Search results for: nucleophilic substitution
390 Theoretical Evaluation of the Effect of Solvent on the Feasibility of the Reaction of 2-Chlorobenzimidazole With Four N,N′-Cyclic Azomethine Imines to Construct Polycyclic Benzimidazoles
Authors: Mohamed Abdoul-Hakim, A. Zeroual, H. Garmes
Abstract:In this work, we theoretically evaluated the reactivity of four 4-methyl-3-oxo-1,2-pyrazolidinium ylides with 2-Chlorobenzimidazole in MeOH in basic medium using DFT at the B3LYP/6-311+G(d,p) level. The analysis of the results shows that apart from its ability to retain its electrons, the deprotonated 2-Chlorobenzimidazole has a higher nucleophilic character. The reaction requires energy input to initiate the nucleophilic attack of the 2-Chlorobenzimidazole anion, and the inclusion of the solvent effect facilitates the formation of two regioisomers via an intramolecular vinyl nucleophilic substitution (SNVi). The transition states of this latter step are stabilized by charge transfer interactions σ(N-C) →σ*(C-Cl) for the more favorable regioisomer and n(N)→σ*(C-Cl) for the other regioisomer.
Keywords: benzonitrile N-oxide, DFT, intramolecular vinyl nucleophilic substitution (SNVi), 4-methyl-3-OXO-1, 2-pyrazolidinium ylidesProcedia PDF Downloads 78
389 Theoretical Evaluation of the Preparation of Polycyclic Benzimidazole Derivatives
Authors: M. Abdoul-Hakim, A. Zeroual, H. Garmes
Abstract:In this work, the reaction of 2-chlorobenzimidazole with two distinct 1,3-dipoles such as benzonitrile N-oxide and an azomethine imine was carried out by DFT at the B3LYP/6-311+G(d, p) level to understand the effect of solvent (MeOH). The results show that MeOH has a significant effect on the evolution of the reaction. The charge transfer interactions n(O) → σ*(C-Cl), n(N)→σ*(C-Cl) and σ(N-C) →σ*(C-Cl) stabilize the transition states in an intramolecular nucleophilic substitution (SNi) step of the imidoyl group. Finally, this study provides a theoretical basis for the design of different polycyclic benzimidazole.
Keywords: azomethine imine, benzonitrile N-oxide, DFT, intramolecular nucleophilic substitution (SNi), polycyclic benzimidazoleProcedia PDF Downloads 57
388 Theoretical Evaluation of Oxirane and Aziridine Opening Regioselectivity, Solvent Effect, and Strength of Nucleophilic and Nucleofugal Groups for the Preparation of Benzimidazole-Fused 1,4-Benzoxazepine
Authors: M. Abdoul-Hakim, a. Zeroual, H. Garmes
Abstract:In a route for the preparation of 1,4-benzoxazepine fused to benzimidazole, the use of 2-(2-methoxyphenyl)-benzimidazole or styrene-derived N-tosylaziridine does not give the desired products. On this basis, we theoretically studied this reaction using DFT at the B3LYP/6-31+G(d) level. The analysis of the results shows a preferential nucleophilic attack of 2-(2-fluorophenyl)-benzimidazole on the terminal carbon atom of the Alkylepoxides and on the substituted carbon of N-tosylaziridine. Taking into account the solvent effect (DMF) makes the reactions spontaneous for the opening of epoxides and N-tosylaziridine and disfavors the intramolecularnucleophilic aromatic substitution reaction step of the products of the attack of 2-(2-methoxyphenyl)benzimidazole on an epoxide and those of the opening of N-tosylaziridine, which is consistent with the experiment.
Keywords: alkylepoxides, 4-benzoxazepine fused to benzimidazole imine, benzonitrile N-oxide, DFT, intramolecular nucleophilic aromatic substitution, N-tosyl aziridineProcedia PDF Downloads 71
387 Regioselective Nucleophilic Substitution of the Baylis-Hillman Adducts with Iodine
Authors: Zahid Shafiq, Li Liu, Dong Wang, Yong-Jun Chen
Abstract:As synthetic organic methods are increasingly concerned with the growing importance of sustainable chemistry, iodine recently has emerged as an inexpensive, non-toxic, readily available and environmentally benign catalyst for various organic transformations to afford the corresponding products in high yields with high regio- and chemoselectivity. Iodine has found widespread applications in various organic synthesis such as Michael addition, coupling reaction and also in the multicomponent synthesis where it can efficiently activate C=C, C=O, C=N, and so forth. Iodine not only has been shown to be an efficient mild Lewis acid in various processes, but also due to its moderate nature, and water tolerance, reactions catalyzed by iodine can be effectively carried out in neutral media under very mild conditions. We have successfully described an efficient procedure for the nucleophilic substitution of the Baylis-Hillman (BH) adducts and their corresponding acetates with indoles to get α-substitution product using catalytic Silver Triflate (AgOTf) as Lewis acid. At this point, we were interested to develop an environmentally benign catalytic system to effect this substitution reaction and to avoid the use of metal Lewis acid as a catalyst. Since, we observed the formation of -product during the course of the reaction, we also became interested to explore the reaction conditions in order to control regioselectivity and to obtain both regioisomers. The developed methodology resulted in regioselective substitution products with controlled selectivity. Further, the substitution products were used to synthesize various Tri- and Tetracyclo Azepino indole derivatives via reductive amination.
Keywords: indole, regioselective, Baylis-Hillman, substitutionProcedia PDF Downloads 95
386 Evolutional Substitution Cipher on Chaotic Attractor
Authors: Adda Ali-Pacha, Naima Hadj-Said
Abstract:Nowadays, the security of information is primarily founded on the calculation of algorithms that confidentiality depend on the number of bits necessary to define a cryptographic key. In this work, we introduce a new chaotic cryptosystem that we call evolutional substitution cipher on a chaotic attractor. In this research paper, we take the Henon attractor. The evolutional substitution cipher on Henon attractor is based on the principle of monoalphabetic cipher and it associates the plaintext at a succession of real numbers calculated from the attractor equations.
Keywords: cryptography, substitution cipher, chaos theory, Henon attractor, evolutional substitution cipherProcedia PDF Downloads 358
385 The Evaluation of Substitution of Acacia villosa in Ruminants Ration
Authors: Hadriana Bansi, Elizabeth Wina, Toto Toharmat
Abstract:Acacia villosa is thornless shrub legume which contents high crude protein. However, the utilization of A. villosa as ruminant feed is limited by its secondary compounds. The aim of this article is to find out the maximum of substitution A. villosa in sheep ration. The nutritional evaluation consisted of in vitro two stages, in vivo, and in vitro gas production trials. The secondary compounds of A. villosa also were analyzed. Evaluating digestibility of increasing level of substitution A. villosa replacing Pennisetum purpureum was using in vitro two stages. The substitution of 30% A. villosa was compared to 100% P. purpureum by in vitro gas production technique and in vivo digestibility. The results of two stages in vitro showed that total phenol, condensed tannin, and non-protein amino acid (NPAA) were high. Substitution 15% A. villosa reached the highest digestibility for both dry matter (DM) and crude protein (CP) which were 67% and 86% respectively, but it was shown that DM and CP digestibility of substitution 30% of A. villosa was still high which were 61.82% and 75-67% respectively. The pattern of gas production showed that first 8 hours total gas production substitution of 30% A. villosa was higher than 100% P. purpureum and declined after 10 hours incubation. In vivo trials showed that substitution of 30% A. villosa significantly increased CP intake, CP digestibility, and nitrogen retention. It can be concluded that substitution A. villosa until 30% still gave the good impact even though it has high secondary compounds.
Keywords: Acacia villosa, digestibility, gas production, secondary compoundsProcedia PDF Downloads 92
384 Substitution of Silver-Thiosulfate (STS) with Some Essential Oils on Vase-Life of Cut Carnation cv. Liberty
Authors: Mohammad Bagher Hassanpouraghdam, Mohammad Ali Aazami Mavaloo
Abstract:Due to the huge side-effects of chemicals; essential oils have been considered as suitable alternatives for keeping the vase-life of cut flowers mainly owing to the availability and environment-friend nature of these bio-chemicals. In the present experiment, 50% substitution of STS was achieved and tested on cut carnation flowers cv. Liberty by using the essential oils from four plants; Satureja sahendica Bornm., Echinophora platyloba DC., Tanacetum balsamita L. and Cupressus arizonica Greene., as CRD with five treatments and 3 replications. Vase-life and flower diameter were affected with 50% substitution of STS by essential oils from C. arizonica and T. balsamita. Membrane stability index, Malondialdehyde (MDA) content and Hydrogen peroxide (H2O2) amounts were affected by the substitution treatments as well. The main preservative effect belonged to the substitution with C. arizonica. So that, 50% STS substitution with Cupressus oil holds the highest membrane integrity and the least data for MDA and H2O2 content.
Keywords: Carnation, essential oil, Membrane stability index (MSI), vase lifeProcedia PDF Downloads 417
383 The Role of Labour Substitution by Age in the Effect of Fertility on Living Standards: Simulations for Scandinavia
Authors: Ross Guest, Bjarne Jensen
Abstract:This paper analyses a potentially new consumption dividend from lower fertility arising from imperfect labour substitution by age. A smaller proportion of young workers relative to older workers raises relative youth wages given imperfect labour substitution by age. Discounted lifetime labour income rises which provides a consumption dividend. Simulation results are reported for the four Scandinavian countries, adopting a simple overlapping generations model. Imperfect labour substitution is modelled using a CRESH functional form of an aggregate labour index. The magnitudes of this new consumption dividend from a Low fertility projection compared with a high fertility projection are found to be approximately 4 percent annually, on average over the Scandinavian countries in the very long run, but somewhat lower in the short term. There is some sensitivity to the interest rate and the degree of consumption smoothing.
Keywords: fertility, consumption, productivity, labour substitutionProcedia PDF Downloads 280
382 Chemical Modification of PVC and Its Surface Analysis by Means of XPS and Contact Angle Measurements
Authors: Ali Akrmi, Mohamed Beji, Ahmed Baklouti, Fatma Djouani, Philippe Lang, Mohamed M. Chehimi
Abstract:Poly(vinyl chloride) (PVC) is a highly versatile polymer with excellent balance of properties and numerous applications such as water pipes, packaging and polymer materials of importance in the biomedical sector. However, depending on the applications, it is necessary to modify PVC by mixing with a plasticizer; surface modification using plasma, surface grafting or flame treatment; or bulk chemical modification which affects the entire PVC chains at an extent that can be tuned by the polymer chemist. The targeted applications are improvement of chemical resistance, avoiding or limitation of migration of toxic plasticizers, improvement of antibacterial properties, or control of blood compatibility.
Keywords: poly(vinyl chloride), nucleophilic substitution, sulfonylcarbamates, XPSProcedia PDF Downloads 527
381 Study on the Carboxymethylation of Glucomannan from Porang
Authors: Fadilah Fadilah, Sperisa Distantina, Santi T. Wijayanti, Rahmawati Andayani
Abstract:Chemical modification process on glucomannan from porang via carboxymethylation have been conducted. The process was done in two stages, the alkalization, and the carboxymethylation. The alkalization was done by adding NaOH solution into the medium which was contained glucomannan and then stirred it in ambient temperature for thirty minutes. The carboxymethylation process was done by adding sodium mono chloroacetate solution into the alkalization product. The carboxymethylation process was conducted for a certain time, and the product was then analyzed for determining the degree of substitution. In this research, the influence of medium to the degree of substitution was studied. Three different medium were used, namely water, 70% ethanol, and 90% ethanol. The results show that 70% ethanol was a better medium than two others because give a higher degree of substitution. Using 70% ethanol as a medium, the experiments for studying the influence of temperature on the carboxymethylation stages were conducted. The results show that the degree of substitution at 65°C is higher than at 45°C.
Keywords: carboxymethylation, degree of substitution, ethanol medium, glucomannanProcedia PDF Downloads 151
380 Synthesis and Characterization of Magnesium and Strontium Doped Sulphate-Hydroxyapatite
Authors: Ammar Z. Alshemary, Yi-Fan Goh, Rafaqat Hussain
Abstract:Magnesium (Mg2+), strontium (Sr2+) and sulphate ions (SO42-) were successfully substituted into hydroxyapatite (Ca10-x-y MgxSry(PO4)6-z(SO4)zOH2-z) structure through ion exchange process at cationic and anionic sites. Mg2+and Sr2+ ions concentrations were varied between (0.00-0.10), keeping concentration of SO42- ions at z=0.05. [Mg (NO3)2], [Sr (NO3)2] and (Na2SO4) were used as Mg2+, Sr2+, and SO42- sources respectively. The synthesized white precipitate were subjected to heat treatment at 500ºC and finally characterized by X-ray diffraction (XRD) and Fourier Transform infra-red spectroscopy (FTIR). The results showed that the substitution of Mg2+, Sr2+ and SO42- ions into the HA lattice resulted in an increase in the broadness and reduction of XRD peaks. This confirmed that the crystallinity was reduced due to the substitution of ions. Similarly, FTIR result showed the effect of substitution on phosphate bands as well as exchange of hydroxyl group by SO42- ions to balance the charges on HA surface.
Keywords: hydroxyapatite, substitution, characterization, XRD, FTIRProcedia PDF Downloads 374
379 Use of Recycled Aggregates in Current Concretes
Authors: K. Krizova, R. Hela
Abstract:The paper a summary of the results of concretes with partial substitution of natural aggregates with recycled concrete is solved. Design formulas of the concretes were characterised with 20, 40 and 60% substitution of natural 8-16 mm fraction aggregates with a selected recycled concrete of analogous coarse fractions. With the product samples an evaluation of coarse fraction aggregates influence on fresh concrete consistency and concrete strength in time was carried out. The results of concretes with aggregates substitution will be compared to reference formula containing only the fractions of natural aggregates.
Keywords: recycled concrete, natural aggregates, fresh concrete, properties of concreteProcedia PDF Downloads 328
378 Influence of Substitution on Structure of Tin Lantanium Pyrochlore La₂₋ₓSrₓSn₂O₇₋δ(0 ≤ x ≤ 0.25) Solid-Oxide Fuel Cells
Authors: Bounar Nedjemeddine
Abstract:Materials with the pyrochlore lattice structure have attracted much recent attention due to their wide applications in ceramic thermal barrier coatings, high-permittivity dielectrics, and potential solid electrolytes in solid-oxide fuel cells. The work described in this paper is devoted to the synthesis and characterization of a pyrochlore structure based on lanthanum (La₂O₃) and tin (SnO₂) oxides of general formula La₂Sn₂O₇, substituted by Sr at the site La. Their structures were determined from X-ray powder diffraction using CELFER analysis. All the compositions present the space group Fd-3m. The substitution of La by Sr in the La₂Sn₂O₇ compound causes a variation of the cell parameters. The difference in charge between La³⁺ and Sr²⁺ and the difference in size cause the cell parameters to decrease from a=10.7165 A° to a=10.6848 A° for the substitution rates (x = 0.05, 0.1, 0.15 ...), which leads to a decrease in the volume of the mesh. For a substitution rate x = 0.25, there is an increase in the cell parameters (a=10.7035A°), which can be explained by a competitiveness of the size effect and the presence of a gap in the structure which go in the opposite direction.
Keywords: solid-oxide fuel cells, structure, pyrochlore, X-ray diffractionProcedia PDF Downloads 68
377 Reactions of 4-Aryl-1H-1,2,3-Triazoles with Cycloalkenones and Epoxides: Synthesis of 2,4- and 1,4-Disubstituted 1,2,3-Triazoles
Authors: Ujjawal Kumar Bhagat, Kamaluddin, Rama Krishna Peddinti
Abstract:The Huisgen’s 1,3-dipolar [3+2] cycloaddition of organic azides and alkynes often give the mixtures of both the regioisomers 1,4- and 1,5- disubstituted 1,2,3-triazoles. Later, in presence of metal salts (click chemistry) such as copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) was used for the synthesis of 1,4-disubstituted 1,2,3-triazoles as a sole products regioselectively. Also, the ‘click reactions’ of Ruthenium-catalyzed azides-alkynes cycloaddition (RuAAC) is used for the synthesis of 1,5-disubstituted 1,2,3-triazoles as a single isomer. The synthesis of 1,4- and 1.5-disubstituted 1,2,3-triazoles has become the gold standard of ‘click chemistry’ due to its reliability, specificity, and biocompatibility. The 1,4- and 1,5-disubstituted 1,2,3-triazoles have emerged as one of the most powerful entities in the varieties of biological properties like antibacterial, antitubercular, antitumor, antifungal and antiprotozoal activities. Some of the 1,4,5-trisubstituted 1,2,3-triazoles exhibit Hsp90 inhibiting properties. The 1,4-disubstituted 1,2,3-triazoles also play a big role in the area of material sciences. The triazole-derived oligomeric, polymeric structures are the potential materials for the preparation of organic optoelectronics, silicon elastomers and unimolecular block copolymers. By the virtue of hydrogen bonding and dipole interactions, the 1,2,3-triazole moiety readily associates with the biological targets. Since, the 4-aryl-1H-1,2,3-triazoles are stable entities, they are chemically robust and very less reactive. In this regard, the addition of 4-aryl-1H-1,2,3-triazoles as nucleophiles to α,β-unsaturated carbonyls and nucleophilic substitution with the epoxides constitutes a powerful and challenging synthetic approach for the generation of disubstituted 1,2,3-triazoles. Herein, we have developed aza-Michael addition of 4-aryl-1H-1,2,3-triazoles to 2-cycloalken-1-ones in the presence of an organic base (DABCO) in acetonotrile solvent leading to the formation of disubstituted 1,2,3-triazoles. The reaction provides 1,4-disubstituted triazoles, 3-(4-aryl-1H-1,2,3-triazol-1-yl)cycloalkanones in major amount along with 1,5-disubstituted 1,2,3-triazoles, minor regioisomers with excellent combined chemical yields (upto99%). The nucleophilic behavior of 4-aryl-1H-1,2,3-triazoles was also tested in the ring opening of meso-epoxides in the presence of organic bases (DABCO/Et3N) in acetonotrile solvent furnishing the two regioisomers1,4- and 1,5-disubstituted 1,2,3-triazoles. Thus, the novelty of this methodology is synthesis of diversified disubstituted 1,2,3-triazoles under metal free condition.The results will be presented in detail.
Keywords: aza-Michael addition, cycloalkenones, epoxides, triazolesProcedia PDF Downloads 248
376 Substitution Effects of Baijiu and Cigarette Consumption on Anti-Corruption Campaigns: Evidence from China
Authors: Xiaohan Gu
Abstract:China is perceived as one of the most politically corrupt countries in the world. The 2021 Transparency International Corruption Perceptions Index China (RPC) ranks the country in 66th place out of 180 countries in the Index, where the 180 countries are perceived to have the most corrupt public sector. This paper proposes a theory on the impact of corruption on the consumption of luxury goods. We test the theory and evaluate the effectiveness of China’s anti-corruption campaign in 2012 by conducting a difference-in-differences analysis of product-city-level alcohol and cigarette consumption from 2013 to 2022. We find that the campaign increased sales of middle-end baijiu and cigarettes but decreased sales of luxury baijiu and cigarettes, contrasting with the trend for low-end products. This substitution pattern may be attributable to decreased public spending on luxury goods. This substitution pattern is moderated by officials’ wages and anti-corruption efforts, which supports the theoretical predictions.
Keywords: substitution effect, baijiu, corruption, anti-corruption, chinese political connectionProcedia PDF Downloads 10
375 Impact of Gd³⁺ Substitution on Structural, Optical and Magnetic Properties of ZnFe₂O₄ Nanoparticles
Authors: Raghvendra Singh Yadav, Ivo Kuřitka, Jarmila Vilcakova, Pavel Urbanek, Michal Machovsky, David Skoda
Abstract:In this report, the impact of Gd³⁺ substitution in ZnFe₂O₄ spinel ferrite nanoparticles on structural, optical and magnetic properties was investigated. ZnFe₂₋ₓGdₓO₄ (x=0.00, 0.05, 0.10, 0.15, 0.20) nanoparticles were synthesized by honey-mediated sol-gel combustion method. X-ray diffraction, Raman Spectroscopy and Fourier Transform Infrared Spectroscopy confirmed the formation of cubic spinel ferrite crystal structure. The morphology and elemental analysis were studied using field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy, respectively. UV-Visible reflectance spectroscopy revealed band gap variation with concentration of Gd³⁺ substitution in ZnFe₂O₄ nanoparticles. Magnetic property was studied using vibrating sample magnetometer at room temperature. The synthesized spinel ferrite nanoparticles showed ferromagnetic behaviour. The evaluated magnetic parameters such as saturation magnetization, coercivity and remanence showed variation with Gd³⁺ substitution in spinel ferrite nanoparticles. This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic – Program NPU I (LO1504).
Keywords: sol-gel combustion method, nanoparticles, magnetic property, optical propertyProcedia PDF Downloads 227
374 Global Analysis in a Growth Economic Model with Perfect-Substitution Technologies
Authors: Paolo Russu
Abstract:The purpose of the present paper is to highlight some features of an economic growth model with environmental negative externalities, giving rise to a three-dimensional dynamic system. In particular, we show that the economy, which is based on a Perfect-Substitution Technologies function of production, has no neither indeterminacy nor poverty trap. This implies that equilibrium select by economy depends on the history (initial values of state variable) of the economy rather than on expectations of economies agents. Moreover, by contrast, we prove that the basin of attraction of locally equilibrium points may be very large, as they can extend up to the boundary of the system phase space. The infinite-horizon optimal control problem has the purpose of maximizing the representative agent’s instantaneous utility function depending on leisure and consumption.
Keywords: Hopf bifurcation, open-access natural resources, optimal control, perfect-substitution technologies, Poincarè compactificationProcedia PDF Downloads 94
373 Prediction of the Regioselectivity of 1,3-Dipolar Cycloaddition Reactions of Nitrile Oxides with 2(5H)-Furanones Using Recent Theoretical Reactivity Indices
Authors: Imad Eddine Charif, Wafaa Benchouk, Sidi Mohamed Mekelleche
Abstract:The regioselectivity of a series of 16 1,3-dipolar cycloaddition reactions of nitrile oxides with 2(5H)-furanones has been analysed by means of global and local electrophilic and nucleophilic reactivity indices using density functional theory at the B3LYP level together with the 6-31G(d) basis set. The local electrophilicity and nucleophilicity indices, based on Fukui and Parr functions, have been calculated for the terminal sites, namely the C1 and O3 atoms of the 1,3-dipole and the C4 and C5 atoms of the dipolarophile. These local indices were calculated using both Mulliken and natural charges and spin densities. The results obtained show that the C5 atom of the 2(5H)-furanones is the most electrophilic site whereas the O3 atom of the nitrile oxides is the most nucleophilic centre. It turns out that the experimental regioselectivity is correctly reproduced, indicating that both Fukui- and Parr-based indices are efficient tools for the prediction of the regiochemistry of the studied reactions and could be used for the prediction of newly designed reactions of the same kind.
Keywords: 1, 3-dipolar cycloaddition, density functional theory, nitrile oxides, regioselectivity, reactivity indicesProcedia PDF Downloads 105
372 The Effect of Substitution of CaO/MgO and CaO/SrO on in vitro Bioactivity of Sol-Gel Derived Bioactive Glass
Authors: Zeinab Hajifathali, Moghan Amirhosseinian
Abstract:This study had two main aims: firstly, to determine how the individual substitution of CaO/MgO and CaO/SrO can affect the in vitro bioactivity of sol-gel derived substituted 58S bioactive glass (BG) and secondly to introduce a composition in the 60SiO2–(36-x)CaO–4P2O5–(x)MgO and 60SiO2–(36-x)CaO–4P2O5–(x)SrO quaternary systems (where x= 0, 5, 10 mol.%) with enhanced biocompatibility, alkaline phosphatase (ALP) activity, and more efficient antibacterial activity against MRSA bacteria. Results showed that both magnesium-substituted bioactive glasses (M-BGs) and strontium- substituted bioactive glasses (S-BGs) retarded the Hydroxyapatite (HA) formation. Meanwhile, magnesium had more pronounced effect. The 3-(4, 5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and ALP assays revealed that the presence of moderate amount (5 mol%) of Mg and Sr had a stimulating effect on increasing of both proliferation and differentiation of MC3T3-E1 cells. Live dead and Dapi/actin staining revealed both substitution of CaO/MgO and CaO/SrO resulted in more biocompatibility and stimulation potential of the MC3T3 cells compared with control. Taken together, among all of the synthesized magnesium substituted (MBGs) and strontium substituted (SBGs), the sample 58- BG with 5 mol% CaO/MgO substitution (BG-5M) was considered as a multifunctional biomaterial in bone tissue regeneration field with enhanced biocompatibility, ALP activity as well as the highest antibacterial efficiency against methicillin-resistant Staphylococcus aureus (MRSA) bacteria.
Keywords: apatite, alkaline earth, bioactivity, biomedical applications, Sol-gelProcedia PDF Downloads 76
371 Theoretical Study of Acetylation of P-Methylaniline Catalyzed by Cu²⁺ Ions
Authors: Silvana Caglieri
Abstract:Theoretical study of acetylation of p-methylaniline catalyzed by Cu2+ ions from the analysis of intermediate of the reaction was carried out. The study of acetylation of amines is of great interest by the utility of its products of reaction and is one of the most frequently used transformations in organic synthesis as it provides an efficient and inexpensive means for protecting amino groups in a multistep synthetic process. Acetylation of amine is a nucleophilic substitution reaction. This reaction can be catalyzed by Lewis acid, metallic ion. In reaction mechanism, the metallic ion formed a complex with the oxygen of the acetic anhydride carbonyl, facilitating the polarization of the same and the successive addition of amine at the position to form a tetrahedral intermediate, determining step of the rate of the reaction. Experimental work agreed that this reaction takes place with the formation of a tetrahedral intermediate. In the present theoretical work were investigated the structure and energy of the tetrahedral intermediate of the reaction catalyzed by Cu2+ ions. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the DFT/B3LYP level of theory and the method MP2. Were adopted the 6-31+G* basis sets. Energies were calculated using the Mechanics-UFF method. Following the same procedure it was identified the geometric parameters and energy of reaction intermediate. The calculations show 61.35 kcal/mol of energy for the tetrahedral intermediate and the energy of activation for the reaction was 15.55 kcal/mol.
Keywords: amides, amines, DFT, MP2Procedia PDF Downloads 191
370 Elvis Improved Method for Solving Simultaneous Equations in Two Variables with Some Applications
Authors: Elvis Adam Alhassan, Akos Konadu, Ernest Zamanah, David Alemzero, Michael Jackson Adjabui, Ibrahim Justice Musah
Abstract:In this paper, how to solve simultaneous equations using the Elvis improved method is shown. The Elvis improved method says; Make one variable in the first equation the subject; Make the same variable in the second equation the subject; Equate the results and simplify to obtain the value of the unknown variable; Put the value of the variable found into one equation from the first or second steps and simplify for the remaining unknown variable. The difference between our Elvis improved method and the Substitution method is that: with Elvis improved method, the same variable is made the subject in both equations and the two resulting equations equated, unlike the substitution method where one variable is made the subject of only one equation and substituted into the other equation. After describing the Elvis improved method, findings from 100 secondary students and the views of 5 secondary tutors to demonstrate the effectiveness of the method are presented. The study purpose is proved by hypothetical examples.
Keywords: simultaneous equations, substitution method, elimination method, graphical method, Elvis improved methodProcedia PDF Downloads 18
369 A Novel Environmentally Benign Positive Electrode Material with Improved Energy Density for Lithium Ion Batteries
Authors: Wassima El Mofid, Svetlozar Ivanov, Andreas Bund
Abstract:The increasing requirements for high power and energy lithium ion batteries have led to the development of several classes of positive electrode materials. Among those one promising material is LiNixMnyCo1−x−yO2 due to its high reversible capacity and remarkable cycling performance. Further structural stabilization and improved electrochemical performance of this class of cathode materials can be achieved by cationic substitution to a transition metal such as Al, Mg, Cr, etc. The current study discusses a novel NMC type material obtained by simultaneous cationic substitution of the cobalt which is a toxic element, with aluminum and iron. A compound with the composition LiNi0.6Mn0.2Co0.15Al0.025Fe0.025O2 (NMCAF) was synthesized by the self-combustion method using sucrose as fuel. The material has a layered α-NaFeO2 type structure with a good hexagonal ordering. Rietveld refinement analysis of the XRD patterns revealed a very low cationic mixing compared to the non-substituted material LiNi0.6Mn0,2Co0.2O2 suggesting a structural stabilization. Galvanostatic cycling measurements indicate improved electrochemical performance after the metal substitution. An initial discharge capacity of about 190 mAh.g−1 at slow rate (C/20), and a good cycling stability even at moderately faster rates (C/5 and C) have been observed. The long term cycling displayed a capacity retention of about 90% after 10 cycles.
Keywords: cationic substitution, lithium ion batteries, positive electrode material, self-combustion synthesis methodProcedia PDF Downloads 342
368 Amplitude Versus Offset (AVO) Modeling as a Tool for Seismic Reservoir Characterization of the Semliki Basin
Authors: Hillary Mwongyera
Abstract:The Semliki basin has become a frontier for petroleum exploration in recent years. Exploration efforts have resulted into extensive seismic data acquisition and drilling of three wells namely; Turaco 1, Turaco 2 and Turaco 3. A petrophysical analysis of the Turaco 1 well was carried out to identify two reservoir zones on which AVO modeling was performed. A combination of seismic modeling and rock physics modeling was applied during reservoir characterization and monitoring to determine variations of seismic responses with amplitude characteristics. AVO intercept gradient analysis applied on AVO synthetic CDP gathers classified AVO anomalies associated with both reservoir zones as Class 1 AVO anomalies. Fluid replacement modeling was carried out on both reservoir zones using homogeneous mixing and patchy saturation patterns to determine effects of fluid substitution on rock property interactions. For both homogeneous mixing and saturation patterns, density (ρ) showed an increasing trend with increasing brine substitution while Shear wave velocity (Vs) decreased with increasing brine substitution. A study of compressional wave velocity (Vp) with increasing brine substitution for both homogeneous mixing and patchy saturation gave quite interesting results. During patchy saturation, Vp increased with increasing brine substitution. During homogeneous mixing however, Vp showed a slightly decreasing trend with increasing brine substitution but increased tremendously towards and at full brine saturation. A sensitivity analysis carried out showed that density was a very sensitive rock property responding to brine saturation except at full brine saturation during homogeneous mixing where Vp showed greater sensitivity with brine saturation. Rock physics modeling was performed to predict diagnostics of reservoir quality using an inverse deterministic approach which showed low shale content and a high degree of shale stiffness within reservoir zones.
Keywords: Amplitude Versus Offset (AVO), fluid replacement modelling, reservoir characterization, AVO attributes, rock physics modelling, reservoir monitoringProcedia PDF Downloads 441
367 Influence of the Substitution of C for Mg and Ni on the Microstructure and Hydrogen Storage Characteristics of Mg2Ni Alloys
Authors: Sajad Haghanifar, Seyed-Farshid Kashani Bozorg
Abstract:Nano-crystalline Mg2Ni-based powder was produced by mechanical alloying technique using binary and ternary powder mixtures with stoichiometric compositions of Mg2Ni, Mg1.9C0.1Ni and Mg2C0.1Ni0.9. The structures and morphologies of the milled products were studied by XRD, SEM and HRTEM. Their electrochemical hydrogen storage characteristics were investigated in 6 M KOH solution. X-Ray diffraction, scanning and transmission electron microscopy of the milled products showed the formation of Mg2Ni-based nano-crystallites after 5, 15 and 30 h of milling using the initial powder mixtures of Mg1.9C0.1Ni, Mg2Ni and Mg2C0.1Ni0.9, respectively. It was found that partial substitution of C for Mg has beneficial effect on the formation kinetic of nano-crystalline Mg2Ni. Contrary to this, partial substitution of C for Ni was resulted in retardation of formation kinetic of nano-crystalline Mg2Ni. In addition, the negative electrode made from Mg1.9C0.1Ni ternary milled product after 30 hour of milling exhibited the highest initial discharge capacity and longest discharge life. Thus, partial substitution of C for Mg is beneficial to electrode properties of the Mg2Ni-based crystallites. The relation between the discharge capacity and cycling number of mechanically alloyed products was proposed on the basis of the fact that the degradation of discharge capacity was mainly caused by the oxidation of magnesium and nickel. The experimental data fitted the deduced equation well.
Keywords: Mg2Ni, hydrogen absorbing materials, electrochemical properties, nano-crystalline, amorphous, mechanical alloying, carbonProcedia PDF Downloads 369
366 The Study of Magnetic and Transport Properties in Normal State Eu1.85+yCe0.15-yCu1-yFeyO4+α-δ
Authors: Risdiana, D. Suhendar, S. Pratiwi, W. A. Somantri, T. Saragi
Abstract:Superconductor is a promising material for future applications especially for energy saving because of their advantages properties such as zero electrical resistivity when they are cooled down to sufficiently low temperatures. However, the mechanism describing the role of physical properties in superconductor is far from being understood clearly, so that the application of this material for wider benefit in various industries is very limited. Most of superconductors are cuprate compounds, which has CuO2 as a conducting plane in their crystal structures. The study of physical properties through the partially substitution of impurity for Cu in superconducting cuprates has been one of great interests in relation to the mechanism of superconductivity. Different behaviors between the substitution of nonmagnetic impurity and magnetic impurity for Cu are observed. For examples, the superconductivity and Cu-spin fluctuations in the electron-doped system are suppressed through the substitution of magnetic Ni for Cu more markedly than through the substitution of nonmagnetic Zn for Cu, which is contrary to the result in the hole-doped system. Here, we reported the effect of partially substitution of magnetic impurity Fe for Cu to the magnetic and transport properties in electron-doped superconducting cuprates of Eu1.85+yCe0.15-yCu1-yFeyO4+α-δ (ECCFO) with y = 0.01, 0.02, and 0.05, in order to investigate the mechanism of magnetic and transport properties of ECCFO in normal-state. Magnetic properties are investigated by DC magnetic-susceptibility measurements that carried out at low temperatures down to 2 K using a standard SQUID magnetometer in a magnetic field of 5 Oe on field cooling. Transport properties addressed to electron mobility, are extracted from radius of electron localization calculated from temperature dependence of resistivity. For y = 0, temperature dependence of dc magnetic-susceptibility indicated the change of magnetic behavior from paramagnetic to diamagnetic below 15 K. Above 15 K, all samples show paramagnetic behavior with the values of magnetic moment in every volume unit increased with increasing y. Electron mobility decreased with increasing y. Some reasons for these results will be discussed.
Keywords: DC magnetic-susceptibility, electron mobility, Eu1.85+yCe0.15-yCu1-yFeyO4+α-δ, normal stateProcedia PDF Downloads 200
365 Comparative Evaluation on in vitro Bioactivity, Proliferation and Antibacterial Efficiency of Sol-Gel Derived Bioactive Glass Substituted by Li and Mg
Authors: Amirhossein Moghanian, Morteza Elsa, Mehrnaz Aminitabar
Abstract:Modified bioactive glass has been considered as a promising multifunctional candidate in bone repair and regeneration due to its attractive properties. The present study mainly aims to evaluate how the individual substitution of lithium (L-BG) and magnesium (M-BG) for calcium can affect the in vitro bioactivity of sol-gel derived substituted 58S bioactive glass (BG); and to present one composition in both of the 60SiO2–(36-x)CaO–4P₂O₅–(x)Li₂O and 60SiO₂ –(36-x)CaO–4P₂O₅–(x)MgO quaternary systems (where x= 0, 5, 10 mol.%) with improved biocompatibility, enhanced alkaline phosphatase (ALP) activity, and the most efficient antibacterial activity against methicillin-resistant staphylococcus aureus bacteria. To address these aims, and study the effect of CaO/Li₂O and CaO/MgO substitution up to 10 mol % in 58S-BGs, the samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectrometry and scanning electron microscopy after immersion in simulated body fluid up to 14 days. Results indicated that substitution of either CaO/ Li₂O and CaO/ MgO had a retarding effect on in vitro hydroxyapatite (HA) formation due to the lower supersaturation degree for nucleation of HA compared with 58s-BG. Meanwhile, magnesium had a more pronounced effect. The 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and alkaline phosphatase (ALP) assays showed that both substitutions of CaO/ Li₂O and CaO/ MgO up to 5mol % in 58s-BGs led to increased biocompatibility and stimulated proliferation of the pre-osteoblast MC3T3 cells with respect to the control. On the other hand, the substitution of either Li or Mg for Ca in the 58s BG composition resulted in improved bactericidal efficiency against MRSA bacteria. Taken together, sample 58s-BG with 5 mol % CaO/Li₂O substitution (BG-5L) was considered as a multifunctional biomaterial in bone repair/regeneration with improved biocompatibility, enhanced ALP activity as well as significant antibacterial activity against methicillin-resistant staphylococcus aureus (MRSA) bacteria.
Keywords: alkaline, alkaline earth, bioactivity, biomedical applications, sol-gel processesProcedia PDF Downloads 84
364 Sol-Gel Derived 58S Bioglass Substituted by Li and Mg: A Comparative Evaluation on in vitro Bioactivity, MC3T3 Proliferation and Antibacterial Efficiency
Authors: Amir Khaleghipour, Amirhossein Moghanian, Elhamalsadat Ghaffari
Abstract:Modified bioactive glass has been considered as a promising multifunctional candidate in bone repair and regeneration due to its attractive properties. The present study mainly aims to evaluate how the individual substitution of lithium (L-BG) and magnesium (M-BG) for calcium can affect the in vitro bioactivity of sol-gel derived substituted 58S bioactive glass (BG); and to present one composition in both of the 60SiO₂–(36-x)CaO–4P₂O₅–(x)Li₂O and 60SiO₂–(36-x)CaO–4P₂O₅–(x)MgO quaternary systems (where x= 0, 5, 10 mol.%) with improved biocompatibility, enhanced alkaline phosphatase (ALP) activity, and the most efficient antibacterial activity against methicillin-resistant Staphylococcus aureus bacteria. To address these aims, and study the effect of CaO/Li₂O and CaO/MgO substitution up to 10 mol % in 58S-BGs, the samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectrometry and scanning electron microscopy after immersion in simulated body fluid up to 14 days. Results indicated that substitution of either CaO/ Li₂O and CaO/ MgO had a retarding effect on in vitro hydroxyapatite (HA) formation due to the lower supersaturation degree for nucleation of HA compared with 58s-BG. Meanwhile, magnesium had a more pronounced effect. The 3-(4, 5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and alkaline phosphatase (ALP) assays showed that both substitutions of CaO/ Li₂O and CaO/ MgO up to 5mol % in 58s-BGs led to increased biocompatibility and stimulated proliferation of the pre-osteoblast MC3T3 cells with respect to the control. On the other hand, substitution of either Li or Mg for Ca in the 58s BG composition resulted in improved bactericidal efficiency against MRSA bacteria. Taken together, sample 58s-BG with 5 mol % CaO/Li₂O substitution (BG-5L) was considered as a multifunctional biomaterial in bone repair/regeneration with improved biocompatibility, enhanced ALP activity as well enhanced antibacterial efficiency against methicillin-resistant Staphylococcus aureus (MRSA) bacteria among all of the synthesized L-BGs and M-BGs.
Keywords: alkaline, alkaline earth, bioactivity, biomedical applications, sol-gel processesProcedia PDF Downloads 115
363 Contrasting Infrastructure Sharing and Resource Substitution Synergies Business Models
Authors: Robin Molinier
Abstract:Industrial symbiosis (I.S) rely on two modes of cooperation that are infrastructure sharing and resource substitution to obtain economic and environmental benefits. The former consists in the intensification of use of an asset while the latter is based on the use of waste, fatal energy (and utilities) as alternatives to standard inputs. Both modes, in fact, rely on the shift from a business-as-usual functioning towards an alternative production system structure so that in a business point of view the distinction is not clear. In order to investigate the way those cooperation modes can be distinguished, we consider the stakeholders' interplay in the business model structure regarding their resources and requirements. For infrastructure sharing (following economic engineering literature) the cost function of capacity induces economies of scale so that demand pooling reduces global expanses. Grassroot investment sizing decision and the ex-post pricing strongly depends on the design optimization phase for capacity sizing whereas ex-post operational cost sharing minimizing budgets are less dependent upon production rates. Value is then mainly design driven. For resource substitution, synergies value stems from availability and is at risk regarding both supplier and user load profiles and market prices of the standard input. Baseline input purchasing cost reduction is thus more driven by the operational phase of the symbiosis and must be analyzed within the whole sourcing policy (including diversification strategies and expensive back-up replacement). Moreover, while resource substitution involves a chain of intermediate processors to match quality requirements, the infrastructure model relies on a single operator whose competencies allow to produce non-rival goods. Transaction costs appear higher in resource substitution synergies due to the high level of customization which induces asset specificity, and non-homogeneity following transaction costs economics arguments.
Keywords: business model, capacity, sourcing, synergiesProcedia PDF Downloads 121
362 Influence of CA, SR and BA Substitution on lafeo3Performances During Chemical Looping Processes
Authors: Rong Sun, Laihong Shen
Abstract:La-based perovskite oxygen carriers, especially the doped-La(M)FeO₃, showed excellent performances during chemical looping processes. However, the mechanisms of the undoped and doped La(M)FeO₃ are not clear at present, making the mechanisms clear may help the development of chemical looping technologies. In this paper, the method based on the density function theory (DFT) was used to analysis the influence of Ca, Sr, and Ba doping of La on the electronic structure, while the CO oxidation mechanisms on the surface of LaFeO₃ and Ca-doped LaFeO₃ oxygen carriers were also analyzed. The results showed that the band gap was decreased by the doping of low valence. While the doping of low valence element Ca, Sr, and Ba at La site simultaneously resulted to the moving of the valence band toward high energy and made the valence band cross the Fermi energy level. This was resulted from the holes generated by divalent ion substitution. The holes can change the total magnetization from antiferromagnet to weakly ferromagnetism. The calculation results about the formation of oxygen vacancy showed that substitutions of Ca, Sr, and Ba caused a large drop in oxygen vacancy formation energy, indicating that the bulk oxygen transport was improved. Based on the optimized bulk of the undoped and Ca-doped LaFeO₃(010) surface, the CO adsorption was analyzed. The results indicated that the adsorption energy increased by divalent ion substitution, meaning that the adsorption stability decreased. The results can provide a certain theoretical basis for the development of perovskite oxides in chemical looping technologies.
Keywords: chemical looping technologies, lanthanum ferrate (LaFeO₃), divalent ion substitution, CO oxidationProcedia PDF Downloads 28
361 Experimental Evaluation of Workability and Compressive Strength of Concrete With Sediments From Dam
Authors: Khouadjia Mohamed Lyes Kamel, Bensalem Sara, Abdou Kamel, Belkadi Ahmed Abderraouf, Kessal Oussama
Abstract:The experimental study was conducted on sediments dredging from the dam of Bni Haroun, the most important and the largest dam in Algeria. The first phase of the work was to substitution of crushed sand with sediments to study the workability and compressive strength of ordinary concretes. The second phase of the work is to study the behavior of concrete with sediment under the effect of the freeze-thaw cycles. The results showed that the mechanical performance of concretes with sediments is better with a substitution rate of 10%.
Keywords: sediments, concrete, dam, workability, compressive strength, freeze-thaw cyclesProcedia PDF Downloads 17