% of the population in Urban systems and the aging of the rural population, combined with climate change, exacerbates the problem and paradigm of rural and wildfires, especially in Portugal. The Portuguese territory is characterized by (1) 28% of marginal land, (2) the soil quality of 70% of the territory not being appropriate for agricultural activity, (3) a micro smallholding, with less than 1 ha per proprietor, with mainly familiar and traditional agriculture in the North and Centre regions, and (4) having the most vulnerable areas for rural fires in these same regions. The most important difference between the South, North and Centre of Portugal, referring to rural and wildfires, is the agricultural activity, which has a higher level in the South. In Portugal, rural and wildfires represent an average annual economic loss of around 800 to 1000 million euros. The WinBio model is an agrienvironmental metabolism design, with the capacity to create a new agri-food metabolism through Agricultural Organized Areas, a privatepublic partnership. This partnership seeks to grow agricultural activity in regions with (1) abandoned territory, (2) micro smallholding, (3) water and nutrient management necessities, and (4) low agri-food literacy. It also aims to support planning and monitoring of resource use efficiency and sustainability of territories, using agriculture as a barrier for rural and wildfires in order to protect rural population.

Keywords: agricultural organized areas, residues, climate change, drought, nutrients, rural and wild fires

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Authors: Lucia Steenkamp, Chris V. D. Westhuyzen, Kgama Mathiba

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Ambergris, and more specifically its oxidation product (–)-ambrafuran, is a scarce, valuable, and sought-after perfumery ingredient. The material is used as a fixative agent to stabilise perfumes in formulations by reducing the evaporation rate of volatile substances. Ambergris is a metabolic product of the sperm whale (Physeter macrocephatus L.), resulting from intestinal irritation. Chemically, (–)-ambrafuran is produced from the natural product sclareol in eight synthetic steps – in the process using harsh and often toxic chemicals to do so. An overall yield of no more than 76% can be achieved in some routes, but generally, this is lower. A new 'green' route has been developed in our laboratory in which sclareol, extracted from the Clary sage plant, is converted to (–)-ambrafuran in two steps with an overall yield in excess of 80%. The first step uses a microorganism, Hyphozyma roseoniger, to bioconvert sclareol to an intermediate diol using substrate concentrations up to 50g/L. The yield varies between 90 and 67% depending on the substrate concentration used. The purity of the diol product is 95%, and the diol is used without further purification in the next step. The intermediate diol is then cyclodehydrated to the final product (–)-ambrafuran using a zeolite, which is not harmful to the environment and is readily recycled. The yield of the product is 96%, and following a single recrystallization, the purity of the product is > 99.5%. A preliminary LC-MS study of the bioconversion identified several intermediates produced in the fermentation broth under oxygen-restricted conditions. Initially, a short-lived ketone is produced in equilibrium with a more stable pyranol, a key intermediate in the process. The latter is oxidised under Norrish type I cleavage conditions to yield an acetate, which is hydrolysed either chemically or under lipase action to afford the primary fermentation product, an intermediate diol. All the intermediates identified point to the likely CYP450 action as the key enzyme(s) in the mechanism. This invention is an exceptional example of how the power of biocatalysis, combined with a mild, benign chemical step, can be deployed to replace a total chemical synthesis of a specific chiral antipode of a commercially relevant material.

Keywords: ambrafuran, biocatalysis, fragrance, microorganism

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Authors: B. Hammouti, H. Oudda, A. Benabdellah, A. Benayada, A. Aouniti

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Corrosion behaviour of carbon steel was studied in various concentrated HClO4 solutions. To explain the acid attack in relation of H+ activity, new sensor was realised: two carbon paste electrodes (CPE) were constructed by incorporating ferrocene (Fc) and orthoquinone into the carbon paste matrix and crossed by weak current to stabilize potential difference. The potentiometric method at imposed weak current between these two electrodes permits the in situ determination of both concentration and acidity level of various concentrated HClO4 solutions. The different factors affecting the potential at imposed current as current intensity, temperature and H+ ion concentration are studied. The potentials measured between ferrocene and chloranil electrodes are directly linked to the acid concentration. The acidity Ri(H) function defined represents the determination of the H+ activity and constitutes the extend of pH is concentrated acid solutions. Ri(H) has been determined and compared to Strehlow Ro(H), Janata HGF and Hammett Ho functions. The collected data permit to give a scale of strength of mineral concentrated acids at a given concentration. Ri(H) is numerically equal to the thermodynamic Ro(H), but deviated from Hammett functions based on indicator determination. The CPE electrode with inserted ferrocene in presence of ferricinium (Fc+) ion in concentrated HClO4 at various concentrations is realized without junction potential and may plays the role of a practical reference electrode (FRE) in concentrated acids. Fc+ was easily prepared in biphasic medium HClO4-acid by the quantitative oxidation of ferrocene by the ortho-chloranil (oQ). Potential of FRE is stable with time. The variation of equilibrium potential of the interface Fc/ Fc+ at various concentrations of Fc+ (10-4 - 2 10-2 M) obeyed to the Nernst equation with a slope 0.059 Volt per decade. Corrosion rates obtained by weight loss and electrochemical techniques were then easily linked to acidity level.

Keywords: ferrocene, strehlow, concentrated acid, corrosion, Generalised pH, sensor carbon paste electrode

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Authors: Ebuwa Osagie, Chet Biliyok, Yeung Hoi

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Regeneration energy requirement and ways to reduce it is the main aim of most CO2 capture researches currently being performed and thus, post-combustion carbon capture (PCC) option is identified to be the most suitable for the natural gas-fired power plants. From current research and development (R&D) activities worldwide, two main areas are being examined in order to reduce the regeneration energy requirement of amine-based PCC, namely: (a) development of new solvents with better overall performance than 30wt% monoethanolamine (MEA) aqueous solution, which is considered as the base-line solvent for solvent-based PCC, (b) Integration of the PCC Plant to the power plant. In scaling-up a PCC pilot plant to the size required for a commercial-scale natural gas-fired power plant, process modelling and simulation is very essential. In this work, an integrated process made up of a 482MWe natural gas-fired power plant, an MEA-based PCC plant which is developed and validated has been modelled and simulated. The PCC plant has four absorber columns and a single stripper column, the modelling and simulation was performed with Aspen Plus® V8.4. The gas turbine, the heat recovery steam generator and the steam cycle were modelled based on a 2010 US DOE report, while the MEA-based PCC plant was modelled as a rate-based process. The scaling of the amine plant was performed using a rate based calculation in preference to the equilibrium based approach for 90% CO2 capture. The power plant was integrated to the PCC plant in three ways: (i) flue gas stream from the power plant which is divided equally into four stream and each stream is fed into one of the four absorbers in the PCC plant. (ii) Steam draw-off from the IP/LP cross-over pipe in the steam cycle of the power plant used to regenerate solvent in the reboiler. (iii) Condensate returns from the reboiler to the power plant. The integration of a PCC plant to the NGCC plant resulted in a reduction of the power plant output by 73.56 MWe and the net efficiency of the integrated system is reduced by 7.3 % point efficiency. A secondary aim of this study is the parametric studies which have been performed to assess the impacts of natural gas on the overall performance of the integrated process and this is achieved through investigation of the capture efficiencies.

Keywords: natural gas-fired, power plant, MEA, CO2 capture, modelling, simulation

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Authors: Ons Triki, Fathi Abid

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Along with the increase in the use of leasing contracts in corporate finance, multiple studies aim to model the credit risk of the lease in order to cover the losses of the lessor of the asset if the lessee goes bankrupt. In the current research paper, a convertible lease contract is elaborated in a continuous time stochastic universe aiming to ensure the financial stability of the firm and quickly recover the losses of the counterparties to the lease in case of default. This work examines the term structure of the lease rates taking into account the credit default risk and the capital structure of the firm. The interaction between the lessee's capital structure and the equilibrium lease rate has been assessed by applying the competitive lease market argument developed by Grenadier (1996) and the endogenous structural default model set forward by Leland and Toft (1996). The cumulative probability of default was calculated by referring to Leland and Toft (1996) and Yildirim and Huan (2006). Additionally, the link between lessee credit risk and lease rate was addressed so as to explore the impact of convertible lease financing on the term structure of the lease rate, the optimal leverage ratio, the cumulative default probability, and the optimal firm value by applying an endogenous conversion threshold. The numerical analysis is suggestive that the duration structure of lease rates increases with the increase in the degree of the market price of risk. The maximal value of the firm decreases with the effect of the optimal leverage ratio. The results are indicative that the cumulative probability of default increases with the maturity of the lease contract if the volatility of the asset service flows is significant. Introducing the convertible lease contract will increase the optimal value of the firm as a function of asset volatility for a high initial service flow level and a conversion ratio close to 1.

Keywords: convertible lease contract, lease rate, credit-risk, capital structure, default probability

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Authors: Erwin San Juan Martinez, Miguel Angel Aguilar Mendez, Manuel Sandoval Villa, Libia Iris Trejo Tellez

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Some nanomaterials may improve the vegetal growth in certain concentration intervals, and could be used as nanofertilizers in order to increase crops yield, and decreasing the environmental pollution due to non-controlled use of conventional fertilizers, therefore the present investigation’s objective was to synthetize and characterize gelatin nanoparticles loaded with calcium generated through pulverization technique and be used as nanofertilizers. To obtain these materials, a fractional factorial design 27-4 was used in order to evaluate the largest number of factors (concentration of Ca2+, temperature and agitation time of the solution and calcium concentration, drying temperature, and % spray) with a possible effect on the size, distribution and morphology of nanoparticles. For the formation of nanoparticles, a Nano Spray-Dryer B - 90® (Buchi, Flawil, Switzerland), equipped with a spray cap of 4 µm was used. Size and morphology of the obtained nanoparticles were evaluated using a scanning electron microscope (JOEL JSM-6390LV model; Tokyo, Japan) equipped with an energy dispersive x-ray X (EDS) detector. The total quantification of Ca2+ as well as its release by the nanoparticles was carried out in an equipment of induction atomic emission spectroscopy coupled plasma (ICP-ES 725, Agilent, Mulgrave, Australia). Of the seven factors evaluated, only the concentration of fertilizer, % spray and concentration of polymer presented a statistically significant effect on particle size. Micrographs of SEM from six of the eight conditions evaluated in this research showed particles separated and with a good degree of sphericity, while in the other two particles had amorphous morphology and aggregation. In all treatments, most of the particles showed smooth surfaces. The average size of smallest particle obtained was 492 nm, while EDS results showed an even distribution of Ca2+ in the polymer matrix. The largest concentration of Ca2+ in ICP was 10.5%, which agrees with the theoretical value calculated, while the release kinetics showed an upward trend within 24 h. Using the technique employed in this research, it was possible to obtain nanoparticles loaded with calcium, of good size, sphericity and with release controlled properties. The characteristics of nanoparticles resulted from manipulation of the conditions of synthesis which allow control of the size and shape of the particles, and provides the means to adapt the properties of the materials to an specific application.

Keywords: calcium, controlled release, gelatin, nano spraydryer, nanofertilizer

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Authors: Marco Soto-Arriaza, Eduardo Cena-Ahumada, Jaime Melendez-Rojel

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Background: Liposomes have been widely used as a model of lipid bilayer to study the physicochemical properties of biological membrane, encapsulation, transport and release of different molecules. Furthermore, extensive research has focused on improving the efficiency in the transport of drugs, developing tools that improve the release of the encapsulated drug from liposomes. In this context, the enzymatic activity of PLA₂, despite having been shown to be an effective tool to promote the release of drugs from liposomes, is still an open field of research. Aim: The aim of the present study is to explore the effect of cholesterol (Cho) and amphipathic di- and tri-block copolymers, on calcein release mediated by enzymatic activity of PLA2 in Dipalmitoylphosphatidylcholine (DPPC) liposomes under physiological conditions. Methods: Different dispersions of DPPC, cholesterol, di-block POE₄₅-PCL₅₂ or tri-block PCL₁₂-POE₄₅-PCL₁₂ were prepared by the extrusion method after five freezing/thawing cycles; in Phosphate buffer 10mM pH 7.4 in presence of calcein. DPPC liposomes/Calcein were centrifuged at 15000rpm 10 min to separate free calcein. Enzymatic activity assays of PLA₂ were performed at 37°C using the TBS buffer pH 7.4. The size distribution, polydispersity, Z-potential and Calcein encapsulation of DPPC liposomes was monitored. Results: PLA₂ activity showed a slower kinetic of calcein release up to 20 mol% of cholesterol, evidencing a minimum at 10 mol% and then a maximum at 18 mol%. Regardless of the percentage of cholesterol, up to 18 mol% a one-hundred percentage release of calcein was observed. At higher cholesterol concentrations, PLA₂ showed to be inefficient or not to be involved in calcein release. In assays where copolymers were added in a concentration lower than their cmc, a similar behavior to those showed in the presence of Cho was observed, that is a slower kinetic in calcein release. In both experimental approaches, a one-hundred percentage of calcein release was observed. PLA₂ was shown to be sensitive to the 4-(4-Octadecylphenyl)-4-oxobutenoic acid inhibitor and calcium, reducing the release of calcein to 0%. Cell viability of HeLa cells decreased 7% in the presence of DPPC liposomes after 3 hours of incubation and 17% and 23% at 5 and 15 hours, respectively. Conclusion: Calcein release from DPPC liposomes, mediated by PLA₂ activity, depends on the percentage of cholesterol and the presence of copolymers. Both, cholesterol up to 20 mol% and copolymers below it cmc could be applied to the regulation of the kinetics of antitumoral drugs release without inducing cell toxicity per se.

Keywords: amphipathic copolymers, calcein release, cholesterol, DPPC liposome, phospholipase A₂

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Authors: Zahid Ullah, Atlas Khan

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This research endeavors to explore the regularity properties associated with a specific class of equations, namely extremely degenerate elliptic equations. These equations hold significance in understanding complex physical systems like porous media flow, with applications spanning various branches of mathematics. The focus is on unraveling and analyzing regularity results to gain insights into the smoothness of solutions for these highly degenerate equations. Elliptic equations, fundamental in expressing and understanding diverse physical phenomena through partial differential equations (PDEs), are particularly adept at modeling steady-state and equilibrium behaviors. However, within the realm of elliptic equations, the subset of extremely degenerate cases presents a level of complexity that challenges traditional analytical methods, necessitating a deeper exploration of mathematical theory. While elliptic equations are celebrated for their versatility in capturing smooth and continuous behaviors across different disciplines, the introduction of degeneracy adds a layer of intricacy. Extremely degenerate elliptic equations are characterized by coefficients approaching singular behavior, posing non-trivial challenges in establishing classical solutions. Still, the exploration of extremely degenerate cases remains uncharted territory, requiring a profound understanding of mathematical structures and their implications. The motivation behind this research lies in addressing gaps in the current understanding of regularity properties within solutions to extremely degenerate elliptic equations. The study of extreme degeneracy is prompted by its prevalence in real-world applications, where physical phenomena often exhibit characteristics defying conventional mathematical modeling. Whether examining porous media flow or highly anisotropic materials, comprehending the regularity of solutions becomes crucial. Through this research, the aim is to contribute not only to the theoretical foundations of mathematics but also to the practical applicability of mathematical models in diverse scientific fields.

Keywords: elliptic equations, extremely degenerate, regularity results, partial differential equations, mathematical modeling, porous media flow

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Authors: N. Azouaou, H. Mokaddem, D. Senadjki, K. Kedjit, Z. Sadaoui

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Introduction: Water contamination caused by dye industries, including food, leather, textile, plastic, cosmetics, paper-making, printing and dye synthesis, has caused more and more attention, since most dyes are harmful to human being and environments. Untreated coffee grounds were used as a high-efficiency adsorbent for the removal of a cationic dye (methylene blue, MB) from aqueous solution. Characterization of the adsorbent was performed using several techniques such as SEM, surface area (BET), FTIR and pH zero charge. The effects of contact time, adsorbent dose, initial solution pH and initial concentration were systematically investigated. Results showed the adsorption kinetics followed the pseudo-second-order kinetic model. Langmuir isotherm model is in good agreement with the experimental data as compared to Freundlich and D–R models. The maximum adsorption capacity was found equal to 52.63mg/g. In addition, the possible adsorption mechanism was also proposed based on the experimental results. Experimental: The adsorption experiments were carried out in batch at room temperature. A given mass of adsorbent was added to methylene blue (MB) solution and the entirety was agitated during a certain time. The samples were carried out at quite time intervals. The concentrations of MB left in supernatant solutions after different time intervals were determined using a UV–vis spectrophotometer. The amount of MB adsorbed per unit mass of coffee grounds (qt) and the dye removal efficiency (R %) were evaluated. Results and Discussion: Some chemical and physical characteristics of coffee grounds are presented and the morphological analysis of the adsorbent was also studied. Conclusions: The good capacity of untreated coffee grounds to remove MB from aqueous solution was demonstrated in this study, highlighting its potential for effluent treatment processes. The kinetic experiments show that the adsorption is rapid and maximum adsorption capacities qmax= 52.63mg/g achieved in 30min. The adsorption process is a function of the adsorbent concentration, pH and metal ion concentration. The optimal parameters found are adsorbent dose m=5g, pH=5 and ambient temperature. FTIR spectra showed that the principal functional sites taking part in the sorption process included carboxyl and hydroxyl groups.

Keywords: adsorption, methylene blue, coffee grounds, kinetic study

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Authors: Kailas L. Wasewar

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Biobutanol has been considered as a potential and alternative biofuel relative to the most popular biodiesel and bioethanol. End product toxicity is the major problems in commercialization of fermentation based process which can be reduce to some possible extent by removing biobutanol simultaneously. Several techniques have been investigated for removing butanol from fermentation broth such as stripping, adsorption, liquid–liquid extraction, pervaporation, and membrane solvent extraction. Liquid–liquid extraction can be performed with high selectivity and is possible to carry out inside the fermenter. Conventional solvents have few drawbacks including toxicity, loss of solvent, high cost etc. Hence alternative solvents must be explored for the same. Room temperature ionic liquids (RTILs) composed entirely of ions are liquid at room temperature having negligible vapor pressure, non-flammability, and tunable physiochemical properties for a particular application which term them as “designer solvents”. Ionic liquids (ILs) have recently gained much attention as alternatives for organic solvents in many processes. In particular, ILs have been used as alternative solvents for liquid–liquid extraction. Their negligible vapor pressure allows the extracted products to be separated from ILs by conventional low pressure distillation with the potential for saving energy. Morpholinium, imidazolium, ammonium, phosphonium etc. based ionic liquids have been employed for the separation biobutanol. In present chapter, basic concepts of ionic liquids and application in separation have been presented. Further, type of ionic liquids including, conventional, functionalized, polymeric, supported membrane, and other ionic liquids have been explored. Also the effect of various performance parameters on separation of biobutanol by ionic liquids have been discussed and compared for different cation and anion based ionic liquids. The typical methodology for investigation have been adopted such as contacting the equal amount of biobutanol and ionic liquids for a specific time say, 30 minutes to confirm the equilibrium. Further, biobutanol phase were analyzed using GC to know the concentration of biobutanol and material balance were used to find the concentration in ionic liquid.

Keywords: biobutanol, separation, ionic liquids, sustainability, biorefinery, waste biomass

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Authors: Montree Bunruanses, Preecha Yupapin

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In this work, the quantum material called Amrita (elixir) is made from top-down gold into nanometer particles by fusing 99% gold with a laser and mixing it with drinking water using the atmospheric water (AWG) production system, which is made of water with air. The high energy laser power destroyed the four natural force bindings from gravity-weak-electromagnetic and strong coupling forces, where finally it was the purified Bose-Einstein condensate (BEC) states. With this method, gold atoms in the form of spherical single crystals with a diameter of 30-50 nanometers are obtained and used. They were modulated (activated) with a frequency generator into various matrix structures mixed with AWG water to be used in the upstream conversion (quantum reversible) process, which can be applied on humans both internally or externally by drinking or applying on the treated surfaces. Doing both space (body) and time (mind) will go back to the origin and start again from the coupling of space-time on both sides of time at fusion (strong coupling force) and push out (Big Bang) at the equilibrium point (singularity) occurs as strings and DNA with neutrinos as coupling energy. There is no distortion (purification), which is the point where time and space have not yet been determined, and there is infinite energy. Therefore, the upstream conversion is performed. It is reforming DNA to make it be purified. The use of Amrita is a method used for people who cannot meditate (quantum meditation). Various cases were applied, where the results show that the Amrita can make the body and the mind return to their pure origins and begin the downstream process with the Big Bang movement, quantum communication in all dimensions, DNA reformation, frequency filtering, crystal body forming, broadband quantum communication networks, black hole forming, quantum consciousness, body and mind healing, etc.

Keywords: quantum materials, quantum meditation, quantum reversible, Bose-Einstein condensate

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Authors: Jason Clarke, Michaela Porubanova, Angela Mazzoli, Gulsah Kut

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What accounts for our perception that time inexorably passes in one direction, from the past to the future, the so-called arrow of time, given that the laws of physics permit motion in one temporal direction to also happen in the reverse temporal direction? Modern physics says that the reason for time’s unidirectional physical arrow is the relationship between time and entropy, the degree of disorder in the universe, which is evolving from low entropy (high order; thermal disequilibrium) toward high entropy (high disorder; thermal equilibrium), the second law of thermodynamics. Accordingly, our perception of the direction of time, from past to future, is believed to emanate as a result of the natural evolution of entropy from low to high, with low entropy defining our notion of ‘before’ and high entropy defining our notion of ‘after’. Here we explored this proposed relationship between entropy and the perception of time’s arrow. We predicted that if the brain has some mechanism for detecting entropy, whose output feeds into processes involved in constructing our perception of the direction of time, presentation of violations to the expectation that low entropy defines ‘before’ and high entropy defines ‘after’ would alert this mechanism, leading to measurable behavioral effects, namely a disruption in duration perception. To test this hypothesis, participants were shown briefly-presented (1000 ms or 500 ms) computer-generated visual dynamic events: novel 3D shapes that were seen either to evolve from whole figures into parts (low to high entropy condition) or were seen in the reverse direction: parts that coalesced into whole figures (high to low entropy condition). On each trial, participants were instructed to reproduce the duration of their visual experience of the stimulus by pressing and releasing the space bar. To ensure that attention was being deployed to the stimuli, a secondary task was to report the direction of the visual event (forward or reverse motion). Participants completed 60 trials. As predicted, we found that duration reproduction was significantly longer for the high to low entropy condition compared to the low to high entropy condition (p=.03). This preliminary data suggests the presence of a neural mechanism that detects entropy, which is used by other processes to construct our perception of the direction of time or time’s arrow.

Keywords: time perception, entropy, temporal illusions, duration perception

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Authors: Samuel Abebe Ebebo

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Scale precipitation causes a major issue for geothermal power plants because it reduces the production rate of geothermal energy. Each geothermal power plant's different chemical and physical conditions can cause the scale to precipitate under a particular set of fluid-rock interactions. Depending on the mineral, it is possible to have scale in the production well, steam separators, heat exchangers, reinjection wells, and everywhere in between. The scale consists mainly of smectite and trace amounts of chlorite, magnetite, quartz, hematite, dolomite, aragonite, and amorphous silica. The smectite scale is one of the difficult scales at injection wells in geothermal power plants. X-ray diffraction and chemical composition identify this smectite as Stevensite. The characteristics and the scale of each injection well line are different depending on the fluid chemistry. The smectite scale has been widely distributed in pipelines and surface plants. Mineral water equilibrium showed that the main factors controlling the saturation indices of smectite increased pH and dissolved Mg concentration due to the precipitate on the equipment surface. This study aims to characterize the scales and geothermal fluids collected from the Onuma geothermal power plant in Akita Prefecture, Japan. Field tests were conducted on October 30–November 3, 2021, at Onuma to determine the pH control methods for preventing magnesium silicate scaling, and as exemplified, the formation of magnesium silicate hydrates (M-S-H) with MgO to SiO2 ratios of 1.0 and pH values of 10 for one day has been studied at 25 °C. As a result, M-S-H scale formation could be suppressed, and stevensite formation could also be suppressed when we can decrease the pH of the fluid by less than 8.1, 7.4, and 8 (at 97 °C) in the fluid from O-3Rb and O-6Rb, O-10Rg, and O-12R, respectively. In this context, the scales and fluids collected from injection wells at a geothermal power plant in Japan were analyzed and characterized to understand the formation conditions of Mg-silicate scales with on-site synthesis experiments. From the results of the characterizations and on-site synthesis experiments, the inhibition method of their scale formation is discussed based on geochemical modeling in this study.

Keywords: magnesium silicate, scaling, inhibitor, geothermal power plant

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Authors: Joulié Aurélien, Jourdain Elsa, Bailly Xavier, Gasqui Patrick, Yang Elise, Leblond Agnès, Rousset Elodie, Sidi-Boumedine Karim

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Q fever is a worldwide zoonosis caused by the gram-negative obligate intracellular bacterium Coxiella burnetii. Following the recent outbreaks in the Netherlands, a hyper virulent clone was found to be the cause of severe human cases of Q fever. In livestock, Q fever clinical manifestations are mainly abortions. Although the abortion rates differ between ruminant species, C. burnetii’s virulence remains understudied, especially in enzootic areas. In this study, the infectious potential of three C. burnetii isolates collected from French farms of small ruminants were compared to the reference strain Nine Mile (in phase II and in an intermediate phase) using an in vivo (CD1 mice) model. Mice were challenged with 105 live bacteria discriminated by propidium monoazide-qPCR targeting the icd-gene. After footpad inoculation, spleen and popliteal lymph node were harvested at 10 days post-inoculation (p.i). The strain invasiveness in spleen and popliteal nodes was assessed by qPCR assays targeting the icd-gene. Preliminary results showed that the avirulent strains (in phase 2) failed to pass the popliteal barrier and then to colonize the spleen. This model allowed a significant differentiation between strain’s invasiveness on biological host and therefore identifying distinct virulence profiles. In view of these results, we plan to go further by testing fifteen additional C. burnetii isolates from French farms of sheep, goat and cattle by using the above-mentioned in vivo model. All 15 strains display distant MLVA (multiple-locus variable-number of tandem repeat analysis) genotypic profiles. Five of the fifteen isolates will bee also tested in vitro on ovine and bovine macrophage cells. Cells and supernatants will be harvested at day1, day2, day3 and day6 p.i to assess in vitro multiplication kinetics of strains. In conclusion, our findings might help the implementation of surveillance of virulent strains and ultimately allow adapting prophylaxis measures in livestock farms.

Keywords: Q fever, invasiveness, ruminant, virulence

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Authors: Mehrzad Soltani, Pegah Rezaei

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In response to the escalating challenges posed by resource scarcity, urban congestion, and the dearth of green spaces, contemporary urban areas have undergone a remarkable transformation into smart cities. This evolution necessitates a strategic and forward-thinking approach to urban development, with the primary objective of diminishing and eventually eradicating dependence on non-renewable energy sources. This steadfast commitment to sustainable development is geared toward the continual enhancement of our global urban milieu, ensuring a healthier and more prosperous environment for forthcoming generations. This transformative vision has been meticulously shaped by an extensive research framework, incorporating in-depth field studies and investigations conducted at both neighborhood and city levels. Our holistic strategy extends its purview to encompass major cities and states, advocating for the realization of exceptional development firmly rooted in the principles of sustainable intelligence. At its core, this approach places a paramount emphasis on stringent pollution control measures, concurrently safeguarding ecological equilibrium and regional cohesion. Central to the realization of this vision is the widespread adoption of environmentally friendly materials and components, championing the cultivation of plant life and harmonious green spaces, and the seamless integration of intelligent lighting and irrigation systems. These systems, including solar panels and solar energy utilization, are deployed wherever feasible, effectively meeting the essential lighting and irrigation needs of these dynamic urban ecosystems. Overall, the transformation of urban areas into smart cities necessitates a holistic and innovative approach to urban development. By actively embracing sustainable intelligence and adhering to strict environmental standards, these cities pave the way for a brighter and more sustainable future, one that is marked by resilient, thriving, and eco-conscious urban communities.

Keywords: smart city, green urban, sustainability, urban management

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Authors: Aravind Kumar

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The high terrains of Garhwal (Uttarakhand) Himalaya are the niches of a number of rare and endemic plant species of great therapeutic importance. However, the wild flora of the area is still under a constant threat due to rapid upsurge in human interferences, especially through multifarious tourism growth and peri-urban encroachments. After getting the status of a ‘Special State’ of the country since its inception in the year 2000, this newly borne State led to very rapid infrastructural growth and development. Consequently, its townships started expanding in an unmanaged way grabbing nearby agricultural lands and forest areas into peri-urban landscapes. Simultaneously, a boom in tourism and pilgrimage in the state and the infrastructural facilities raised by the government for tourists/pilgrims are destroying its biodiversity. Field survey revealed 242 plant species of therapeutic significance naturally growing in the area and being utilized by local inhabitants as traditional medicines. On conservation scale, 6 species (2.2%) were identified as critically endangered, 19 species (7.1%) as the endangered ones, 8 species (3.0%) under rare category, 17 species (6.4%) as threatened and 14 species (5.2%) as vulnerable. The Government of India has brought mega-biodiversity hot spots of the state under Biosphere Reserve, National Parks, etc. restricting all kinds of human interferences; however, the two most sacred shrines of Hindus and Sikhs viz. Shri Badrinath and Shri Hemkunt Sahib, and two great touristic attractions viz. Valley of Flowers and Auli-Joshimath Skiing Track oblige the government to maintain equilibrium between entries of visitors vis-à-vis biodiversity conservation in high terrains of Uttarakhand Himalaya.

Keywords: biodiversity conservation, ethno-botany, Garhwal (Uttarakhand) Himalaya, peri-urban encroachment, pilgrimage and tourism

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Authors: Mohammad Ehsani, Elham Karimi, Hashem Koozechian

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Aim: The purpose of current semi-experimental study was a survey on effect of 16 week walking on psychosocial function related quality of life among 60 to 75 years old men. Methodology: For this reason, short from of health – related quality of life questionnaire (SF – 36) and Geriatric Depression Scale (GDS) had been distributed to the subjects at 2 times of pre – test and posttest. Statistical sample of current study was 60 to 75 years old men who placed at Kahrizak house and assessed by considering physically and medical background. Also factors of entrance to the intervention like age range, have satisfaction and have intent to participating in walking program, lack of having diabetic, cardiovascular, Parkinsonism diseases and postural, neurological, musculoskeletal disorders, lack of having clinical background like visual disorders or disordering on equilibrium system, lack of motor limitation, foot print disorders, having surgery and mental health had been determined and assessed. Finally after primary studies, 80 persons selected and categorized accidentally to the 3 experimental group (1, 2, 3 sessions per week, 30 min walking with moderate intension at every sessions) and one control group (without physical activity in period of 16 weeks). Data analysed by employing ANOVA, Pearson coefficient and Scheffe Post – Hoc tests at the significance level of p < 0.05. Results: Results showed that psychosocial function of men with 60 to 75 years old increase by influence of 16 week walking and increase of exercise sessions lead to more effectiveness of walking. Also there was no significant difference between psychosocial function of subjects within 1 session and 3 sessions experimental groups (p > 0.05). Conclusion: On the basis of results, we can say that doing regular walking with efficient and standard dosage for elderly people, can increase their quality of life. Furthermore, designing and action operation regular walking program for elderly men on the basis of special, logical and systematic pattern under the supervision of aware coaches have been recommended on the basis of results.

Keywords: walking, quality of life, psychosocial function, elders

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Authors: Katarzyna Falkowicz

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The work focused on the original concept of a thin-walled plate element with a cut-out, for use as a spring or load-bearing element. The subject of the study were rectangular plates with a cut-out with variable geometrical parameters and with a variable angle of fiber arrangement, made of a carbon-epoxy composite with high strength properties in an asymmetrical arrangement, subjected to uniform compression. The influence of geometrical parameters of the cut-out and the angle of fiber arrangement on the value of critical load of the structure and buckling form was investigated. Uniform thin plates are relatively cheap to manufacture, however due to their low bending stiffness; they can carry relatively small loads. The lowest form of loss of plate stability, which is the bending form, leads to its rapid destruction due to high deflection increases, with a slight increase in compressive load - low rigidity of the structure. However, the stiffness characteristics of the structure change significantly when the work of plate is forcing according to the higher flexural-torsional form of buckling. The plate is able to carry a much higher compressive load while maintaining much stiffer work characteristics in the post-critical range. The calculations carried out earlier show that plates with forced higher form of buckling are characterized by stable, progressive paths of post-critical equilibrium, enabling their use as elastic elements. The characteristics of such elements can be designed in a wide range by changing the geometrical parameters of the cut-out, i.e. height and width as well as by changing the angle of fiber arrangement The commercial ABAQUS program using the finite element method was used to develop the discrete model and perform numerical calculations. The obtained results are of significant practical importance in the design of structures with elastic elements, allowing to achieve the required maintenance characteristics of the device.

Keywords: buckling mode, numerical method, unsymmetrical laminates, thin-walled elastic elements

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Authors: Hasan Ziari, Hassan Fazaeli, Seyed Javad Vaziri Kang Olyaei, Asma Sadat Dabiri

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The presence of cracks in concrete pavements is a place for the ingression of corrosive substances, acids, oils, and water into the pavement and reduces its long-term durability and level of service. One of the causes of early cracks in concrete pavements is the plastic shrinkage. This shrinkage occurs due to the formation of negative capillary pressures after the equilibrium of the bleeding and evaporation rates at the pavement surface. These cracks form if the tensile stresses caused by the restrained shrinkage exceed the tensile strength of the concrete. Different climate conditions change the rate of evaporation and thus change the balance time of the bleeding and evaporation, which changes the severity of cracking in concrete. The present study examined the relationship between the balance time of bleeding and evaporation and the area of cracking in the concrete slabs using the standard method ASTM C1579 in 27 different environmental conditions by using continuous video recording and digital image analyzing. The results showed that as the evaporation rate increased and the balance time decreased, the crack severity significantly increased so that by reducing the balance time from the maximum value to its minimum value, the cracking area increased more than four times. It was also observed that the cracking area- balance time curve could be interpreted in three sections. An examination of these three parts showed that the combination of climate conditions has a significant effect on increasing or decreasing these two variables. The criticality of a single factor cannot cause the critical conditions of plastic cracking. By combining two mild environmental factors with a severe climate factor (in terms of surface evaporation rate), a considerable reduction in balance time and a sharp increase in cracking severity can be prevented. The results of this study showed that balance time could be an essential factor in controlling and predicting plastic shrinkage cracking in concrete pavements. It is necessary to control this factor in the case of constructing concrete pavements in different climate conditions.

Keywords: bleeding and cracking severity, concrete pavements, climate conditions, plastic shrinkage

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Authors: Sangwoo Han, Saeed Khaleghi Rahimian, Ying Liu

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Vehicle electrification is gaining momentum, and many car manufacturers promise to deliver more electric vehicle (EV) models to consumers in the coming years. In controlling the battery pack, the battery management system (BMS) must maintain optimal battery performance while ensuring the safety of a battery pack. Tasks related to battery performance include determining state-of-charge (SOC), state-of-power (SOP), state-of-health (SOH), cell balancing, and battery charging. Safety related functions include making sure cells operate within specified, static and dynamic voltage window and temperature range, derating power, detecting faulty cells, and warning the user if necessary. The BMS often utilizes an RC circuit model to model a Li-ion cell because of its robustness and low computation cost among other benefits. Because an equivalent circuit model such as the RC model is not a physics-based model, it can never be a prognostic model to predict battery state-of-health and avoid any safety risk even before it occurs. A physics-based Li-ion cell model, on the other hand, is more capable at the expense of computation cost. To avoid the high computation cost associated with a full-order model, many researchers have demonstrated the use of a single particle model (SPM) for BMS applications. One drawback associated with the single particle modeling approach is that it forces to use the average current density in the calculation. The SPM would be appropriate for simulating drive cycles where there is insufficient time to develop a significant current distribution within an electrode. However, under a continuous or high-pulse electrical load, the model may fail to predict cell voltage or Li⁺ plating potential. To overcome this issue, a multi-particle reduced-order model is proposed here. The use of multiple particles combined with either linear or nonlinear charge-transfer reaction kinetics enables to capture current density distribution within an electrode under any type of electrical load. To maintain computational complexity like that of an SPM, governing equations are solved sequentially to minimize iterative solving processes. Furthermore, the model is validated against a full-order model implemented in COMSOL Multiphysics.

Keywords: battery management system, physics-based li-ion cell model, reduced-order model, single-particle and multi-particle model

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Authors: Kirill D. Semavin, Norbert S. Chilingarov, Eugene.V. Skokan

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The ionic liquids (ILs) based on imidazolium cation are well known nowadays. The changing anions and substituents in imidazolium ring may lead to different physical and chemical properties of ILs. It is important that such ILs with halogen as anion are characterized by a low thermal stability. The data about thermal stability of 1-ethyl-3-methylimidazolium chloride are ambiguous. In the works of last years, thermal stability of this IL was investigated by thermogravimetric analysis and obtained results are contradictory. Moreover, in the last study, it was shown that the observed temperature of the beginning of decomposition significantly depends on the experimental conditions, for example, the heating rate of the sample. The vapor pressure of this IL is not presented at the literature. In this study, the vapor pressure of 1-ethyl-3-methylimidazolium chloride was obtained by Knudsen effusion mass-spectrometry (KEMS). The samples of [ЕMIm]Cl (purity > 98%) were supplied by Sigma–Aldrich and were additionally dried at dynamic vacuum (T = 60 0C). Preliminary procedures with Il were derived into glove box. The evaporation studies of [ЕMIm]Cl were carried out by KEMS with using original research equipment based on commercial MI1201 magnetic mass spectrometer. The stainless steel effusion cell had an effective evaporation/effusion area ratio of more than 6000. The cell temperature, measured by a Pt/Pt−Rh (10%) thermocouple, was controlled by a Termodat 128K5 device with an accuracy of ±1 K. In first step of this study, the optimal temperature of experiment and heating rate of samples were customized: 449 K and 5 K/min, respectively. In these conditions the sample is decomposed, but the experimental measurements of the vapor pressures are possible. The thermodynamic activity of [ЕMIm]Cl is close to 1 and products of decomposition don’t affect it at firstly 50 hours of experiment. Therefore, it lets to determine the saturated vapor pressure of IL. The electronic ionization mass-spectra shows that the decomposition of [ЕMIm]Cl proceeds with two ways. Nonetheless, the MALDI mass spectra of the starting sample and residue in the cell were similar. It means that the main decomposition products are gaseous under experimental conditions. This result allows us to obtain information about the kinetics of [ЕMIm]Cl decomposition. Thus, the original KEMS-based procedure made it possible to determine the IL vapor pressure under decomposition conditions. Also, the loss of sample mass due to the evaporation was obtained.

Keywords: ionic liquids, Knudsen effusion mass spectrometry, thermal stability, vapor pressure

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Authors: Victor Alves Barros Galvão, Israel Da Silveira Rego, Antonio Carlos Oliveira, Paulo Gilberto De Paula Toro

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The Brazilian hypersonic aerospace vehicle 14-X B, VHA 14-X B, is a vehicle integrated with the hypersonic airbreathing propulsion system based on supersonic combustion (scramjet), developing in Aerothermodynamics and hypersonic Prof. Henry T. Nagamatsu Laboratory, to conduct demonstration in atmospheric flight at the speed corresponding to Mach number 7 at an altitude of 30km. In the experimental procedure the hypersonic shock tunnel T3 was used, installed in that laboratory. This device simulates the flow over a model is fixed in the test section and can also simulate different atmospheric conditions. The scramjet technology offers substantial advantages to improve aerospace vehicle performance which flies at a hypersonic speed through the Earth's atmosphere by reducing fuel consumption on board. Basically, the scramjet is an aspirated aircraft engine fully integrated that uses oblique/conic shock waves generated during hypersonic flight, to promote the deceleration and compression of atmospheric air in scramjet inlet. During the hypersonic flight, the vehicle VHA 14-X will suffer atmospheric influences, promoting changes in the vehicle's angles of attack (angle that the mean line of vehicle makes with respect to the direction of the flow). Based on this information, a study is conducted to analyze the influences of changes in the vehicle's angle of attack during the atmospheric flight. Analytical theoretical analysis, simulation computational fluid dynamics and experimental investigation are the methodologies used to design a technological demonstrator prior to the flight in the atmosphere. This paper considers analysis of the thermodynamic properties (pressure, temperature, density, sound velocity) in lower surface of the VHA 14-X B. Also, it considers air as an ideal gas and chemical equilibrium, with and without boundary layer, considering changes in the vehicle's angle of attack (positive and negative in relation to the flow) and bi-dimensional expansion wave theory at the expansion section (Theory of Prandtl-Meyer).

Keywords: angle of attack, experimental hypersonic, hypersonic airbreathing propulsion, Scramjet

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