Search results for: fiscal reaction function

Authors: Jamal Abd Awadallak, Thiago Olinek Reinehr, Eduardo Raizer, Deise Molinari, Edson Antonio, Camila da Silva da Silva

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The hydrolysis of soy oil catalyzed by 1,3-specific enzyme (Lecitase Ultra) in a well-stirred bioreactor was studied. Two forms of applications of the ultrasound were evaluated aiming to increase reaction rates, wherein the use of probe ultrasound associated with the use of surfactant to pre-emulsify the substrate showed the best results. Two different reaction periods were found: the first where the ultrasound has great influence on reaction rates, and the second where ultrasound influence is minimal. Studies on the time of pre-emulsification, surfactant concentration and enzyme concentration showed that the initial rate of hydrolysis depends on the interfacial area between the oil phase and the aqueous phase containing the enzyme.

Keywords: specific enzyme, free fatty acids, Hydrolysis, lecitase ultra, ultrasound

Procedia PDF Downloads 582

Authors: Bina Kumari, Subir K. Sarkar, Pradipta Bandyopadhyay

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The autocorrelation function of the density fluctuation is studied in each of the two phases in a Gibbs Ensemble Monte Carlo (GEMC) simulation of the problem of phase separation for a square well potential with various values of its range. We find that the normalized autocorrelation function is described very well as a linear combination of an exponential function with a time scale τ₂ and a stretched exponential function with a time scale τ₁ and an exponent α. Dependence of (α, τ₁, τ₂) on the parameters of the GEMC algorithm and the range of the square well potential is investigated and interpreted. We also analyse the issue of how to choose the parameters of the GEMC simulation optimally.

Keywords: autocorrelation function, density fluctuation, GEMC, simulation

Procedia PDF Downloads 194

Authors: Karim Hrratha, Khaled Essalahb, Christophe Morellc, Henry Chermettec, Salima Boughdiria

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Among the carbon-carbon bond formation types, allylation of active methylene compounds with cyclic Baylis-Hillman (BH) alcohols is a reliable and widely used method. This reaction is a very attractive tool in organic synthesis of biological and biodiesel compounds. Thus, in view of an insistent and peremptory request for an efficient and straightly method for synthesizing the desired product, a thorough analysis of various aspects of the reaction processes is an important task. The product afforded by the reaction of active methylene with BH alcohols depends largely on the experimental conditions, notably on the catalyst properties. All experiments reported that catalysis is needed for this reaction type because of the poor ability of alcohol hydroxyl group to be as a suitable leaving group. Within the catalysts, several transition- metal based have been used such as palladium in the presence of acid or base and have been considered as reliable methods. Furthemore, acid catalysts such as BF3.OEt2, BiX3 (X= Cl, Br, I, (OTf)3), InCl3, Yb(OTf)3, FeCl3, p-TsOH and H-montmorillonite have been employed to activate the C-C bond formation through the alkylation of active methylene compounds. Interestingly a report of a smoothly process for the ability of 4-imethyaminopyridine(DMAP) to catalyze the allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol appeared recently. However, the reaction mechanism remains ambiguous, since the C- allylation process leads to an unexpected product (noted P1), corresponding to a direct allylation instead of conjugate allylation, which involves the most electrophilic center according to the electron withdrawing group CO effect. The main objective of the present theoretical study is to better understand the role of the DMAP catalytic activity as well as the process leading to the end- product (P1) for the catalytic reaction of a cyclic BH alcohol with active methylene compounds. For that purpose, we have carried out computations of a set of active methylene compounds varying by R1 and R2 toward the same alcohol, and we have attempted to rationalize the mechanisms thanks to the acid–base approach, and conceptual DFT tools such as chemical potential, hardness, Fukui functions, electrophilicity index and dual descriptor, as these approaches have shown a good prediction of reactions products.The present work is then organized as follows: In a first part some computational details will be given, introducing the reactivity indexes used in the present work, then Section 3 is dedicated to the discussion of the prediction of the selectivity and regioselectivity. The paper ends with some concluding remarks. In this work, we have shown, through DFT method at the B3LYP/6-311++G(d,p) level of theory that: The allylation of active methylene compounds with cyclic BH alcohol is governed by orbital control character. Hence the end- product denoted P1 is generated by direct allylation.

Keywords: DFT calculation, gas phase pKa, theoretical mechanism, orbital control, charge control, Fukui function, transition state

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Authors: Mustafa Sertçelik, Hacali Necefoğlu, Turan Çalban, Soner Kuşlu

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In this study, Chevreul’s salt was dissolved in ammonium chloride solutions. All experiments were performed in a batch reactor. The obtained results were optimized. Parameters used in the experiments were the reaction temperature, the ammonium chloride concentration, the reaction time and the solid-to-liquid ratio. The optimum conditions were determined by 2⁴ factorial experimental design method. The best values of four parameters were determined as based on the experiment results. After the evaluation of experiment results, all parameters were found as effective in experiment conditions selected. The optimum conditions on the maximum Chevreul’s salt dissolution were the ammonium chloride concentration 4.5 M, the reaction time 13.2 min., the reaction temperature 25 ^oC, and the solid-to-liquid ratio 9/80 g.mL^-1. The best dissolution yield in these conditions was 96.20%.

Keywords: Chevreul's salt, factorial experimental design method, ammonium chloride, dissolution, optimization

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Authors: Haseen Siddiqui, Sanjay M. Mahajani

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Various important reactions in chemical and metallurgical industries fall in the category of gas-solid reactions. These reactions can be categorized as catalytic and non-catalytic gas-solid reactions. In gas-solid reaction systems, heat and mass transfer limitations put an appreciable influence on the rate of the reaction. The consequences can be unavoidable for overlooking such effects while collecting the reaction rate data for the design of the reactor. Pyrolysis reaction comes in this category that involves the production of gases due to the interaction of heat and solid substance. Pyrolysis is also an important step in the gasification process and therefore, the gasification reactivity majorly influenced by the pyrolysis process that produces the char, as a feed for the gasification process. Therefore, in the present study, a non-isothermal transient 1-D model is developed for a single biomass pellet to investigate the effect of heat and mass transfer limitations on the rate of pyrolysis reaction. The obtained set of partial differential equations are firstly discretized using the concept of ‘method of lines’ to obtain a set of ordinary differential equation with respect to time. These equations are solved, then, using MATLAB ode solver ode15s. The model is capable of incorporating structural changes, porosity variation, variation in various thermal properties and various pellet shapes. The model is used to analyze the effectiveness factor for different values of Lewis number and heat of reaction (G factor). Lewis number includes the effect of thermal conductivity of the solid pellet. Higher the Lewis number, the higher will be the thermal conductivity of the solid. The effectiveness factor was found to be decreasing with decreasing Lewis number due to the fact that smaller Lewis numbers retard the rate of heat transfer inside the pellet owing to a lower rate of pyrolysis reaction. G factor includes the effect of the heat of reaction. Since the pyrolysis reaction is endothermic in nature, the G factor takes negative values. The more the negative value higher will be endothermic nature of the pyrolysis reaction. The effectiveness factor was found to be decreasing with more negative values of the G factor. This behavior can be attributed to the fact that more negative value of G factor would result in more energy consumption by the reaction owing to a larger temperature gradient inside the pellet. Further, the analytical expressions are also derived for gas and solid concentrations and effectiveness factor for two limiting cases of the general model developed. The two limiting cases of the model are categorized as the homogeneous model and unreacted shrinking core model.

Keywords: effectiveness factor, G-factor, homogeneous model, lewis number, non-catalytic, shrinking core model

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Authors: Hamad Almohamadi, Nabeel H. Alharthi, Abdulrahman Aljabri

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In this study, two-dimensional CuFeOx is deposited on nickel foam for the fabrication of electrocatalyst for oxygen evolution reaction (OER). The in-situ hydrothermal synthesis of CuFeOx in presence of aloe vera extract was found to yield unique nano-rose-like morphology which aided to improve the electrochemical surface area of the electrode. The phytochemical assisted synthesis of CuFeOx using 75% aloe vera extract resulted in improved OER electrocatalytic performance by attaining the overpotential of 310 mV for 50 mA cm−2 and 410 mV for 100 mA cm−2. The electrode also sustained robust stability throughout the 50 h of chronopotentiometry studies under alkaline electrolyte conditions, thus proving to be prospective electrode material for efficient OER in electrochemical water splitting.

Keywords: water splitting, phytochemicals, oxygen evaluation reaction, Tafel's slope, stability

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Authors: Yuan Zheng

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3D model-based vehicle matching provides a new way for vehicle recognition, localization and tracking. Its key is to construct an evaluation function, also called fitness function, to measure the degree of vehicle matching. The existing fitness functions often poorly perform when the clutter and occlusion exist in traffic scenarios. In this paper, we present a practical and efficient fitness function. Unlike the existing evaluation functions, the proposed fitness function is to study the vehicle matching problem from both local and global perspectives, which exploits the pixel gradient information as well as the silhouette information. In view of the discrepancy between 3D vehicle model and real vehicle, a weighting strategy is introduced to differently treat the fitting of the model’s wireframes. Additionally, a normalization operation for the model’s projection is performed to improve the accuracy of the matching. Experimental results on real traffic videos reveal that the proposed fitness function is efficient and robust to the cluttered background and partial occlusion.

Keywords: 3D-2D matching, fitness function, 3D vehicle model, local image gradient, silhouette information

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Authors: Valeria Butera, Norihisa Fukaya, Jun-Chu Choi, Kazuhiko Sato, Yoong-Kee Choe

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Several silicon dioxide sources can react with dimethyl carbonate (DMC) in presence of alkali bases catalysts to ultimately produce tetramethoxysilane (TMOS). Experimental findings suggested that the reaction proceeds through several steps in which the first molecule of DMC is converted to dimethylsilyloxide (DMOS) and CO₂. Following the same mechanistic steps, a second molecule of DMC reacts with the DMOS to afford the final product TMOS. Using a cluster model approach, a quantum-mechanical investigation of the first part of the reaction leading to DMOS formation is reported with a twofold purpose: (1) verify the viability of the reaction mechanism proposed on the basis of experimental evidences .(2) compare the behaviors of three different alkali hydroxides MOH, where M=Li, K and Cs, to determine whether diverse ionic radius and charge density can be considered responsible for the observed differences in reactivity. Our findings confirm the observed experimental trend and furnish important information about the effective role of the alkali hydroxides giving an explanation of the different catalytic activity of the three metal cations.

Keywords: Alcoxysilanes production, cluster model approach, DFT, DMC conversion

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Authors: Julia R. Beulig, Stefan Ohla, Detlev Belder

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In contrast to off-line analytical methods, lab-on-a-chip technology delivers direct information about the observed reaction. Therefore, microfluidic devices make an important scientific contribution, e.g. in the field of synthetic chemistry. Herein, the rapid generation of analytical data can be applied for the optimization of chemical reactions. These microfluidic devices enable a fast change of reaction conditions as well as a resource saving method of operation. In the presented work, we focus on the investigation of multiphase regimes, more specifically on a biphasic microfluidic droplet systems. Here, every single droplet is a reaction container with customized conditions. The biggest challenge is the rapid qualitative and quantitative readout of information as most detection techniques for droplet systems are non-specific, time-consuming or too slow. An exception is the electrospray mass spectrometry (ESI-MS). The combination of a reaction screening platform with a rapid and specific detection method is an important step in droplet-based microfluidics. In this work, we present a novel approach for synthesis optimization on the nanoliter scale with direct ESI-MS detection. The development of a droplet-based microfluidic device, which enables the modification of different parameters while simultaneously monitoring the effect on the reaction within a single run, is shown. By common soft- and photolithographic techniques a polydimethylsiloxane (PDMS) microfluidic chip with different functionalities is developed. As an interface for the MS detection, we use a steel capillary for ESI and improve the spray stability with a Teflon siphon tubing, which is inserted underneath the steel capillary. By optimizing the flow rates, it is possible to screen parameters of various reactions, this is exemplarity shown by a Domino Knoevenagel Hetero-Diels-Alder reaction. Different starting materials, catalyst concentrations and solvent compositions are investigated. Due to the high repetition rate of the droplet production, each set of reaction condition is examined hundreds of times. As a result, of the investigation, we receive possible reagents, the ideal water-methanol ratio of the solvent and the most effective catalyst concentration. The developed system can help to determine important information about the optimal parameters of a reaction within a short time. With this novel tool, we make an important step on the field of combining droplet-based microfluidics with organic reaction screening.

Keywords: droplet, mass spectrometry, microfluidics, organic reaction, screening

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Authors: Y. J. Song, Q. S. Xu, X. C. Wang, H. Wang, C. Q. Li

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The catalyst of copper oxide loaded on HZSM-5 was developed for nitrous oxide (N₂O) direct decomposition. The kinetic of nitrous oxide decomposition was studied for CuO/HZSM-5 catalyst prepared by incipient wetness impregnation method. The external and internal diffusion of catalytic reaction were considered in the investigation. Experiment results indicated that the external diffusion was basically eliminated when the reaction gas mixture gas hourly space velocity (GHSV) was higher than 9000h⁻¹ and the influence of the internal diffusion was negligible when the particle size of the catalyst CuO/HZSM-5 was small than 40-60 mesh. The experiment results showed that the kinetic of catalytic decomposition of N₂O was a first-order reaction and the activation energy and the pre-factor of the kinetic equation were 115.15kJ/mol and of 1.6×109, respectively.

Keywords: catalytic decomposition, CuO/HZSM-5, kinetic, nitrous oxide

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Authors: Gabor Varga, Krisztina Karadi, Zoltan Konya, Akos Kukovecz, Pal Sipos, Istvan Palinko

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Nickel can efficiently replace palladium in the Heck, Suzuki and Negishi reactions. This study focuses on the synthesis and catalytic application of Ni(II)-containing layered double hydroxides (LDHs) and layered triple hydroxides (LTHs). Our goals were to incorporate Ni(II) ions among the layers of LDHs or LTHs, or binding it to their surface or building it into their layers in such a way that their catalytic activities are maintained or even increased. The LDHs and LTHs were prepared by the co-precipitation method using ethylene glycol as co-solvent. In several cases, post-synthetic modifications (e.g., thermal treatment) were performed. After optimizing the synthesis conditions, the composites displayed good crystallinity and were free of byproducts. The success of the syntheses and the post-synthetic modifications was confirmed by relevant characterization methods (XRD, SEM, SEM-EDX and combined IR techniques). Catalytic activities of the produced and well-characterized solids were investigated through the Heck reaction. The composites behaved as efficient, recyclable catalysts in the Heck reaction between 4-bromoanisole and styrene. Through varying the reaction parameters, we were able to obtain acceptable conversions under mild conditions. Our study highlights the possibility of the application of Ni(II)-containing composites as efficient catalysts in coupling reactions.

Keywords: layered double hydroxide, layered triple hydroxide, heterogeneous catalysis, heck reaction

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Authors: A. Amar

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Analysis of the elastic scattering of protons on ¹⁰B nuclei has been done in the framework of the optical model and single folding model at the beam energies up to 17 MeV. We could enhance the optical potential parameters using Esis88 Code, as well as SPI GENOA Code. Linear relationship between volume real potential (V₀) and proton energy (E_p) has been obtained. Also, surface imaginary potential W_D is proportional to the proton energy (E_p) in the range 0.400 and 17 MeV. The radiative reaction ¹⁰B(p,γ)¹¹C has been analyzed using potential model. A comparison between ¹⁰B(p,γ)¹¹C and ⁶Li(p,γ)⁷Be has been made. Good agreement has been found between theoretical and experimental results in the whole range of energy. The radiative resonance reaction ⁷Li(p,γ)⁸Be has been studied.

Keywords: elastic scattering of protons on 10B nuclei, optical potential parameters, potential model, radiative reaction

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Authors: E. Moroydor Derun, N. Tugrul, F. T. Senberber, A. S. Kipcak, S. Piskin

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In this research, copper borates are synthesized by the reaction of copper sulfate pentahydrate (CuSO4.5H2O) and tincalconite (Na2O4B7.10H2O). The experimental parameters are selected as 80°C reaction temperature and 60 of reaction time. The effect of mole ratio of CuSO4.5H2O to Na2O4B7.5H2O is studied. For the identification analyses X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques are used. At the end of the experiments, synthesized copper borate is matched with the powder diffraction file of “00-001-0472” [Cu(BO2)2] and characteristic vibrations between B and O atoms are seen. The proper crystals are obtained at the mole ratio of 3:1. This study showed that simplified synthesis process is suitable for the production of copper borate minerals.

Keywords: hydrothermal synthesis, copper borates, copper sulfate, tincalconite

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Authors: Adrien Cornille, Marine Blain, Bernard Boutevin, Sylvain Caillol

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Generally, linear polyurethanes (PUs) are obtained by the reaction between an oligomeric diol, a short diol as chain extender and a diisocyanate. However the use of diisocyanate should be avoided since they are generally very harmful for human health. Therefore the synthesis of NIPUs (non isocyanate PUs) from step growth polymerization of dicyclocarbonates and diamines should be favoured. This method is particularly interesting since no hazardous isocyanates are used. Thus, this reaction, extensively studied by Endo et al. is currently gaining a lot of attention as a substitution route for the synthesis of NIPUs, both from industrial and academic community. However, the reactivity of reaction between amine and cyclic carbonate is a major scientific issue, since cyclic carbonates are poorly reactive. Thus, our team developed several synthetic ways for the synthesis of various di-cyclic carbonates based on C5-, C6- and dithio- cyclic carbonates, from different biobased raw materials (glycerin isosorbide, vegetable oils…). These monomers were used to synthesize NIPUs with various mechanical and thermal properties for various applications. We studied the reactivity of reaction with various catalysts and find optimized conditions for room temperature reaction. We also studied the radical copolymerization of cyclic carbonate monomers in styrene-acrylate copolymers for coating applications. We also succeeded in the elaboration of biobased NIPU flexible foams. To the best of our knowledge, there is no report in literature on the preparation of non-isocyanate polyurethane foams.

Keywords: foam, nonisocyanate polyurethane, cyclic carbonate, blowing agent, scanning electron microscopy

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Authors: S. S. L. Andrade, E. A. Souza, L. C. L. Santos, C. Moraes, A. K. C. L. Lobato

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Biodiesel may be produced through transesterification reaction (or alcoholysis), that is the transformation of a long chain fatty acid in an alkyl ester. This reaction can occur in the presence of acid catalysts, alkali, or enzyme. Currently, for industrial processes, biodiesel is produced by alkaline route. The alkali most commonly used in these processes is hydroxides and methoxides of sodium and potassium. In this work, biodiesel production was conducted in two different systems. The first consisted of a batch reactor operating with a traditional washing system and the second consisted of a semi-continuous flow reactor operating with a membrane separation system. Potassium hydroxides was used as catalyst at a concentration of 1% by weight, the molar ratio oil/alcohol was 1/9 and temperature of 55 °C. Tests were performed using soybeans and palm oil and the ester conversion results were compared for both systems. It can be seen that the results for both oils are similar when using the batch reator or the semi-continuous flow reactor. The use of the semi-continuous flow reactor allows the removal of the formed products. Thus, in the case of a reversible reaction, with the removal of reaction products, the concentration of the reagents becomes higher and the equilibrium reaction is shifted towards the formation of more products. The higher conversion to ester with soybean and palm oil using the batch reactor was approximately 98%. In contrast, it was observed a conversion of 99% when using the same operating condition on a semi-continuous flow reactor.

Keywords: biodiesel, batch reactor, semi-continuous flow reactor, transesterification

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Authors: Yongde Xia, Laicong Deng, Zhuxian Yang

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Developing cost-effective electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is vital in energy conversion and storage applications. Herein, we report a simple method for the synthesis of graphene-reinforced cobalt sulfide/carbon nanocomposites and the evaluation of their electrocatalytic performance for typical electrocatalytic reactions. Nanocomposites of cobalt sulfide embedded in N, S co-doped porous carbon and graphene (CoS@C/Graphene) were generated via simultaneous sulfurization and carbonization of one-pot synthesized graphite oxide-ZIF-67 precursors. The obtained CoS@C/Graphene nanocomposite was characterized by X-ray diffraction, Raman spectroscopy, Thermogravimetric analysis-Mass spectroscopy, Scanning electronic microscopy, Transmission electronic microscopy, X-ray photoelectron spectroscopy and gas sorption. It was found that cobalt sulfide nanoparticles were homogenously dispersed in the in-situ formed N, S co-doped porous carbon/Graphene matrix. The CoS@C/10Graphene composite not only shows excellent electrocatalytic activity toward ORR with high onset potential of 0.89 V, four-electron pathway and superior durability of maintaining 98% current after continuously running for around 5 hours, but also exhibits good performance for OER and HER, due to the improved electrical conductivity, increased catalytic active sites and connectivity between the electrocatalytic active cobalt sulfide and the carbon matrix. This work offers a new approach for the development of novel multifunctional nanocomposites for the next generation of energy conversion and storage applications.

Keywords: MOF derivative, graphene, electrocatalyst, oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction

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Authors: Jiahui You, Kyung Jae Lee

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Hydraulic fracturing fluid (HFF) is widely used in shale reservoir productions. HFF contains diverse chemical additives, which result in the dissolution and precipitation of minerals through multiple chemical reactions. In this study, a new pore-scale Darcy–Brinkman–Stokes (DBS) model coupled with Level Set Method (LSM) is developed to address the microscopic phenomena occurring during the iron–HFF interaction, by numerically describing mass transport, chemical reactions, and pore structure evolution. The new model is developed based on OpenFOAM, which is an open-source platform for computational fluid dynamics. Here, the DBS momentum equation is used to solve for velocity by accounting for the fluid-solid mass transfer; an advection-diffusion equation is used to compute the distribution of injected HFF and iron. The reaction–induced pore evolution is captured by applying the LSM, where the solid-liquid interface is updated by solving the level set distance function and reinitialized to a signed distance function. Then, a smoothened Heaviside function gives a smoothed solid-liquid interface over a narrow band with a fixed thickness. The stated equations are discretized by the finite volume method, while the re-initialized equation is discretized by the central difference method. Gauss linear upwind scheme is used to solve the level set distance function, and the Pressure–Implicit with Splitting of Operators (PISO) method is used to solve the momentum equation. The numerical result is compared with 1–D analytical solution of fluid-solid interface for reaction-diffusion problems. Sensitivity analysis is conducted with various Damkohler number (DaII) and Peclet number (Pe). We categorize the Fe (III) precipitation into three patterns as a function of DaII and Pe: symmetrical smoothed growth, unsymmetrical growth, and dendritic growth. Pe and DaII significantly affect the location of precipitation, which is critical in determining the injection parameters of hydraulic fracturing. When DaII<1, the precipitation uniformly occurs on the solid surface both in upstream and downstream directions. When DaII>1, the precipitation mainly occurs on the solid surface in an upstream direction. When Pe>1, Fe (II) transported deeply into and precipitated inside the pores. When Pe<1, the precipitation of Fe (III) occurs mainly on the solid surface in an upstream direction, and they are easily precipitated inside the small pore structures. The porosity–permeability relationship is subsequently presented. This pore-scale model allows high confidence in the description of Fe (II) dissolution, transport, and Fe (III) precipitation. The model shows fast convergence and requires a low computational load. The results can provide reliable guidance for injecting HFF in shale reservoirs to avoid clogging and wellbore pollution. Understanding Fe (III) precipitation, and Fe (II) release and transport behaviors give rise to a highly efficient hydraulic fracture project.

Keywords: reactive-transport , Shale, Kerogen, precipitation

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Authors: Risikat Oladoyin S. Dauda, Onyebuchi Iwegbu

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This study investigates the response of human development outcomes to selected macroeconomic indicators in Nigeria. Human development outcomes is measured by human development index while the selected macroeconomic variables are inflation rate, real interest rate, government capital expenditure, real exchange rate, current account balance, and savings. Structural Vector Autoregression (SVAR) technique is employed in examining the response of human development index to the macroeconomic shocks. The result from the forecast error variance decomposition and Impulse-Response analysis reveals that fiscal policy (government capital expenditure) shock is the greatest determinant of human development outcomes. This result reiterates the role which the government plays in improving the welfare of the citizenry. The fiscal policy tool is pivotal in human development which comes in the form of investment in education, health, housing, and infrastructure. Further conclusion drawn from this study is that human development outcome positively and significantly responds to shocks from real interest rate, a monetary policy transmission variable and is felt greatly in the short run period. The policy implication of this study is that if capital budget implementation falls below expectations, human development will be engendered. Hence, efforts should be made to ensure that full implementation and appraisal of government capital expenditure is taken sacrosanct as any shock from such plan, engenders human development outcome.

Keywords: human development outcome, macroeconomic outcomes, structural vector autoregression, SVAR

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Authors: Mohammedi Ferhate

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This paper deals with the generalized the notion of the function of wave a micro particle moving free, the concept of the linear operator in the representation function delta of Dirac which is a generalization of the symbol of Kronecker to the case of a continuous variation of the sizes concerned with the condition of orthonormation of the Eigen functions the use of linear operators and their Eigen functions in connection with the solution of given differential equations, it is of interest to study the properties of the operators themselves and determine which of them follow purely from the nature of the operators, without reference to specific forms of Eigen functions. The models simulation examples are also presented.

Keywords: function, operator, simulation, wave

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Authors: Vishal D. Bharud, B. J. Patil, S. S. Dahiwale, V. N. Bhoraskar, S. D. Dhole

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Photon induced average reaction cross section of ¹¹¹Cd (γ, γ`) ¹¹¹ᵐCd reaction was experimentally determined for the bremsstrahlung energy spectrum of 6 MeV by utilizing the activation and offline γ-ray spectrometric techniques. The 6 MeV electron accelerator Racetrack Microtron of Savitribai Phule Pune University, Pune was used for the experimental work. The bremsstrahlung spectrum generated by bombarding 6 MeV electrons on lead target was theoretically estimated by FLUKA code. Bremsstrahlung radiation can have energies exceeding the threshold of the particle emission, which is normally above 6 MeV. Photons of energies below the particle emission threshold undergo absorption into discrete energy levels, with possibility of exciting nuclei to excited state including metastable state. The ¹¹¹Cd (γ, γ`) ¹¹¹ᵐCd reaction cross sections were calculated at different energies of bombarding Photon by using the TALYS 1.8 computer code with a default parameter. The focus of the present work was to study the (γ,γ’) reaction for exciting ¹¹¹Cd nuclei to metastable states which have threshold energy below 3 MeV. The flux weighted average cross section was obtained from the theoretical values of TALYS 1.8 and TENDL 2017 and is found to be in good agreement with the present experimental cross section.

Keywords: bremsstrahlung, cross section, FLUKA, TALYS-1.8

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Authors: Aleksandra Łochowicz, Daria Świętochowska, Loredano Pollegioni, Nazim Ocal, Franck Charmantray, Laurence Hecquet, Katarzyna Szymańska

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Multienzymatic cascade reactions are nowadays widely used in pharmaceutical, chemical and cosmetics industries to produce high valuable compounds. They can be carried out in two ways, step by step and one-pot. If two or more enzymes are in the same reaction vessel is necessary to work out the compromise to run the reaction in optimal conditions for each enzyme. So far most of the reports of multienzymatic cascades concern on usage of free enzymes. Unfortunately using free enzymes as catalysts of reactions accomplish high cost. What is more, free enzymes are soluble in solvents which makes reuse impossible. To overcome this obstacle enzymes can be immobilized what provides heterogeneity of biocatalyst that enables reuse and easy separation of the enzyme from solvents and reaction products. Usually, immobilization increase also the thermal and operational stability of enzyme. The advantages of using immobilized multienzymes are enhanced enzyme stability, improved cascade enzymatic activity via substrate channeling, and ease of recovery for reuse. The one-pot immobilized multienzymatic cascade can be carried out in mixed or coimmobilized type. When biocatalysts are coimmobilized on the same carrier the are in close contact to each other which increase the reaction rate and catalytic efficiency, and eliminate the lag time. However, in this type providing the optimal conditions both in the process of immobilization and cascade reaction for each enzyme is complicated. Herein, we examined immobilization of 3 enzymes: D-amino acid oxidase from Rhodotorula gracilis, commercially available catalase and transketolase from Geobacillus stearothermophilus. As a support we used silica monoliths with hierarchical structure of pores. Then we checked their stability and reusability in one-pot cascade of L-erythrulose and hydroxypuryvate acid synthesis.

Keywords: biocatalysts, enzyme immobilization, multienzymatic reaction, silica carriers

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Authors: A. M. Iordache, S. M. Iordache, V. Barna, M. Elisa, I. C. Vasiliu, C. R. Stefan, I. Chilibon, I. Stamatin, S. Caramizoiu, C. E. A. Grigorescu

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The general objective of the presentation is the development of an e-tongue like sensor based on modified screen printed electrode (SPE) structures with a receptor part made of porphyrins/metalloporphyrins chemically bound to graphene (the sensitive assembly) to act as antennas and “capture” the histamine molecules. Using a single, ultra-sensitive electrochemical sensor, we measured the concentration of histamine, a compound which is strongly connected to the level of freshness in foods (the caution level of histamine is 50 ppm, whereas the maximum accepted levels range from 200 ppm to 500 ppm). Our approach for the chemical immobilization of the porphyrins onto the surface of the graphenes was via substitution reaction: a solution of graphene in SOCl2 was heated to 800C for 6 hours. Upon cooling, the metallo-porphyrins were added and ultrasonicated for 4 hours. The solution was then allowed to cool to room temperature and then centrifuged in order to separate the deposit. The sensitive assembly was drop casted onto the carbon SPE and cyclic voltammetry was performed in the presence of histamine. The reaction is quasi-reversible and the sensor showed an oxidation potential for histamine at 600 mV. The results indicate a linear dependence of concentration of histamine as function of intensity. The results are reproducible; however the chemical stability of the sensitive assembly is low.

Keywords: histamine, cyclic voltammetry, metallo-porphyrin, food freshness

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Authors: Md. Rashidul Hasan, Atikur Rahman Baizid

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The Bayesian estimation approach is a non-classical estimation technique in statistical inference and is very useful in real world situation. The aim of this paper is to study the Bayes estimators of the parameter of exponential distribution under different loss functions and then compared among them as well as with the classical estimator named maximum likelihood estimator (MLE). In our real life, we always try to minimize the loss and we also want to gather some prior information (distribution) about the problem to solve it accurately. Here the gamma prior is used as the prior distribution of exponential distribution for finding the Bayes estimator. In our study, we also used different symmetric and asymmetric loss functions such as squared error loss function, quadratic loss function, modified linear exponential (MLINEX) loss function and non-linear exponential (NLINEX) loss function. Finally, mean square error (MSE) of the estimators are obtained and then presented graphically.

Keywords: Bayes estimator, maximum likelihood estimator (MLE), modified linear exponential (MLINEX) loss function, Squared Error (SE) loss function, non-linear exponential (NLINEX) loss function

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Authors: Betül Özgenç, Soner Kuşlu, Sabri Çolak, Turan Çalban

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The aim of this study was investigate the leaching kinetics of ulexite in disodium hydrogen phosphate solutions in a mechanical agitation system. Reaction temperature, concentration of disodium hydrogen phosphate solutions, stirring speed, solid/liquid ratio and ulexite particle size were selected as parameters. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase the dissolution rate of ulexite. The activation energy was found to be 63.4 kJ/mol. The leaching of ulexite was controlled by chemical reaction.

Keywords: ulexite, disodium hydrogen phosphate, leaching kinetics

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Authors: Takeyuki Suzuki, Ismiyarto, Da-Yang Zhou, Kaori Asano, Hiroaki Sasai

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The development of catalytic asymmetric reaction is important for the synthesis of natural products. To construct the multiple stereogenic centers, the desymmetrization of meso compounds is powerful strategy for the synthesis of chiral molecules. Oxidative desymmetrization of meso diols using chiral iridium catalyst provides a chiral hydroxyl ketone. The reaction is practical and an environmentally benign method which does not require the use of stoichiometric amount of heavy metals. This time we report here catalytic asymmetric synthesis of catalponol based on tandem coupling of meso-diols and an aldehyde. The tandem reaction includes oxidative desymmetrization of meso-diols, aldol condensation with an aldehyde. The reaction of meso-diol, benzaldehyde in the presence of a catalytic amount of chiral Ir complex and CsOH in tetrahydrofuran afforded the desired benzylidene ketone in 82% yield with 96% ee (enantiomeric excess). Next, we applied this benzylidene ketone derivative to the synthesis of catalponol. The corresponding benzylidene ketone was obtained in 87% yield with 99% ee. Finally, catalponol was synthesized by the regio- and stereo-selective reduction of dienone moiety in good yield.

Keywords: catalponol, desymmetrization, iridium, oxidation

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Authors: Hossein Anaraki-Ardakani, Tayebe Heidari-Rakati

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An environmentally benign protocol for the one-pot, three-component synthesis of Triazolo[1,2-a]indazole-1,3,8-trione derivatives by condensation of dimedone, urazole and aromatic aldehydes catalyzed by HClO4/SiO2 NPS as an ecofriendly catalyst with high catalytic activity and reusability at 100 ºC under solvent-free conditions is reported. The reaction proceeds to completion within 20-30 min in 77-86 % yield.

Keywords: one-pot reaction, dimedone, triazoloindazole, urazole

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Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das

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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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Authors: Parikshit Gogo, N. N. Dutta

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The oxidative enzymes specially laccase (benzenediol: oxygen oxidoreductase, E.C.1.10.3.2) from bacteria, fungi and plants have been playing an important role in green technologies due to their specific advantageous properties. Laccase from different sources and in different forms was used as a biocatalyst in many oxidation and conjugation reactions starting from phenol to hydrocarbons. Tea polyphenols and its derivatives attract the scientific community because of their potential use as antioxidants in food, pharmaceutical and cosmetic industries. Conjugate of polyphenols emerged as a novel materials which shows better stability and antioxidant properties in applied fields. The conjugation reaction of catechin with poly (allylamine) has been studied using free, immobilized and cross-linked enzyme crystals (CLEC) of laccase from Trametes versicolor with particular emphasis on the effect of pertinent variables and kinetic aspects of the reaction. The stability and antioxidant property of the conjugated product was improved as compared to the unconjugated tea polyphenols. The reaction was studied in 11 different solvents in order to deduce the solvent effect through an attempt to correlate the initial reaction rate with solvent properties such as hydrophobicity (logP), water solubility (logSw), electron pair acceptance (ETN) and donation abilities (DNN), polarisibility and dielectric constant which exhibit reasonable correlations. The study revealed, in general that polar solvents favour the initial reaction rate. The kinetics of the conjugation reaction conformed to the so-called Ping-Pong-Bi-Bi mechanism with catechin inhibition. The stability as well as activity of the CLEC was better than the free enzymes and immobilized laccase for practical application. In case of immobilized laccase system marginal diffusional limitation could be inferred from the experimental data. The kinetic parameters estimated by non-linear regression analysis were found to be KmPAA(mM) = 0.75, 1.8967 and Kmcat (mM) = 11.769, 15.1816 for free and immobilized laccase respectively. An attempt has been made to assess the activity of the laccase for the conjugation reaction in relation to other reactions such as dimerisation of ferulic acids and develop a protocol to enhance polyphenol antioxidant activity.

Keywords: laccase, catechin, conjugation reaction, antioxidant properties

Procedia PDF Downloads 273

Authors: Adeola Adenikinju, Olusanya E. Olubusoye, Lateef O. Akinpelu, Dilinna L. Nwobi

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Since the enactment of the Fiscal Responsibility Act (2007), the Federal Government of Nigeria (FGN) has made public its fiscal budget and the subsequent implementation report. A critical review of these documents shows significant variations in the five macroeconomic variables which are inputs in each Presidential budget; oil Production target (mbpd), oil price ($), Foreign exchange rate(N/$), and Gross Domestic Product growth rate (%) and inflation rate (%). This results in underperformance of the Federal budget expected output in terms of non-oil and oil revenue aggregates. This paper evaluates first the existing variance between budgeted and actuals, then the relationship and causality between the determinants of Federal fiscal budget assumptions, and finally the determinants of FGN’s Gross Oil Revenue. The paper employed the use of descriptive statistics, the Autoregressive distributed lag (ARDL) model, and a Profit oil probabilistic model to achieve these objectives. This model permits for both the static and dynamic effect(s) of the independent variable(s) on the dependent variable, unlike a static model that accounts for static or fixed effect(s) only. It offers a technique for checking the existence of a long-run relationship between variables, unlike other tests of cointegration, such as the Engle-Granger and Johansen tests, which consider only non-stationary series that are integrated of the same order. Finally, even with small sample size, the ARDL model is known to generate a valid result, for it is the dependent variable and is the explanatory variable. The results showed that there is a long-run relationship between oil revenue as a proxy for budget performance and its determinants; oil price, produced oil quantity, and foreign exchange rate. There is a short-run relationship between oil revenue and its determinants; oil price, produced oil quantity, and foreign exchange rate. There is a long-run relationship between non-oil revenue and its determinants; inflation rate, GDP growth rate, and foreign exchange rate. The grangers’ causality test results show that there is a mono-directional causality between oil revenue and its determinants. The Federal budget assumptions only explain 68% of oil revenue and 62% of non-oil revenue. There is a mono-directional causality between non-oil revenue and its determinants. The Profit oil Model describes production sharing contracts, joint ventures, and modified carrying arrangements as the greatest contributors to FGN’s gross oil revenue. This provides empirical justification for the selected macroeconomic variables used in the Federal budget design and performance evaluation. The research recommends other variables, debt and money supply, be included in the Federal budget design to explain the Federal budget revenue performance further.

Keywords: ARDL, budget performance, oil price, oil quantity, oil revenue

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Authors: Jihad H. Asad

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An expression for the Green’s function (GF) of anisotropic face cantered cubic (IFCC) lattice is evaluated analytically and numerically for a single impurity problem. The density of states (DOS), phase shift and scattering cross section are expressed in terms of complete elliptic integrals of the first kind.

Keywords: lattice Green's function, elliptic integral, physics, cubic lattice

Procedia PDF Downloads 469