Search results for: sodium phosphate solution
5186 Modification of a Commercial Ultrafiltration Membrane by Electrospray Deposition for Performance Adjustment
Authors: Elizaveta Korzhova, Sebastien Deon, Patrick Fievet, Dmitry Lopatin, Oleg Baranov
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Filtration with nanoporous ultrafiltration membranes is an attractive option to remove ionic pollutants from contaminated effluents. Unfortunately, commercial membranes are not necessarily suitable for specific applications, and their modification by polymer deposition is a fruitful way to adapt their performances accordingly. Many methods are usually used for surface modification, but a novel technique based on electrospray is proposed here. Various quantities of polymers were deposited on a commercial membrane, and the impact of the deposit is investigated on filtration performances and discussed in terms of charge and hydrophobicity. The electrospray deposition is a technique which has not been used for membrane modification up to now. It consists of spraying small drops of polymer solution under a high voltage between the needle containing the solution and the metallic support on which membrane is stuck. The advantage of this process lies in the small quantities of polymer that can be coated on the membrane surface compared with immersion technique. In this study, various quantities (from 2 to 40 μL/cm²) of solutions containing two charged polymers (13 mmol/L of monomer unit), namely polyethyleneimine (PEI) and polystyrene sulfonate (PSS), were sprayed on a negatively charged polyethersulfone membrane (PLEIADE, Orelis Environment). The efficacy of the polymer deposition was then investigated by estimating ion rejection, permeation flux, zeta-potential and contact angle before and after the polymer deposition. Firstly, contact angle (θ) measurements show that the surface hydrophilicity is notably improved by coating both PEI and PSS. Moreover, it was highlighted that the contact angle decreases monotonously with the amount of sprayed solution. Additionally, hydrophilicity enhancement was proved to be better with PSS (from 62 to 35°) than PEI (from 62 to 53°). Values of zeta-potential (ζ were estimated by measuring the streaming current generated by a pressure difference on both sides of a channel made by clamping two membranes. The ζ-values demonstrate that the deposits of PSS (negative at pH=5.5) allow an increase of the negative membrane charge, whereas the deposits of PEI (positive) lead to a positive surface charge. Zeta-potentials measurements also emphasize that the sprayed quantity has little impact on the membrane charge, except for very low quantities (2 μL/m²). The cross-flow filtration of salt solutions containing mono and divalent ions demonstrate that polymer deposition allows a strong enhancement of ion rejection. For instance, it is shown that rejection of a salt containing a divalent cation can be increased from 1 to 20 % and even to 35% by deposing 2 and 4 μL/cm² of PEI solution, respectively. This observation is coherent with the reversal of the membrane charge induced by PEI deposition. Similarly, the increase of negative charge induced by PSS deposition leads to an increase of NaCl rejection from 5 to 45 % due to electrostatic repulsion of the Cl- ion by the negative surface charge. Finally, a notable fall in the permeation flux due to the polymer layer coated at the surface was observed and the best polymer concentration in the sprayed solution remains to be determined to optimize performances.Keywords: ultrafiltration, electrospray deposition, ion rejection, permeation flux, zeta-potential, hydrophobicity
Procedia PDF Downloads 1875185 A Study on the Synthesis and Antioxidant Activity of Hybrid Pyrazoline Integrated with Pyrazole and Thiazole Nuclei
Authors: Desta Gebretekle Shiferaw, Balakrishna Kalluraya
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Pyrazole is an aromatic five-membered heterocycle with two nitrogen and three carbon atoms in its ring structure. According to the literature, pyrazoline, pyrazole, and thiazole-containing moieties are found in various drug structures and are responsible for nearly all pharmacological effects. The pyrazoline linked to pyrazole moiety carbothioamides was synthesized via the reaction of pyrazole-bearing chalcones (3-(5-chloro-3-methyl-¹-phenyl-1H-pyrazol-4-yl)-¹-(substituted aryl) prop-2-ene-¹-one derivatives) with a nucleophile thiosemicarbohyrazide by heating in ethanol using fused sodium acetate as a catalyst. Then the carbothioamide derivatives were converted into the pyrazoline hybrid to pyrazole and thiazole derivatives by condensing with substituted phenacyl bromide in alcohol in a basic medium. Next, the chemical structure of the newly synthesized molecules was confirmed by IR, 1H-NMR, and mass spectral data. Further, they were screened for their in vitro antioxidant activity. Compared to butylated hydroxy anisole (BHA)., the antioxidant data showed that the synthesized compounds had good to moderate activity.Keywords: pyrazoline-pyrazole carbothioamide derivatives, pyrazoline-pyrazole-thiazole derivatives, spectral studies, antioxidant activity
Procedia PDF Downloads 725184 Chemical Hazards Impact on Efficiency of Energy Storage Battery and its Possible Mitigation's
Authors: Abirham Simeneh Ayalew, Seada Hussen Adem, Frie Ayalew Yimam
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Battery energy storage has a great role on storing energy harnessed from different alternative resources and greatly benefit the power sector by supply energy back to the system during outage and regular operation in power sectors. Most of the study shows that there is an exponential increase in the quantity of lithium - ion battery energy storage system due to their power density, economical aspects and its performance. But this lithium ion battery failures resulted in fire and explosion due to its having flammable electrolytes (chemicals) which can create those hazards. Hazards happen in these energy storage system lead to minimize battery life spans or efficiency. Identifying the real cause of these hazards and its mitigation techniques can be the solution to improve the efficiency of battery technologies and the electrode materials should have high electrical conductivity, large surface area, stable structure and low resistance. This paper asses the real causes of chemical hazards, its impact on efficiency, proposed solution for mitigating those hazards associated with efficiency improvement and summery of researchers new finding related to the field.Keywords: battery energy storage, battery energy storage efficiency, chemical hazards, lithium ion battery
Procedia PDF Downloads 795183 Effect of Atmospheric Pressure on the Flow at the Outlet of a Propellant Nozzle
Authors: R. Haoui
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The purpose of this work is to simulate the flow at the exit of Vulcan 1 engine of European launcher Ariane 5. The geometry of the propellant nozzle is already determined using the characteristics method. The pressure in the outlet section of the nozzle is less than atmospheric pressure on the ground, causing the existence of oblique and normal shock waves at the exit. During the rise of the launcher, the atmospheric pressure decreases and the shock wave disappears. The code allows the capture of shock wave at exit of nozzle. The numerical technique uses the Flux Vector Splitting method of Van Leer to ensure convergence and avoid the calculation instabilities. The Courant, Friedrichs and Lewy coefficient (CFL) and mesh size level are selected to ensure the numerical convergence. The nonlinear partial derivative equations system which governs this flow is solved by an explicit unsteady numerical scheme by the finite volume method. The accuracy of the solution depends on the size of the mesh and also the step of time used in the discretized equations. We have chosen in this study the mesh that gives us a stationary solution with good accuracy.Keywords: finite volume, lunchers, nozzles, shock wave
Procedia PDF Downloads 2895182 Sensitive Determination of Copper(II) by Square Wave Anodic Stripping Voltammetry with Tetracarbonylmolybdenum(0) Multiwalled Carbon Nanotube Paste Electrode
Authors: Illyas Md Isa, Mohamad Idris Saidin, Mustaffa Ahmad, Norhayati Hashim
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A highly selective and sensitive carbon paste electrode modified with multiwall carbon nanotubes and 2,6–diacetylpyridine-di-(1R)–(-)–fenchone diazine tetracarbonylmolybdenum(0) complex was used for determination of trace amounts of Cu(II) using square wave anodic stripping voltammetry (SWASV). The influences of experimental variables on the proposed electrode such as pH, supporting electrolyte, preconcentration potential and time, and square wave parameters were investigated. Under optimal conditions, the proposed electrode showed a linear relationship with concentration in the range of 1.0 × 10–10 to 1.0 × 10– 6 M Cu(II) with a limit of detection 8.0 × 10–11 M. The relative standard deviation (n = 5) for a solution containing 1.0 × 10– 6 M of Cu(II) was 0.036. The presence of various cations (in 10 and 100-folds concentration) did not interfere. Electrochemical impedance spectroscopy (EIS) showed that the charge transfer at the electrode-solution interface was favourable. The proposed electrode was applied for the determination of Cu(II) in several water samples. Results agreed very well with those obtained by inductively coupled plasma-optical emission spectrometry. The modified electrode was then proposed as an alternative for determination of Cu(II).Keywords: chemically modified electrode, Cu(II), square wave anodic stripping voltammetry, tetracarbonylmolybdenum(0)
Procedia PDF Downloads 2705181 Recovery of Chromium(III) from Tannery Wastewater by Nanoparticles and Whiskers of Chitosan
Authors: El Montassir Dahmane, Nadia Eladlani, Aziz Ouahrouch, Mohammed Rhazi, Moha Taourirte
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The present study was aimed to approximate the optimal conditions to chromium recovery from wastewater by nanoparticles and whiskers of chitosan. Chitosan with an average molecular weight of 63 kDa and a 96% deacetylation degree was prepared according to our previous study. Chromium recovery is influenced by different parameters. In our search, we determined the appropriate range of pH to form chitosan–Cr(III), nanoparticles Cr(III), and whiskers– Cr(III) complex. We studied also the influence of chromium concentration and the nature of chitosan-based materials on the complexation process. Our main aim is to approximate the optimal conditions to remove chromium(III) from the tanning bath, recuperated from tannery wastewater of Marrakech in Morocco. A Perkin Elmer optima 2000 Inductively Coupled Plasma- Optical Emission Spectrometer (ICP-OES), was used to determine the quantity of chromium persistent in tannery wastewater after complexation phenomenon. To the best of our knowledge, this is the first report interested in the optimal conditions for chromium recovery from wastewater by nanoparticles and whiskers of chitosan. From our research, we found that in chromium solution, the appropriate range of pH to form complex is between 5.6 and 6.7. Also, the complexation of Cr(III) is depending on the nature of complexing ligand and chromium concentration. The obtained results reveal that nanoparticles present an excellent adsorption capacity regardless of chromium concentration. In addition, after a critical chromium concentration (250 mg/l), our ligand becomes saturated, that requires an increase of ligand mass for increasing chromium concentration in order to have a better adsorption capacity. Hence, in the same conditions, we used chitosan, its nanoparticles, whiskers, and chitosan based films to remove Cr(III) from tannery wastewater. The pH of this effluent was around 6, and its chromium concentration was 300 mg/l. The results expose that the sequence of complexing ligand in the effluent is the same in chromium solution, determined via our previous study. However, the adsorbed quantity is less due to the presence of other metallic ions in tannery wastewater. We conclude that the best complexing ligand-based chitosan is chitosan nanoaprticles whether it’s in chromium solution or in tannery wastewater. Nanoparticles are the best complexing ligand after 24 h of contact nanoparticles can remove 70% of chromium from this tannery wastewater.Keywords: nanoparticles, whiskers, chitosan, chromium
Procedia PDF Downloads 1375180 Kirchoff Type Equation Involving the p-Laplacian on the Sierpinski Gasket Using Nehari Manifold Technique
Authors: Abhilash Sahu, Amit Priyadarshi
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In this paper, we will discuss the existence of weak solutions of the Kirchhoff type boundary value problem on the Sierpinski gasket. Where S denotes the Sierpinski gasket in R² and S₀ is the intrinsic boundary of the Sierpinski gasket. M: R → R is a positive function and h: S × R → R is a suitable function which is a part of our main equation. ∆p denotes the p-Laplacian, where p > 1. First of all, we will define a weak solution for our problem and then we will show the existence of at least two solutions for the above problem under suitable conditions. There is no well-known concept of a generalized derivative of a function on a fractal domain. Recently, the notion of differential operators such as the Laplacian and the p-Laplacian on fractal domains has been defined. We recall the result first then we will address the above problem. In view of literature, Laplacian and p-Laplacian equations are studied extensively on regular domains (open connected domains) in contrast to fractal domains. In fractal domains, people have studied Laplacian equations more than p-Laplacian probably because in that case, the corresponding function space is reflexive and many minimax theorems which work for regular domains is applicable there which is not the case for the p-Laplacian. This motivates us to study equations involving p-Laplacian on the Sierpinski gasket. Problems on fractal domains lead to nonlinear models such as reaction-diffusion equations on fractals, problems on elastic fractal media and fluid flow through fractal regions etc. We have studied the above p-Laplacian equations on the Sierpinski gasket using fibering map technique on the Nehari manifold. Many authors have studied the Laplacian and p-Laplacian equations on regular domains using this Nehari manifold technique. In general Euler functional associated with such a problem is Frechet or Gateaux differentiable. So, a critical point becomes a solution to the problem. Also, the function space they consider is reflexive and hence we can extract a weakly convergent subsequence from a bounded sequence. But in our case neither the Euler functional is differentiable nor the function space is known to be reflexive. Overcoming these issues we are still able to prove the existence of at least two solutions of the given equation.Keywords: Euler functional, p-Laplacian, p-energy, Sierpinski gasket, weak solution
Procedia PDF Downloads 2345179 Aerodynamic Design of Axisymmetric Supersonic Nozzle Used by an Optimization Algorithm
Authors: Mohammad Mojtahedpoor
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In this paper, it has been studied the method of optimal design of the supersonic nozzle. It could make viscous axisymmetric nozzles that the quality of their outlet flow is quite desired. In this method, it is optimized the divergent nozzle, at first. The initial divergent nozzle contour is designed through the method of characteristics and adding a suitable boundary layer to the inviscid contour. After that, it is made a proper grid and then simulated flow by the numerical solution and AUSM+ method by using the operation boundary condition. At the end, solution outputs are investigated and optimized. The numerical method has been validated with experimental results. Also, in order to evaluate the effectiveness of the present method, the nozzles compared with the previous studies. The comparisons show that the nozzles obtained through this method are sufficiently better in some conditions, such as the flow uniformity, size of the boundary layer, and obtained an axial length of the nozzle. Designing the convergent nozzle part affects by flow uniformity through changing its axial length and input diameter. The results show that increasing the length of the convergent part improves the output flow uniformity.Keywords: nozzle, supersonic, optimization, characteristic method, CFD
Procedia PDF Downloads 2005178 Chemical Durability of Textured Glass-coat Suitable for Building Application
Authors: Adejo Andrew Ojonugwa, Jomboh Jeff Kator, Garkida Adele Dzikwi
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This study investigates the behaviour of textured glass coat to chemical reactions upon application. Samples of textured glass coat developed from mixed post consumer glass were subjected to pH test (ASTM D5464), Chemical resistance test (ASTM D3260 and D1308), Adhesion test (ASTM D3359), and Abrasion test (ASTM D4060). Results shows a pH of 8.50, Chemical resistance of 5% flick rate when reacted with Sodium hydroxide (NaOH), a 3%, 5%, 10%, and 15% discolouration when reacted with Magnesium hydroxide (Mg(OH)2), Hydrogen fluoride (HF), Potassium hydroxide (KOH) and NaOH respectively, an adhesion of 4A and abrasion of 0.2g. The results confirm that the developed textured glass coat is in line with the standard pH range of 8-9, resistant to acid and base except for HF, NaOH, and Mg(OH)₂, good adhesion and abrasion properties, thereby making the coat resistant to chemical degradation and a good engineering material.Keywords: chemical durability, glass-coat, building, recycling
Procedia PDF Downloads 1135177 A Collaborative Problem Driven Approach to Design an HR Analytics Application
Authors: L. Atif, C. Rosenthal-Sabroux, M. Grundstein
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The requirements engineering process is a crucial phase in the design of complex systems. The purpose of our research is to present a collaborative problem-driven requirements engineering approach that aims at improving the design of a Decision Support System as an Analytics application. This approach has been adopted to design a Human Resource management DSS. The Requirements Engineering process is presented as a series of guidelines for activities that must be implemented to assure that the final product satisfies end-users requirements and takes into account the limitations identified. For this, we know that a well-posed statement of the problem is “a problem whose crucial character arises from collectively produced estimation and a formulation found to be acceptable by all the parties”. Moreover, we know that DSSs were developed to help decision-makers solve their unstructured problems. So, we thus base our research off of the assumption that developing DSS, particularly for helping poorly structured or unstructured decisions, cannot be done without considering end-user decision problems, how to represent them collectively, decisions content, their meaning, and the decision-making process; thus, arise the field issues in a multidisciplinary perspective. Our approach addresses a problem-driven and collaborative approach to designing DSS technologies: It will reflect common end-user problems in the upstream design phase and in the downstream phase these problems will determine the design choices and potential technical solution. We will thus rely on a categorization of HR’s problems for a development mirroring the Analytics solution. This brings out a new data-driven DSS typology: Descriptive Analytics, Explicative or Diagnostic Analytics, Predictive Analytics, Prescriptive Analytics. In our research, identifying the problem takes place with design of the solution, so, we would have to resort a significant transformations of representations associated with the HR Analytics application to build an increasingly detailed representation of the goal to be achieved. Here, the collective cognition is reflected in the establishment of transfer functions of representations during the whole of the design process.Keywords: DSS, collaborative design, problem-driven requirements, analytics application, HR decision making
Procedia PDF Downloads 2955176 Modelling Phytoremediation Rates of Aquatic Macrophytes in Aquaculture Effluent
Authors: E. A. Kiridi, A. O. Ogunlela
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Pollutants from aquacultural practices constitute environmental problems and phytoremediation could offer cheaper environmentally sustainable alternative since equipment using advanced treatment for fish tank effluent is expensive to import, install, operate and maintain, especially in developing countries. The main objective of this research was, therefore, to develop a mathematical model for phytoremediation by aquatic plants in aquaculture wastewater. Other objectives were to evaluate the retention times on phytoremediation rates using the model and to measure the nutrient level of the aquaculture effluent and phytoremediation rates of three aquatic macrophytes, namely; water hyacinth (Eichornia crassippes), water lettuce (Pistial stratoites) and morning glory (Ipomea asarifolia). A completely randomized experimental design was used in the study. Approximately 100 g of each macrophyte were introduced into the hydroponic units and phytoremediation indices monitored at 8 different intervals from the first to the 28th day. The water quality parameters measured were pH and electrical conductivity (EC). Others were concentration of ammonium–nitrogen (NH₄⁺ -N), nitrite- nitrogen (NO₂⁻ -N), nitrate- nitrogen (NO₃⁻ -N), phosphate –phosphorus (PO₄³⁻ -P), and biomass value. The biomass produced by water hyacinth was 438.2 g, 600.7 g, 688.2 g and 725.7 g at four 7–day intervals. The corresponding values for water lettuce were 361.2 g, 498.7 g, 561.2 g and 623.7 g and for morning glory were 417.0 g, 567.0 g, 642.0 g and 679.5g. Coefficient of determination was greater than 80% for EC, TDS, NO₂⁻ -N, NO₃⁻ -N and 70% for NH₄⁺ -N using any of the macrophytes and the predicted values were within the 95% confidence interval of measured values. Therefore, the model is valuable in the design and operation of phytoremediation systems for aquaculture effluent.Keywords: aquaculture effluent, macrophytes, mathematical model, phytoremediation
Procedia PDF Downloads 2255175 Investigation of Film and Mechanical Properties of Poly(Lactic Acid)
Authors: Reyhan Özdoğan, Özgür Ceylan, Mehmet Arif Kaya, Mithat Çelebi
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Food packaging is important for the food industry. Bioplastics have been used as food packaging materials. According to the European Bioplastics organization, bioplastics can be defined as plastics based on renewable resources (bio-based) or as plastics which are biodegradable and/or compostable. Poly(lactic acid) (PLA) has an industrially importance of bioplastic polymers. PLA is a family of biodegradable thermoplastic polyester made from renewable resources. It is produced by conversion of corn, or other carbohydrate sources, into dextrose, followed by fermentation into lactic acid through direct polycondensation of lactic acid monomers or through ring-opening polymerization of lactide. The processing possibilities of this transparent material are very wide, ranging from injection molding and extrusion over cast film extrusion to blow molding and thermoforming. In this study, PLA films were prepared by solution casting method. PLAs which are different molecular weights were plasticized with glycerol and the morphology of films was monitored by optical microscopy. Properties of mechanical and film of PLA were researched with the mechanical testing machine.Keywords: biodegradable, bioplastics, morphology, solution casting, poly(lactic acid)
Procedia PDF Downloads 3785174 Starch-Based Systems for the Nano-Delivery of Quercetin
Authors: Fernando G. Torres, Omar P. Troncoso
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Quercetin is a naturally occurring polyphenol found in many vegetables, such as onion, with antioxidant properties. It is a dietary component with a documented role in reducing different human cancers. However, its low bioavailability, poor water solubility, and chemical instability limit its applications. Different nano-delivery systems such as nanoparticles, micelles, and nanohydrogels have been studied in order to improve the bioavailability of quercetin. Nanoparticles based on natural polymers such as starch have the advantage of being biocompatible, biodegradable, and non-toxic. In this study, quercetin was loaded into starch nanoparticles using a nanoprecipitation method. Different routes, using sodium tripolyphosphate and Tween® 80 as tensioactive agents, were tested in order to obtain an optimized starch-based nano-delivery system. The characterization of the nanoparticles loaded with quercetin was assessed by Fourier Transform Infrared Spectroscopy, Dynamic Light Scattering, Zeta potential, and Differential scanning calorimetry. UV-vis spectrophotometry was used to evaluate the loading efficiency and capacity of the samples. The results showed that starch-based systems could be successfully used for the nano-delivery of quercetin.Keywords: starch nanoparticles, nanoprecipitation, quercetin, biomedical applications
Procedia PDF Downloads 1415173 Preliminary Study of Antimicrobial Activity against Escherichia coli sp. and Probiotic Properties of Lactic Acid Bacteria Isolated from Thailand Fermented Foods
Authors: Phanwipa Pangsri, Yawariyah Weahayee
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The lactic acid bacteria (LAB) were isolated from 10 samples of fermented foods (Sa-tor-dong and Bodo) in South locality of Thailand. The 23 isolates of lactic acid bacteria were selected, which were exhibited a clear zone and growth on MRS agar supplemented with CaCO3. All of lactic acid bacteria were tested on morphological and biochemical. The result showed that all isolates were Gram’s positive, non-spore forming but only 10 isolates displayed catalase negative. The 10 isolates including BD 1.1, BD 1.2, BD 2.1, BD2.2, BD 2.3, BD 3.1, BD 4.1, BD 5.2, ST4.1, and ST 5.2 were selected for inhibition activity determination. Only 2 strains (ST 4.1 and BD 2.3) showed inhibition zone on agar, when using Escherichia coli sp. as target strain. The ST 4.1 showed highest inhibition zone on agar, which was selected for probiotic property testing. The ST4.1 isolate could grow in MRS broth containing a high concentration of sodium chloride 6%, bile salts 7%, pH 4-10 and vary temperature at 15-45^oC.Keywords: lactic acid bacteria, probiotic, antimicrobial, probiotic property testing
Procedia PDF Downloads 3785172 Hydration Behavior of Belitic Cement in the Presence of Na₂CO₃, NaOH, KOH, and Water Glass
Authors: F. Amor, A. Bouregba, N. El Fami, A. Diouri
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This study provides insights into the role of alkalis in modifying the hydration kinetics and microstructural development of β-dicalcium silicate, highlighting potential pathways for enhancing the performance of belite-based cements in various construction applications. It investigates the behavior of β-dicalcium silicates (β-Ca₂SiO₄) when hydrated in various alkaline environments, including deionized water and solutions containing 2M concentrations of Na₂CO₃, NaOH, KOH, and water glass. The dicalcium silicate was synthesized with laboratory reagents, calcium carbonate, and gel silica. The hydration process was carried out over different periods, ranging from 7 to 90 days. The hydrated samples were characterized using X-ray diffraction, infrared spectroscopy, and scanning electron microscopy, while the mechanical strength tests were performed at 28 and 90 days. The results indicate that the presence of alkalis significantly influences the hydration of belite cement. Early hydration is accelerated, which is evident from the faster dissolution of C₂S, a decrease in C₂S peaks, and the formation of C-S-H products, including sodium-containing C-(N)-S-H and potassium-containing C-(K)-S-H.Keywords: dicalcium silicate, alkali activator, hydration, water glass, Na₂CO₃, NaOH, KOH
Procedia PDF Downloads 135171 Simulation Study on Effects of Surfactant Properties on Surfactant Enhanced Oil Recovery from Fractured Reservoirs
Authors: Xiaoqian Cheng, Jon Kleppe, Ole Torsaeter
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One objective of this work is to analyze the effects of surfactant properties (viscosity, concentration, and adsorption) on surfactant enhanced oil recovery at laboratory scale. The other objective is to obtain the functional relationships between surfactant properties and the ultimate oil recovery and oil recovery rate. A core is cut into two parts from the middle to imitate the matrix with a horizontal fracture. An injector and a producer are at the left and right sides of the fracture separately. The middle slice of the core is used as the model in this paper, whose size is 4cm x 0.1cm x 4.1cm, and the space of the fracture in the middle is 0.1 cm. The original properties of matrix, brine, oil in the base case are from Ekofisk Field. The properties of surfactant are from literature. Eclipse is used as the simulator. The results are followings: 1) The viscosity of surfactant solution has a positive linear relationship with surfactant oil recovery time. And the relationship between viscosity and oil production rate is an inverse function. The viscosity of surfactant solution has no obvious effect on ultimate oil recovery. Since most of the surfactant has no big effect on viscosity of brine, the viscosity of surfactant solution is not a key parameter of surfactant screening for surfactant flooding in fractured reservoirs. 2) The increase of surfactant concentration results a decrease of oil recovery rate and an increase of ultimate oil recovery. However, there are no functions could describe the relationships. Study on economy should be conducted because of the price of surfactant and oil. 3) In the study of surfactant adsorption, assume that the matrix wettability is changed to water-wet when the surfactant adsorption is to the maximum at all cases. And the ratio of surfactant adsorption and surfactant concentration (Cads/Csurf) is used to estimate the functional relationship. The results show that the relationship between ultimate oil recovery and Cads/Csurf is a logarithmic function. The oil production rate has a positive linear relationship with exp(Cads/Csurf). The work here could be used as a reference for the surfactant screening of surfactant enhanced oil recovery from fractured reservoirs. And the functional relationships between surfactant properties and the oil recovery rate and ultimate oil recovery help to improve upscaling methods.Keywords: fractured reservoirs, surfactant adsorption, surfactant concentration, surfactant EOR, surfactant viscosity
Procedia PDF Downloads 1745170 Green Production of Chitosan Nanoparticles and their Potential as Antimicrobial Agents
Authors: L. P. Gomes, G. F. Araújo, Y. M. L. Cordeiro, C. T. Andrade, E. M. Del Aguila, V. M. F. Paschoalin
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The application of nanoscale materials and nanostructures is an emerging area, these since materials may provide solutions to technological and environmental challenges in order to preserve the environment and natural resources. To reach this goal, the increasing demand must be accompanied by 'green' synthesis methods. Chitosan is a natural, nontoxic, biopolymer derived by the deacetylation of chitin and has great potential for a wide range of applications in the biological and biomedical areas, due to its biodegradability, biocompatibility, non-toxicity and versatile chemical and physical properties. Chitosan also presents high antimicrobial activities against a wide variety of pathogenic and spoilage microorganisms. Ultrasonication is a common tool for the preparation and processing of polymer nanoparticles. It is particularly effective in breaking up aggregates and in reducing the size and polydispersity of nanoparticles. High-intensity ultrasonication has the potential to modify chitosan molecular weight and, thus, alter or improve chitosan functional properties. The aim of this study was to evaluate the influence of sonication intensity and time on the changes of commercial chitosan characteristics, such as molecular weight and its potential antibacterial activity against Gram-negative bacteria. The nanoparticles (NPs) were produced from two commercial chitosans, of medium molecular weight (CS-MMW) and low molecular weight (CS-LMW) from Sigma-Aldrich®. These samples (2%) were solubilized in 100 mM sodium acetate pH 4.0, placed on ice and irradiated with an ultrasound SONIC ultrasonic probe (model 750 W), equipped with a 1/2" microtip during 30 min at 4°C. It was used on constant duty cycle and 40% amplitude with 1/1s intervals. The ultrasonic degradation of CS-MMW and CS-LMW were followed up by means of ζ-potential (Brookhaven Instruments, model 90Plus) and dynamic light scattering (DLS) measurements. After sonication, the concentrated samples were diluted 100 times and placed in fluorescence quartz cuvettes (Hellma 111-QS, 10 mm light path). The distributions of the colloidal particles were calculated from the DLS and ζ-potential are measurements taken for the CS-MMW and CS-LMW solutions before and after (CS-MMW30 and CS-LMW30) sonication for 30 min. Regarding the results for the chitosan sample, the major bands can be distinguished centered at Radius hydrodynamic (Rh), showed different distributions for CS-MMW (Rh=690.0 nm, ζ=26.52±2.4), CS-LMW (Rh=607.4 and 2805.4 nm, ζ=24.51±1.29), CS-MMW30 (Rh=201.5 and 1064.1 nm, ζ=24.78±2.4) and CS-LMW30 (Rh=492.5, ζ=26.12±0.85). The minimal inhibitory concentration (MIC) was determined using different chitosan samples concentrations. MIC values were determined against to E. coli (106 cells) harvested from an LB medium (Luria-Bertani BD™) after 18h growth at 37 ºC. Subsequently, the cell suspension was serially diluted in saline solution (0.8% NaCl) and plated on solid LB at 37°C for 18 h. Colony-forming units were counted. The samples showed different MICs against E. coli for CS-LMW (1.5mg), CS-MMW30 (1.5 mg/mL) and CS-LMW30 (1.0 mg/mL). The results demonstrate that the production of nanoparticles by modification of their molecular weight by ultrasonication is simple to be performed and dispense acid solvent addition. Molecular weight modifications are enough to provoke changes in the antimicrobial potential of the nanoparticles produced in this way.Keywords: antimicrobial agent, chitosan, green production, nanoparticles
Procedia PDF Downloads 3275169 Comparative Evaluation of Kinetic Model of Chromium and Lead Uptake from Aqueous Solution by Activated Balanitesaegyptiaca Seeds
Authors: Mohammed Umar Manko
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A series of batch experiments were conducted in order to investigate the feasibility of Balanitesaegyptiaca seeds based activated carbon as compared with industrial activated carbon for the removal of chromium and lead ions from aqueous solution by the adsorption process within 30 to 150 minutes contact time. The activated samples were prepared using zinc chloride and tetraoxophophate(VI) acid. The results obtained showed that the activated carbon of Balanitesaegyptiaca seeds studied had relatively high adsorption capacities for these heavy metal ions compared with industrial Activated Carbon. The percentage removal of Cr (VI) and lead (II) ions by the three activated carbon samples were 64%, 70% and 71%; 60%, 66% and 60% respectively. Adsorption equilibrium was established in 90 minutes for the heavy metal ions. The equilibrium data fitted the pseudo second order out of the pseudo first, pseudo second, Elovich ,Natarajan and Khalaf models tested. The investigation also showed that the adsorbents can effectively remove metal ions from similar wastewater and aqueous media.Keywords: activated carbon, pseudo second order, chromium, lead, Elovich model
Procedia PDF Downloads 3215168 Calibration of 2D and 3D Optical Measuring Instruments in Industrial Environments at Submillimeter Range
Authors: Alberto Mínguez-Martínez, Jesús de Vicente y Oliva
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Modern manufacturing processes have led to the miniaturization of systems and, as a result, parts at the micro-and nanoscale are produced. This trend seems to become increasingly important in the near future. Besides, as a requirement of Industry 4.0, the digitalization of the models of production and processes makes it very important to ensure that the dimensions of newly manufactured parts meet the specifications of the models. Therefore, it is possible to reduce the scrap and the cost of non-conformities, ensuring the stability of the production at the same time. To ensure the quality of manufactured parts, it becomes necessary to carry out traceable measurements at scales lower than one millimeter. Providing adequate traceability to the SI unit of length (the meter) to 2D and 3D measurements at this scale is a problem that does not have a unique solution in industrial environments. Researchers in the field of dimensional metrology all around the world are working on this issue. A solution for industrial environments, even if it is not complete, will enable working with some traceability. At this point, we believe that the study of the surfaces could provide us with a first approximation to a solution. Among the different options proposed in the literature, the areal topography methods may be the most relevant because they could be compared to those measurements performed using Coordinate Measuring Machines (CMM’s). These measuring methods give (x, y, z) coordinates for each point, expressing it in two different ways, either expressing the z coordinate as a function of x, denoting it as z(x), for each Y-axis coordinate, or as a function of the x and y coordinates, denoting it as z (x, y). Between others, optical measuring instruments, mainly microscopes, are extensively used to carry out measurements at scales lower than one millimeter because it is a non-destructive measuring method. In this paper, the authors propose a calibration procedure for the scales of optical measuring instruments, particularizing for a confocal microscope, using material standards easy to find and calibrate in metrology and quality laboratories in industrial environments. Confocal microscopes are measuring instruments capable of filtering the out-of-focus reflected light so that when it reaches the detector, it is possible to take pictures of the part of the surface that is focused. Varying and taking pictures at different Z levels of the focus, a specialized software interpolates between the different planes, and it could reconstruct the surface geometry into a 3D model. As it is easy to deduce, it is necessary to give traceability to each axis. As a complementary result, the roughness Ra parameter will be traced to the reference. Although the solution is designed for a confocal microscope, it may be used for the calibration of other optical measuring instruments by applying minor changes.Keywords: industrial environment, confocal microscope, optical measuring instrument, traceability
Procedia PDF Downloads 1565167 Glucose Monitoring System Using Machine Learning Algorithms
Authors: Sangeeta Palekar, Neeraj Rangwani, Akash Poddar, Jayu Kalambe
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The bio-medical analysis is an indispensable procedure for identifying health-related diseases like diabetes. Monitoring the glucose level in our body regularly helps us identify hyperglycemia and hypoglycemia, which can cause severe medical problems like nerve damage or kidney diseases. This paper presents a method for predicting the glucose concentration in blood samples using image processing and machine learning algorithms. The glucose solution is prepared by the glucose oxidase (GOD) and peroxidase (POD) method. An experimental database is generated based on the colorimetric technique. The image of the glucose solution is captured by the raspberry pi camera and analyzed using image processing by extracting the RGB, HSV, LUX color space values. Regression algorithms like multiple linear regression, decision tree, RandomForest, and XGBoost were used to predict the unknown glucose concentration. The multiple linear regression algorithm predicts the results with 97% accuracy. The image processing and machine learning-based approach reduce the hardware complexities of existing platforms.Keywords: artificial intelligence glucose detection, glucose oxidase, peroxidase, image processing, machine learning
Procedia PDF Downloads 2045166 Biochemical Changes in the Liver of Mice after Exposure to Different Doses of Diclofenac Sodium
Authors: Deepak Mohan, Sushma Sharma
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Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) are a group of widely used drugs for the treatment of rheumatoid diseases and to relieve pain and inflammation due to their analgesic anti-pyretic and anti-inflammatory properties. The therapeutic and many of the toxic effects of NSAIDs result from reversible inhibition of enzymes in the cyclooxygenase (COX) group. In the present investigation the effect of the drug on the concentration of lipids, and on the activity of the enzymes i.e. acid and alkaline phosphatase, GOT, GPT and lipid peroxidase were studied. There was a significant enhancement in the activities of both acid and alkaline phosphatase after 21 days of treatment. Proportionate increase in the MDA contents was observed after different days of diclofenac treatment. Cellular damage in the liver resulted in decrease in the activity of both GOT (Glutamate oxaloacetate transaminase) and GPT (Glutamate pyruvate transaminase) in both low and high dose groups. Significant decrease in the liver contents was also observed in both dose groups.Keywords: anti-inflammatory, cyclooxygenase, glutamate oxaloacetate transaminase, malondialdehyde
Procedia PDF Downloads 3025165 The 10,000 Fold Effect of Retrograde Neurotransmission: A New Concept for Cerebral Palsy Revival by the Use of Nitric Oxide Donars
Authors: V. K. Tewari, M. Hussain, H. K. D. Gupta
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Background: Nitric Oxide Donars (NODs) (intrathecal sodium nitroprusside (ITSNP) and oral tadalafil 20mg post ITSNP) has been studied in this context in cerebral palsy patients for fast recovery. This work proposes two mechanisms for acute cases and one mechanism for chronic cases, which are interrelated, for physiological recovery. a) Retrograde Neurotransmission (acute cases): 1) Normal excitatory impulse: at the synaptic level, glutamate activates NMDA receptors, with nitric oxide synthetase (NOS) on the postsynaptic membrane, for further propagation by the calcium-calmodulin complex. Nitric oxide (NO, produced by NOS) travels backward across the chemical synapse and binds the axon-terminal NO receptor/sGC of a presynaptic neuron, regulating anterograde neurotransmission (ANT) via retrograde neurotransmission (RNT). Heme is the ligand-binding site of the NO receptor/sGC. Heme exhibits > 10,000-fold higher affinity for NO than for oxygen (the 10,000-fold effect) and is completed in 20 msec. 2) Pathological conditions: normal synaptic activity, including both ANT and RNT, is absent. A NO donor (SNP) releases NO from NOS in the postsynaptic region. NO travels backward across a chemical synapse to bind to the heme of a NO receptor in the axon terminal of a presynaptic neuron, generating an impulse, as under normal conditions. b) Vasopasm: (acute cases) Perforators show vasospastic activity. NO vasodilates the perforators via the NO-cAMP pathway. c) Long-Term Potentiation (LTP): (chronic cases) The NO–cGMP-pathway plays a role in LTP at many synapses throughout the CNS and at the neuromuscular junction. LTP has been reviewed both generally and with respect to brain regions specific for memory/learning. Aims/Study Design: The principles of “generation of impulses from the presynaptic region to the postsynaptic region by very potent RNT (10,000-fold effect)” and “vasodilation of arteriolar perforators” are the basis of the authors’ hypothesis to treat cerebral palsy cases. Case-control prospective study. Materials and Methods: The experimental population included 82 cerebral palsy patients (10 patients were given control treatments without NOD or with 5% dextrose superfusion, and 72 patients comprised the NOD group). The mean time for superfusion was 5 months post-cerebral palsy. Pre- and post-NOD status was monitored by Gross Motor Function Classification System for Cerebral Palsy (GMFCS), MRI, and TCD studies. Results: After 7 days in the NOD group, the mean change in the GMFCS score was an increase of 1.2 points mean; after 3 months, there was an increase of 3.4 points mean, compared to the control-group increase of 0.1 points at 3 months. MRI and TCD documented the improvements. Conclusions: NOD (ITSNP boosts up the recovery and oral tadalafil maintains the recovery to a well-desired level) acts swiftly in the treatment of CP, acting within 7 days on 5 months post-cerebral palsy either of the three mechanisms.Keywords: cerebral palsy, intrathecal sodium nitroprusside, oral tadalafil, perforators, vasodilations, retrograde transmission, the 10, 000-fold effect, long-term potantiation
Procedia PDF Downloads 3635164 Improving Dyeability of Cotton Fabric with Juglans regia L. Natural Dyestuff
Authors: M. Heysem Arslan, Ikilem Gocek, U. Kivanc Sahin
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Natural dyestuff, extracted from Juglans Regia L., a kind of walnut, was used to dye 100% cotton gabardine fabric. The main goal of this study was to enhance dyeing process of cotton fabric with Juglans Regia L. dyestuff in terms of color fastness values by designing and developing a mordant application process. Within the context of this study, different mordants such as tannic acid, gallic acid, ascorbic acid, potassium sodium tartrate tetrahydrate, calcium carbonate, iron (II) sulphate heptahydrate, aluminum potassium sulphate dodecahydrate and their combinations were applied in the mordanting processes. Spectrophotometric analysis, color fastness to washing and color fastness to light tests were carried out on the fabric samples. In this study, it was shown that by using the right combination of mordants with a proper application process, it is possible to improve color fastness values of cotton fabric samples dyed with natural dyestuff.Keywords: extraction, Juglans Regia L., mordanting process, natural dyestuff
Procedia PDF Downloads 3105163 Synthesis, Characterization and Coating of the Zinc Oxide Nanoparticles on Cotton Fabric by Mechanical Thermo-Fixation Techniques to Impart Antimicrobial Activity
Authors: Imana Shahrin Tania, Mohammad Ali
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The present study reports the synthesis, characterization and application of nano-sized zinc-oxide (ZnO) particles on a cotton fabric surface. The aim of the investigations is to impart the antimicrobial activity on textile cloth. Nanoparticle is synthesized by wet chemical method from zinc sulphate and sodium hydroxide. SEM (scanning electron micrograph) images are taken to demonstrate the surface morphology of nanoparticles. XRD analysis is done to determine the crystal size of the nanoparticle. With the conformation of nanoformation, the cotton woven fabric is treated with ZnO nanoparticle by mechanical thermo-fixation (pad-dry-cure) technique. To increase the wash durability of nano treated fabric, an acrylic binder is used as a fixing agent. The treated fabric shows up to 90% bacterial reduction for S. aureus (Staphylococcus aureus) and 87% for E. coli (Escherichia coli) which is appreciable for bacteria protective clothing.Keywords: nanoparticle, zinc oxide, cotton fabric, antibacterial activity, binder
Procedia PDF Downloads 1325162 Development of a Digital Healthcare Intervention to Reduce Digital and Healthcare Inequality in Rural Communities with a Focus on Hypertensive Management
Authors: Festus Adedoyin, Nana Mbeah Otoo, Sofia Meacham
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Hypertension is one of the main health issues in Ghana, where prevalence is higher in rural than in urban areas. This is due to the challenges rural areas have in accessing technology and healthcare services for hypertension control. This study's goal is to create a digital healthcare solution to alleviate this inequality. Through an analysis of current technology and problems, using the ring onion methodology, the study determined the needs for the intervention and evaluated healthcare disparities. An online application with teleconsultation capabilities, reminder mechanisms, and clinical decision support is part of the suggested solution. In outlying areas, mobile clinics in containers with the required equipment will be established. Heuristic evaluation and think-aloud sessions were used to assess the prototype's usability and navigational problems. This study highlights the need to develop digital health interventions to help manage hypertension in rural locations and decrease healthcare disparities. To develop and improve digital healthcare solutions for rural areas worldwide and in Ghana, this study might be used as a tool for future research.Keywords: digital health, health inequalities, hypertension management, rural areas
Procedia PDF Downloads 1095161 Marine Phytoplankton and Zooplankton from the North-Eastern Bay of Bengal, Bangladesh
Authors: Mahmudur Rahman Khan, Saima Sharif Nilla, Kawser Ahmed, Abdul Aziz
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The marine phyto and zooplankton of the extreme north-eastern part of the Bay of Bengal, off the coast of Bangladesh have been studied. Relative occurrence of phyto and zooplankton and their relationship with physico-chemical conditions (f.e. temperature, salinity, dissolved oxygen, carbonate, phosphate, and sulphate) of the water and Shannon-Weiber diversity indices were also studied. The phytoplankton communities represented by 25 genera with 69 species of Bacillariophyceae, 5 genera with 12 species of Dinophyceae and 6 genera with 16 species of Chlorophyceae have been found. A total of 24 genera of 25 species belonging to Protozoa, Coelenterata, Chaetognatha, Nematoda, Cladocera, Copepoda, and decapoda have been recorded. In addition, the average phytoplankton was 80% of all collections, whereas the zooplankton was 20%, Z ratio of about 4:1. The total numbers of plankton individuals per liter were generally higher during low tide than those of high one. Shannon-Weiber diversity indices were highest (3.675 for phytoplankton and 3.021 for zooplankton) in the north-east part and lowest (1.516 for phytoplankton and 1.302 for zooplankton) in the south-east part of the study area. Principal Component Analysis (PCA) showed the relationship between pH and some species of phyto and zooplankton where all diatoms and copepods have showed positive correlation and dinoflagellates showed negative correlation with pH.Keywords: plankton presence, shannon-weiber diversity index, principal component analysis, Bay of Bengal
Procedia PDF Downloads 6605160 Right to Return and Narrative in Refugee Camps: Case Study in Palestinian Displacement
Authors: Naomi I. Austin
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Following WWII, the Geneva Conventions and Universal Declaration of Human Rights declared the right to return an unalienable right. The right to return has been disputed by the Israeli government and upheld as an individual by prominent Palestinian activists. Those who contest the Palestinian right to return argue that it would effectively end the state of Israel. After the conquest of Lebanon, the concept of a two-state solution has been effectively shut down. This research paper will seek to utilize interviews from NGO actors and those displaced to be gathered from fieldwork conducted in refugee camps and bases of international actors, exploring durable and multilateral solutions for not only the refugee crisis but the forced displacement of Palestinians that go beyond state actors and government entities. The research will center on the perspective of those displaced to generate a plausible solution to mitigate negative effects on displaced persons. This paper will seek to address whether the right to return is plausible with the expansion of Israeli territorial conquest and the impact of the Israeli expansion on migrations within the Mediterranean region and the EU, especially with policies of integration into the host community.Keywords: durable solutions, forced displacement, protracted conflict, refugee studies, narrative building, memory, right to return
Procedia PDF Downloads 165159 Pharmacokinetic Study of Clarithromycin in Human Female of Pakistani Population
Authors: Atifa Mushtaq, Tanweer Khaliq, Hafiz Alam Sher, Asia Farid, Anila Kanwal, Maliha Sarfraz
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The study was designed to assess the various pharmacokinetic parameters of a commercially available clarithromycin Tablet (Klaricid® 250 mg Abbot, Pakistan) in plasma sample of healthy adult female volunteers by applying a rapid, sensitive and accurate HPLC-UV analytical method. The human plasma samples were evaluated by using an isocratic High Performance Liquid Chromatography (HPLC) system of Sykam consisted of a pump with a column C18 column (250×4.6mn, 5µm) UV-detector. The mobile phase comprises of potassium dihydrogen phosphate (50 mM, pH 6.8, contained 0.7% triethylamine), methanol and acetonitrile (30:25:45, v/v/v) was delivered with injection volume of 20µL at flow rate of 1 mL/min. The detection was performed at λmax 275 nm. By applying this method, important pharmacokinetic parameters Cmax, Tmax, Area under curve (AUC), half-life (t1/2), , Volume of distribution (Vd) and Clearance (Cl) were measured. The parameters of pharmacokinetics of clarithromycin were calculated by software (APO) pharmacological analysis. Maximum plasma concentrations Cmax 2.78 ±0.33 µg/ml, time to reach maximum concentration tmax 2.82 ± 0.11 h and Area under curve AUC was 20.14 h.µg/ml. The mean ± SD values obtained for the pharmacokinetic parameters showed a significant difference in pharmacokinetic parameters observed in previous literature which emphasizes the need for dose adjustment of clarithromycin in Pakistani population.Keywords: Pharmacokinetc, Clarothromycin, HPLC, Pakistan
Procedia PDF Downloads 1085158 Green Technologies Developed by JSC “NIUIF”
Authors: Andrey Norov
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In the recent years, Samoilov Research Institute for Mineral Fertilizers JSC “NIUIF”, the oldest (established in September 1919) industry-oriented institute in Russia, has developed a range of sustainable, environment-friendly, zero-waste technologies that ensure minimal consumption of materials and energy resources and fully consistent with the principles of Green Chemistry that include: - Ecofriendly energy and resource saving technology of sulfuric acid from sulfur according to DC-DA scheme (double conversion - double absorption); - Improved zero-waste technology of wet phosphoric acid (WPA) by dihydrate-hemihydrate process applicable to various types of phosphate raw materials; - Flexible, efficient, zero-waste, universal technology of NP / NPS / NPK / NPKS fertilizers with maximum heat recovery from chemical processes; - Novel, zero-waste, no-analogue technology of granular PK / PKS / NPKS fertilizers with controlled dissolution rate and nutrient supply into the soil, which allows to process a number of wastes and by-products; - Innovative resource-saving joint processing of wastes from the production of phosphogypsum and fluorosilicic acid (FSA) into ammonium sulfate with simultaneous neutralization of fluoride compounds with no lime used. - New fertilizer technology of increased environmental and agrochemical efficiency (currently under development). All listed green technologies are patented with Russian and Eurasian patents. The development of ecofriendly, safe, green technologies is ongoing in JSC “NIUIF”.Keywords: NPKS fertilizers, FSA, sulfuric acid, WPA
Procedia PDF Downloads 945157 A Distinct Reversed-Phase High-Performance Liquid Chromatography Method for Simultaneous Quantification of Evogliptin Tartrate and Metformin HCl in Pharmaceutical Dosage Forms
Authors: Rajeshkumar Kanubhai Patel, Neha Sudhirkumar Mochi
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A simple and accurate stability-indicating, reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed and validated for the simultaneous quantitation of Evogliptin tartrate and Metformin HCl in pharmaceutical dosage forms, following ICH guidelines. Forced degradation was performed under various stress conditions including acid, base, oxidation, thermal, and photodegradation. The method utilized an Eclipse C18 column (250 mm × 4.6 mm, 5 µm) with a mobile phase of 5 mM 1-hexane sulfonic acid sodium salt in water and 0.2% v/v TEA (45:55 %v/v), adjusted to pH 3.0 with OPA, at a flow rate of 1.0 mL/min. Detection at 254.4 nm using a PDA detector showed good resolution of degradation products and both drugs. Linearity was observed within 1-5 µg/mL for Evogliptin tartrate and 100-500 µg/mL for Metformin HCl, with % recovery between 99-100% and precision within acceptable limits (%RSD < 2%). The method proved to be specific, precise, accurate, and robust for routine analysis of these drugs.Keywords: stability indicating RP-HPLC, evogliptin tartrate, metformin HCl, validation
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