Search results for: methanol oxidation reaction

Authors: Hua Chai, Qiangling Duan, Huiqi Cao, Mi Li, Jinhua Sun

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Nitrocellulose (NC), a kind of energetic material, has been widely used in the industrial and military fields. However, this material can also cause serious social disasters due to storage conditions. Thermal hazard of nitrocellulose (NC) was experimentally investigated using the CALVET heat flux calorimeter C80, and three kinds of storage conditions were considered in the experiments: (1) drying time, (2) moisture content, (3) cycles. The results showed that the heat flow curves of NC moved to the low-temperature direction firstly and then slightly moved back by increasing the drying hours. Moisture that was responsible for the appearance of small exothermic peaks was proven to be the unfavorable safety factor yet it could increase the onset temperature of the main peak to some extent. And cycles could both lower the onset temperature and the maximum heat flow but enlarged the peak temperature. Besides, relevant kinetic parameters such as the heat of reaction (ΔH) and the activation energy (Ea) were obtained and compared. It was found that all the three conditions could reduce the values of Ea and most of them produced larger reaction heat. In addition, the critical explosion temperature (Tb) of the NC samples were derived. It was clear that not only the drying time but also the cycles would increase the thermal hazard of the NC. Yet, the right amount of water helped to reduce the thermal hazard.

Keywords: C80, nitrocellulose, storage conditions, the critical explosion temperature, thermal hazard

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Authors: Kazunori Takai, Weng Kaiwei, Sadao Araki, Hideki Yamamoto

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HFC and PFC gases have been commonly and widely used as refrigerant of air conditioner and as etching agent of semiconductor manufacturing process, because of their higher heat of vaporization and chemical stability. On the other hand, HFCs and PFCs gases have the high global warming effect on the earth. Therefore, we have to be decomposed these gases emitted from chemical apparatus like as refrigerator. Until now, disposal of these gases were carried out by using combustion method like as Rotary kiln treatment mainly. However, this treatment needs extremely high temperature over 1000 °C. In the recent year, in order to reduce the energy consumption, a hydrolytic decomposition method using catalyst and plasma decomposition treatment have been attracted much attention as a new disposal treatment. However, the decomposition of fluorine-containing gases under the wet condition is not able to avoid the generation of hydrofluoric acid. Hydrofluoric acid is corrosive gas and it deteriorates catalysts in the decomposition process. Moreover, an additional process for the neutralization of hydrofluoric acid is also indispensable. In this study, the decomposition of C2F6 using zeolite and zeolite/CaO mixture as reactant was evaluated in the dry condition at 923 K. The effect of the chemical structure of zeolite on the decomposition reaction was confirmed by using H-Y, H-Beta, H-MOR and H-ZSM-5. The formation of CaF2 in zeolite/CaO mixtures after the decomposition reaction was confirmed by XRD measurements. The decomposition of C2F6 using zeolite as reactant showed the closely similar behaviors regardless the type of zeolite (MOR, Y, ZSM-5, Beta type). There was no difference of XRD patterns of each zeolite before and after reaction. On the other hand, the difference in the C2F6 decomposition for each zeolite/CaO mixtures was observed. These results suggested that the rate-determining process for the C2F6 decomposition on zeolite alone is the removal of fluorine from reactive site. In other words, the C2F6 decomposition for the zeolite/CaO improved compared with that for the zeolite alone by the removal of the fluorite from reactive site. HMOR/CaO showed 100% of the decomposition for 3.5 h and significantly improved from zeolite alone. On the other hand, Y type zeolite showed no improvement, that is, the almost same value of Y type zeolite alone. The descending order of C2F6 decomposition was MOR, ZSM-5, beta and Y type zeolite. This order is similar to the acid strength characterized by NH3-TPD. Hence, it is considered that the C-F bond cleavage is closely related to the acid strength.

Keywords: hexafluoroethane, zeolite, calcium oxide, decomposition

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Authors: Xiaoling Ren, Guidong Yang

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As one of the largest industrial synthetic chemicals in the world, ammonia has the advantages of high energy density, easy liquefaction, and easy transportation, which is widely used in agriculture, chemical industry, energy storage, and other fields. The industrial Haber-Bosch method process for ammonia synthesis is generally conducted under severe conditions. It is essential to develop a green, sustainable strategy for ammonia production to meet the growing demand. In this direction, photocatalytic nitrogen reduction has huge advantages over the traditional, well-established Haber-Bosch process, such as the utilization of natural sun light as the energy source and significantly lower pressure and temperature to affect the reaction process. However, the high activation energy of nitrogen and the low efficiency of photo-generated electron-hole separation in the photocatalyst result in low ammonia production yield. Many researchers focus on improving the catalyst. In addition to modifying the catalyst, improving the dispersion of the catalyst and making full use of active sites are also means to improve the overall catalytic activity. Few studies have been carried out on this, which is the aim of this work. In this work, by making full use of the nitrogen activation ability of WO3-x with defective sites, small size WO3-x photocatalyst with high dispersibility was constructed, while the growth of WO3-x was restricted by using a high specific surface area mesoporous SBA-15 molecular sieve with the regular pore structure as a template. The morphology of pure SBA-15 and WO3-x/SBA-15 was characterized byscanning electron microscopy (SEM). Compared with pure SBA-15, some small particles can be found in the WO3-x/SBA-15 material, which means that WO3-x grows into small particles under the limitation of SBA-15, which is conducive to the exposure of catalytically active sites. To elucidate the chemical nature of the material, the X-ray diffraction (XRD) analysis was conducted. The observed diffraction pattern inWO3-xis in good agreement with that of the JCPDS file no.71-2450. Compared with WO3-x, no new peaks appeared in WO3-x/SBA-15.It can be concluded that WO3-x/SBA-15 was synthesized successfully. In order to provide more active sites, the mass content of WO3-x was optimized. Then the photocatalytic nitrogen reduction performances of above samples were performed with methanol as a hole scavenger. The results show that the overall ammonia production performance of WO3-x/SBA-15 is improved than pure bulk WO3-x. The above results prove that making full use of active sites is also a means to improve overall catalytic activity.This work provides material basis for the design of high-efficiency photocatalytic nitrogen reduction catalysts.

Keywords: ammonia, photocatalytic, nitrogen reduction, WO3-x, high dispersibility

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Authors: Augustus K. Lebechi, Kenneth I. Ozoemena

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Rechargeable zinc-air batteries (RZABs) have been described as one of the most viable next-generation ‘beyond-the-lithium-ion’ battery technologies with great potential for renewable energy storage. It is safe, with a high specific energy density (1086 Wh/kg), environmentally benign, and low-cost, especially in resource-limited African countries. For widespread commercialization, the sluggish oxygen reaction kinetics pose a major challenge that impedes the reversibility of the system. Hence, there is a need for low-cost and highly active bifunctional electrocatalysts. Manganese oxide catalysts on carbon conducting additives remain the best couple for the realization of such low-cost RZABs. In this work, hausmannite Mn₃O₄ nanoparticles were synthesized through the annealing method from commercial electrolytic manganese dioxide (EMD), multi-walled carbon nanotubes (MWCNTs) were synthesized via the chemical vapor deposition (CVD) method and carbon nanofibers (CNFs) were synthesized via the electrospinning process with subsequent carbonization. Both Mn₃O₄ catalysts and the carbon conducting additives (MWCNT and CNF) were thoroughly characterized using X-ray powder diffraction spectroscopy (XRD), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and X-ray photoelectron spectroscopy (XPS). Composite electrocatalysts (Mn₃O₄/CNT and Mn₃O₄/CNF) were investigated for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in an alkaline medium. Using the established electrocatalytic modalities for evaluating the electrocatalytic performance of materials (including double layer, electrochemical active surface area, roughness factor, specific current density, and catalytic stability), CNFs proved to be the most efficient conducting additive material for the Mn₃O₄ catalyst. From the DFT calculations, the higher performance of the CNFs over the MWCNTs is related to the ability of the CNFs to allow for a more favorable distribution of the d-electrons of the manganese (Mn) and enhanced synergistic effect with Mn₃O₄ for weaker adsorption energies of the oxygen intermediates (O*, OH* and OOH*). In a proof-of-concept, Mn₃O₄/CNF was investigated as the air cathode for rechargeable zinc-air battery (RZAB) in a micro-3D-printed cell configuration. The RZAB showed good performance in terms of open circuit voltage (1.77 V), maximum power density (177.5 mW cm-2), areal-discharge energy and cycling stability comparable to Pt/C (20 wt%) + IrO2. The findings here provide fresh physicochemical perspectives on the future design and utility of CNFs for developing manganese-based RZABs.

Keywords: bifunctional electrocatalyst, oxygen evolution reaction, oxygen reduction reactions, rechargeable zinc-air batteries.

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Authors: Fatiha Benghanem, Mokhtar Berarma, Saida Keraghel, Ali Ourari

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Corrosion is the result of the reaction between a material and its environment. Steel in concrete is protected from corrosion by a passive film promoted by concrete alkalinity. For the initiation of corrosion, this protective film must be destroyed and this can be mainly done in two ways: by the attack of chlorides on the steel or by carbonation of the cover concrete due the reaction with carbon dioxide, which causes reduction in the alkalinity of concrete. The literature reports several ways to decrease or to prevent reinforcement corrosion. Among them, the use of corrosion inhibitors has been an envisaged solution. Two approaches are generally used to evaluate the efficiency of inhibitors for concrete application; one uses simulated pore solution testing , and the other uses actual concrete or mortar specimens. Both methods are some times used in conjunction. The aim of this study is to investigate the use of 2,3-diaminopyridine as a corrosion inhibitors of steel in alkaline media which simulate the electrolyte in the concrete pores. The effectiveness of this compound as corrosion inhibitor was investigated by measuring the corrosion potentials, the polarization curves and the corrosion current densities of steel with and without chlorides. The study of corrosion inhibition by this compound led to the conclusion that he has low rates of inhibition in the absence of aggressive ions and high rates in their presence. This type of organic compounds are promoting for the protection of armatures in concrete.

Keywords: corrosion, inhibitors, mild steel, conjunction

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Authors: Manasi Roy, Raju Mondal

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During last two decades the synthesis and design of MOFs or novel coordination polymers (CPs) has flourished as an emerging area of research due to their role as functional materials. Accordingly, ten new cobalt-based MOFs have been synthesized using a simple bispyrazole ligand, 4,4′-methylene-bispyrazole (H2MBP), and isophthalic acid (H2IPA) and its four 5-substituted derivatives R-H2IPA (R = COOH, OH, tBu, NH2). The major aim of this study was to validate the mutual influence of temperature and substitutions on the final structural self-assembly. Five different isophthalic acid derivatives were used to study the influence of substituents while each reaction was carried out at two different temperatures to assess the temperature effect. A clear correlation was observed between the reaction temperature and the coordination number of the cobalt atoms which consequently changes the self assembly pattern. Another fact that the periodical change in coordination number did bring about some systematic changes in the structural network via secondary building unit selectivity. With the presence of a tunable cavity inside the network, and unsaturated metal centers, MOFs show highly encouraging photocatalytic degradation of toxic dye with a potential application in waste water purification. Another fascinating aspect of this work is the construction of magnetic coordination polymers with the occurrence of a not-so-common MCE behavior of cobalt-based MOF.

Keywords: MOFs, temperature effect, MCE, dye degradation

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Authors: Harminder Kaur, Manpreet Kaur, Akanksha Kapila, Reenu

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Schiff base with general formula H₂L was derived from condensation of o-vanillin and 3-nitro-o-phenylenediamine. This Schiff base was used for the synthesis of organotin(IV) complexes with general formula R₂SnL [R=Phenyl or n-octyl] using equimolar quantities. Elemental analysis UV-Vis, FTIR, and multinuclear spectroscopic techniques (¹H, ¹³C, and ¹¹⁹Sn) NMR were carried out for the characterization of the synthesized complexes. These complexes were coloured and soluble in polar solvents. Computational studies have been performed to obtain the details of the geometry and electronic structures of ligand as well as complexes. Geometry of the ligands and complexes have been optimized at the level of Density Functional Theory with B3LYP/6-311G (d,p) and B3LYP/MPW1PW91 respectively followed by vibrational frequency analysis using Gaussian 09. Observed ¹¹⁹Sn NMR chemical shifts of one of the synthesized complexes showed tetrahedral geometry around Tin atom which is also confirmed by DFT. HOMO-LUMO energy distribution was calculated. FTIR, ¹HNMR and ¹³CNMR spectra were also obtained theoretically using DFT. Further IRC calculations were employed to determine the transition state for the reaction and to get the theoretical information about the reaction pathway. Moreover, molecular docking studies can be explored to ensure the anticancer activity of the newly synthesized organotin(IV) complexes.

Keywords: DFT, molecular docking, organotin(IV) complexes, o-vanillin, 3-nitro-o-phenylenediamine

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Authors: Khelladi Hadj Mostefa, Krouf Djamil, Taleb-Dida Nawel

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Background: Obesity results from a prolonged imbalance between energy intake and energy expenditure, as depending on basal metabolic rate. Oils and proteins from sea have important therapeutic (such as obesity and hypercholesterolemia) and antioxidant effects. Sardine are a widely consumed fish in the Mediterranean region. Its consumption provides humans with various nutrients such as oils (rich in omega 3 plyunsaturated fatty acids)) and proteins. Methods: Sardine oil (SO) and sardine proteins (SP) were extracted and purified. Mixture of vegetable oils (olive-walnut-sunflower) were prepared from oils produced in Algeria. Eighteen wistar rats are fed a high fat diet enriched with 1% cholesterol for 30 days to induce obesity and hypercholesterolemia. The rats are divided into 3 groups. The first group consumes 20% sardine protein combined with 5% sardine oil (38% SFA (saturated fatty acids), 31% MIFA (monounsaturated fatty acids) and 31% PIFA (polyunsaturated fatty acids)) (SPso). The second group consumes 20% sardine protein combined with 5% of a mixture of vegetable oils (VO) containing 13% SFA, 58% MIFA and 29% PIFA (PSvo), and the third group consuming 20% casein combined with 5% of the mixture of vegetable oils and serves as a semi-synthetic reference (CASvo). Body weights and glycaemia are measured weekly After 28 days of experimentation, the rats are sacrificed, the blood and the liver removed. Serum assays of total cholesterol (TC) and triglycerides (TG) were performed by enzymatic colorimetric methods. Evaluation of lipid peroxidation was performed by assaying thiobarbituric acid reactive species (TBARS) and hydroperoxides values. The protein oxidation was performed by assaying carbonyl derivatives values. Finally, evaluation of antioxidant defense is made by measuring the activity of antioxidant enzymes, the superoxide dismutase (SOD) and the catalase (CAT).Results: After 28 days, the body weight (BW) of the rats increased significantly in SPso and SPvo groups compared to CAS group, by +11% and 7%, respectively. Cholesterolemia (TC) increased significantly in the SPso and SPvo groups compared to the CAS group (P<0.01), while triglyceridemia (TG) decreased significantly in the SPso group compared to SPvo and CAS groups (P<0.01). Albumin (marker of inflammation) increased in the PSs group compared to SPvo and CAS groups by +35% and +13%, respectively. The serum TBARS levels are -40% lower in SPso group compared to SPvo group, and they are -80% and -76% lower in SPso compared to SPvo and CAS groups, respectively. The level of carbonyls derivatives in the serum and liver are significantly reduced in the SPso group compared to the SPvo and CAS groups. Superoxide dismutase (SOD) activity decreased in liver of SPso group compared to SPvo group (P<0.01). While that of CAT is increased in liver tissue of SPso group compared to SPvo group (P<0.01). Conclusion: Sardine oil combined with sardine protein has a hypotriglyceridemic effect, reduces body weight, attenuates inflammation and seems to protect against lipid peroxidation and protein oxidation and increases antioxidant defense in hypercholesterolemic and obese rats. This could be in favor of a protective effect against obesity and cardiovascular diseases.

Keywords: rat, obesity, hypercholesterolemia, sardine protein, sardine oil, vegetable oils mixture, lipid peroxidation, protein oxidation, antioxidant defense

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Authors: Abdelghani Boucheham, Ahcene Karaali, Amar Manseri

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Nanostructured Titania layers formed on the surface of titanium and titanium alloys by anodic oxidation play an important role in the enhancement of their biocompatibility and osseointegration in the human body. In the current work, highly ordered titania nanotube array films were elaborated on Ti₆Al₄V medical grade alloys in organic electrolyte containing ethylene glycol, 0.2 wt. % NH₄F and 4 vol. % H₂O at an applied potential of 60 V for different durations. The diameters, lengths and wall thicknesses of the obtained nanotubes were characterized by scanning electronic microscopy (SEM).

Keywords: anodization, dental implants, titania nanotubes, titanium alloys, SEM

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Authors: Petr Slobodian, Pavel Riha, Jiri Matyas, Robert Olejnik, Nuri Karakurt

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Thermoelectric devices generate an electrical current when there is a temperature gradient between the hot and cold junctions of two dissimilar conductive materials typically n-type and p-type semiconductors. Consequently, also the polymeric semiconductors composed of polymeric matrix filled by different forms of carbon nanotubes with proper structural hierarchy can have thermoelectric properties which temperature difference transfer into electricity. In spite of lower thermoelectric efficiency of polymeric thermoelectrics in terms of the figure of merit, the properties as stretchability, flexibility, lightweight, low thermal conductivity, easy processing, and low manufacturing cost are advantages in many technological and ecological applications. Polyethylene-octene copolymer based highly elastic composites filled with multi-walled carbon nanotubes (MWCTs) were prepared by sonication of nanotube dispersion in a copolymer solution followed by their precipitation pouring into non-solvent. The electronic properties of MWCNTs were moderated by different treatment techniques such as chemical oxidation, decoration by Ag clusters or addition of low molecular dopants. In this concept, for example, the amounts of oxygenated functional groups attached on MWCNT surface by HNO₃ oxidation increase p-type charge carriers. p-type of charge carriers can be further increased by doping with molecules of triphenylphosphine. For partial altering p-type MWCNTs into less p-type ones, Ag nanoparticles were deposited on MWCNT surface and then doped with 7,7,8,8-tetracyanoquino-dimethane. Both types of MWCNTs with the highest difference in generated thermoelectric power were combined to manufacture polymeric based thermoelectric module generating thermoelectric voltage when the temperature difference is applied between hot and cold ends of the module. Moreover, it was found that the generated voltage by the thermoelectric module at constant temperature gradient was significantly affected when exposed to vapors of different volatile organic compounds representing then a self-powered thermoelectric sensor for chemical vapor detection.

Keywords: carbon nanotubes, polymer composites, thermoelectric materials, self-powered gas sensor

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Authors: Sutar Rani Ananda, M. V. Murugendrappa

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To investigate electrical properties of conducting polypyrrole (PPy) and cobalt aluminum oxide (CAO) nanocomposites, impedance analyzer in frequency range of 100 Hz to 5 MHz is used. In this work, PPy/CAO nanocomposites were synthesized by chemical oxidation polymerization method in different weight percent of CAO in PPy. The dielectric properties and AC conductivity studies were carried out for different nanocomposites in temperature range of room temperature to 180 °C. With the increase in frequency, the dielectric constant for all the nanocomposites was observed to decrease. AC conductivity of PPy was improved by addition of CAO nanopowder.

Keywords: polypyrrole, dielectric constant, dielectric loss, AC conductivity

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Authors: Andrée-Anne Parent, Alain-Steve Comtois

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The Antarctica environment can be a great challenge for human exploration. Explorers need to be focused on the task and require the physical abilities to succeed and survive in complete autonomy in this hostile environment. The aim of this study was to observe cognitive performance and physiological stress with a biomarker (cortisol) and hand grip strength during an expedition in Antarctica. A total of 6 explorers were in complete autonomous exploration on the Forbidden Plateau in Antarctica to reach unknown summits during a 30 day period. The Stroop Test, a simple reaction time, and mood scale (PANAS) tests were performed every week during the expedition. Saliva samples were taken before sailing to Antarctica, the first day on the continent, after the mission on the continent and on the boat return trip. Furthermore, hair samples were taken before and after the expedition. The results were analyzed with SPSS using ANOVA repeated measures. The Stroop and mood scale results are presented in the following order: 1) before sailing to Antarctica, 2) the first day on the continent, 3) after the mission on the continent and 4) on the boat return trip. No significant difference was observed with the Stroop (759±166 ms, 850±114 ms, 772±179 ms and 833±105 ms, respectively) and the PANAS (39.5 ±5.7, 40.5±5, 41.8±6.9, 37.3±5.8 positive emotions, and 17.5±2.3, 18.2±5, 18.3±8.6, 15.8±5.4 negative emotions, respectively) (p>0.05). However, there appears to be an improvement at the end of the second week. Furthermore, the simple reaction time was significantly lower at the end of the second week, a moment where important decisions were taken about the mission, vs the week before (416±39 ms vs 459.8±39 ms respectively; p=0.030). Furthermore, the saliva cortisol was not significantly different (p>0.05) possibly due to important variations and seemed to reach a peak on the first day on the continent. However, the cortisol from the hair pre and post expedition increased significantly (2.4±0.5 pg/mg pre-expedition and 16.7±9.2 pg/mg post-expedition, p=0.013) showing important stress during the expedition. Moreover, no significant difference was observed on the grip strength except between after the mission on the continent and after the boat return trip (91.5±21 kg vs 85±19 kg, p=0.20). In conclusion, the cognitive performance does not seem to be affected during the expedition. Furthermore, it seems to increase for specific important events where the crew seemed to focus on the present task. The physiological stress does not seem to change significantly at specific moments, however, a global pre-post mission measure can be important and for this reason, for long-term missions, a pre-expedition baseline measure is important for crewmembers.

Keywords: Antarctica, cognitive performance, expedition, physiological adaptation, reaction time

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Authors: Carlos A. C. G. Neto, Natan C. G. e Silva , Thaís de O. Costa, Luciana R. B. Gonçalves, Maria V. P. Rocha

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β-galactosidases (E.C. 3.2.1.23) are enzymes that have attracted by catalyzing the hydrolysis of lactose and in producing galacto-oligosaccharides by favoring transgalactosylation reactions. These enzymes, when immobilized, can have some enzymatic characteristics substantially improved, and the coating of supports with multifunctional polymers is a promising alternative to enhance the stability of the biocatalysts, among which polyethylenimine (PEI) stands out. PEI has certain properties, such as being a flexible polymer that suits the structure of the enzyme, giving greater stability, especially for multimeric enzymes such as β-galactosidases. Besides that, protects them from environmental variations. The use of chitosan support coated with PEI could improve the catalytic efficiency of β-galactosidase from Kluyveromyces lactis in the transgalactosylation reaction for the production of prebiotics, such as lactulose since this strain is more effective in the hydrolysis reaction. In this context, the aim of the present work was first to develop biocatalysts of β-galactosidase from K. lactis immobilized on chitosan-coated with PEI, determining the immobilization parameters, its operational and thermal stability, and then to apply it in hydrolysis and transgalactolisation reactions to produce lactulose using whey as a substrate. The immobilization of β-galactosidase in chitosan previously functionalized with 0.8% (v/v) glutaraldehyde and then coated with 10% (w/v) PEI solution was evaluated using an enzymatic load of 10 mg protein per gram support. Subsequently, the hydrolysis and transgalactosylation reactions were conducted at 50 °C, 120 RPM for 20 minutes, using whey supplemented with fructose at a ratio of 1:2 lactose/fructose, totaling 200 g/L. Operational stability studies were performed in the same conditions for 10 cycles. Thermal stabilities of biocatalysts were conducted at 50 ºC in 50 mM phosphate buffer, pH 6.6 with 0.1 mM MnCl2. The biocatalyst whose support was coated was named CHI_GLU_PEI_GAL, and the one that was not coated was named CHI_GLU_GAL. The coating of the support with PEI considerably improved the parameters of immobilization. The immobilization yield increased from 56.53% to 97.45%, biocatalyst activity from 38.93 U/g to 95.26 U/g and the efficiency from 3.51% to 6.0% for uncoated and coated support, respectively. The biocatalyst CHI_GLU_PEI_GAL was better than CHI_GLU_GAL in the hydrolysis of lactose and production of lactulose, converting 97.05% of lactose at 5 min of reaction and producing 7.60 g/L lactulose in the same time interval. QUI_GLU_PEI_GAL biocatalyst was stable in the hydrolysis reactions of lactose during the 10 cycles evaluated, converting 73.45% lactose even after the tenth cycle, and in the lactulose production was stable until the fifth cycle evaluated, producing 10.95 g/L lactulose. However, the thermal stability of CHI_GLU_GAL biocatalyst was superior, with a half-life time 6 times higher, probably because the enzyme was immobilized by covalent bonding, which is stronger than adsorption (CHI_GLU_PEI_GAL). Therefore, the strategy of coating the supports with PEI has proven to be effective for the immobilization of β-galactosidase from K. lactis, considerably improving the immobilization parameters, as well as, the catalytic action of the enzyme. Besides that, this process can be economically viable due to the use of an industrial residue as a substrate.

Keywords: β-galactosidase, immobilization, kluyveromyces lactis, lactulose, polyethylenimine, transgalactosylation reaction, whey

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Authors: Ludmila A. Gavriliuc, Jerry McLarty, Heather E. Kleiner, J. Michael Mathis

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Abstract -- Background: The citrus coumarine Auraptene (Aur) is an effective chemopreventive agent, as manifested in many models of diseases and cancer. Nuclear factor erythroid 2-related factor (Nrf2) is an important regulator of genes induced by oxidative stress, such as glutathione S-transferases, heme oxygenase-1, and peroxiredoxin 1, by activating the antioxidant response element (ARE). Genetic and biochemical evidence has demonstrated that glutathione (GSH) and glutathione-dependent enzymes, glutathione reductase (GR), glutathione peroxidases (GPs), glutathione S-transferases (GSTs) are responsible for the control of intracellular reduction-oxidation status and participate in cellular adaptation to oxidative stress. The effect of Aur on the activity of GR, GPs (Se-GP and Se-iGP), and content of GSH in the liver, kidney, and spleen is insufficiently explored. Aim: Our goal was the examination of the Aur influence on the redox-system of GSH in Nrf2 wild type and Nrf2 knockout mice via activation of Nrf2 and ARE. Methods: Twenty female mice, 10 Nrf2 wild-type (WT) and 10 Nrf2 (-/-) knockout (KO), were bred and genotyped for our study. The activity of GR, Se-GP, Se-iGP, GST, G6PD, CytP450 reductase, catalase (Cat), and content of GSH were analyzed in the liver, kidney, and spleen using Spectrophotometry methods. The results of the specific activity of enzymes and the amount of GSH were analyzed with ANOVA and Spearman statistical methods. Results: Aur (200 mg/kg) treatment induced hepatic GST, GR, Se-GP activity and inhibited their activity in the spleen of mice, most likely via activation of the ARE through Nrf2. Activation in kidney Se-GP and G6PD by Aur is also controlled, apparently through Nrf2. Results of the non-parametric Spearman correlation analysis indicated the strong positive correlation between GR and G6PD only in the liver in WT control mice (r=+0.972; p < 0.005) and in the kidney KO control mice (r=+0.958; p < 0.005). The observed low content of GSH in the liver of KO mice indicated an increase in its participation in the neutralization of toxic substances with the absence of induction of GSH-dependent enzymes, such as GST, GR, Se-GP, and Se-iGP. Activation of CytP450 in kidney and spleen and Cat in the liver in KO mice probably revealed another regulatory mechanism for these enzymes. Conclusion: Thereby, obtained results testify that Aur can modulate the activity of genes and antioxidant enzymatic redox-system of GSH, responsible for the control of intracellular reduction-oxidation status.

Keywords: auraptene, glutathione, GST, Nrf2

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Authors: N. Wijayati, Kusoro Siadi, Hanny Wijaya, Maggy Thenawijjaja Suhartono

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This work describes the lipase-mediated synthesis of α-pinene oxide at ambient temperature. The immobilized lipase from Pseudomonas aeruginosa is used to generate peroxyoctanoic acid directly from octanoic acid and hydrogen peroxide. The peroxy acid formed is then applied for in situ oxidation of α-pinene. High conversion of α-pinene to α-pinene oxide (approximately 78%) was achieved when using 0,1 g enzim lipase, 6 mmol H2O2, dan 5 mmol octanoic acid. Various parameters affecting the conversion of α-pinene to α pinene oxide were studied.

Keywords: α-Pinene; P. aeruginosa; Octanoic acid

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Authors: S. Curteanu, F. Leon, M. Gavrilescu, S. A. Floria

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Optimization algorithms inspired from human behavior were applied in this approach, associated with neural networks models. The algorithms belong to human behaviors of learning and cooperation and human competitive behavior classes. For the first class, the main strategies include: random learning, individual learning, and social learning, and the selected algorithms are: simplified human learning optimization (SHLO), social learning optimization (SLO), and teaching-learning based optimization (TLBO). For the second class, the concept of learning is associated with competitiveness, and the selected algorithms are sports-inspired algorithms (with Football Game Algorithm, FGA and Volleyball Premier League, VPL) and Imperialist Competitive Algorithm (ICA). A real process, the synthesis of polyacrylamide-based multicomponent hydrogels, where some parameters are difficult to obtain experimentally, is considered as a case study. Reaction yield and swelling degree are predicted as a function of reaction conditions (acrylamide concentration, initiator concentration, crosslinking agent concentration, temperature, reaction time, and amount of inclusion polymer, which could be starch, poly(vinyl alcohol) or gelatin). The experimental results contain 175 data. Artificial neural networks are obtained in optimal form with biologically inspired algorithm; the optimization being perform at two level: structural and parametric. Feedforward neural networks with one or two hidden layers and no more than 25 neurons in intermediate layers were obtained with values of correlation coefficient in the validation phase over 0.90. The best results were obtained with TLBO algorithm, correlation coefficient being 0.94 for an MLP(6:9:20:2) – a feedforward neural network with two hidden layers and 9 and 20, respectively, intermediate neurons. Good results obtained prove the efficiency of the optimization algorithms. More than the good results, what is important in this approach is the simulation methodology, including neural networks and optimization biologically inspired algorithms, which provide satisfactory results. In addition, the methodology developed in this approach is general and has flexibility so that it can be easily adapted to other processes in association with different types of models.

Keywords: artificial neural networks, human behaviors of learning and cooperation, human competitive behavior, optimization algorithms

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Authors: Dorothea Voß, Tobias Esser, Michael Huber, Jakob Albert

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The growing world population and the associated increase in demand for energy and consumer goods, as well as increasing waste production, requires the development of sustainable processes. In addition, the increasing environmental awareness of our society is a driving force for the requirement that processes must be as resource and energy efficient as possible. In this context, the use of polyoxometalate catalysts (POMs) has emerged as a promising approach for the development of green processes. POMs are bifunctional polynuclear metal-oxo-anion cluster characterized by a strong Brønsted acidity, a high proton mobility combined with fast multi-electron transfer and tunable redox potential. In addition, POMs are soluble in many commonly known solvents and exhibit resistance to hydrolytic and oxidative degradation. Due to their structure and excellent physicochemical properties, POMs are efficient acid and oxidation catalysts that have attracted much attention in recent years. Oxidation processes with molecular oxygen are worth mentioning here. However, the fact that the POM catalysts are homogeneous poses a challenge for downstream processing of product solutions and recycling of the catalysts. In this regard, nanofiltration membranes have gained increasing interest in recent years, particularly due to their relative sustainability advantage over other technologies and their unique properties such as increased selectivity towards multivalent ions. In order to establish an efficient downstream process for the highly selective separation of homogeneous POM catalysts from aqueous solutions using nanofiltration membranes, a laboratory-scale membrane system was designed and constructed. By varying various process parameters, a sensitivity analysis was performed on a model system to develop an optimized method for the recovery of POM catalysts. From this, process-relevant key figures such as the rejection of various system components were derived. These results form the basis for further experiments on other systems to test the transferability to serval separation tasks with different POMs and products, as well as for recycling experiments of the catalysts in processes on laboratory scale.

Keywords: downstream processing, nanofiltration, polyoxometalates, homogeneous catalysis, green chemistry

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Authors: Aqeela Ashraf, Muhammad Imran, Tahir Yaqub, Muhammad Tayyab, Yung Fu Chang

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For the identification of bovine mastitic pathogen, an economical, rapid and sensitive molecular diagnostic assay is developed by PCR multiplexing of gene and pathogenic species specific DNA sequences. The multiplex PCR assay is developed for detecting nine important bacterial pathogens causing mastitis Worldwide. The bacterial species selected for this study are Streptococcus agalactiae, Streptococcus dysagalactiae, Streptococcus uberis, Staphylococcus aureus, Escherichia coli, Staphylococcus haemolyticus, Staphylococcus chromogenes Mycoplasma bovis and Staphylococcus epidermidis. A single reaction assay was developed and validated by 27 reference strains and further tested on 276 bacterial strains obtained from culturing mastitic milk. The multiplex PCR assay developed here is further evaluated by applying directly on genomic DNA isolated from 200 mastitic milk samples. It is compared with bacterial culturing method and proved to be more sensitive, rapid, economical and can specifically identify 9 bacterial pathogens in a single reaction. It has detected the pathogens in few culture negative mastitic samples. Recognition of disease is the foundation of disease control and prevention. This assay can be very helpful for maintaining the udder health and milk monitoring.

Keywords: multiplex PCR, bacteria, mastitis, milk

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Authors: Laura Salvia Diaz Silvarrey, Anh Phan

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Municipal Plastic Waste (MPW) comprises a mixture of thermoplastics such as high and low density polyethylene (HDPE and LDPE), polypropylene (PP), polystyrene (PS) and polyethylene terephthalate (PET). Recycling rate of these plastics is low, e.g. only 27% in 2013. The remains were incinerated or disposed in landfills. As MPW generation increases approximately 5% per annum, MPW management technologies have to be developed to comply with legislation . Pyrolysis, thermochemical decomposition, provides an excellent alternative to convert MPW into valuable resources like fuels and chemicals. Most studies on waste plastic kinetics only focused on HDPE and LDPE with a simple assumption of first order decomposition, which is not the real reaction mechanism. The aim of this study was to develop a kinetic study for each of the polymers in the MPW mixture using thermogravimetric analysis (TGA) over a range of heating rates (5, 10, 20 and 40°C/min) in N2 atmosphere and sample size of 1 – 4mm. A model-free kinetic method was applied to quantify the activation energy at each level of conversion. Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) equations jointly with Master Plots confirmed that the activation energy was not constant along all the reaction for all the five plastic studied, showing that MPW decomposed through a complex mechanism and not by first-order kinetics. Master plots confirmed that MPW decomposed following a random scission mechanism at conversions above 40%. According to the random scission mechanism, different radicals are formed along the backbone producing the cleavage of bonds by chain scission into molecules of different lengths. The cleavage of bonds during random scission follows first-order kinetics and it is related with the conversion. When a bond is broken one part of the initial molecule becomes an unsaturated one and the other a terminal free radical. The latter can react with hydrogen from and adjacent carbon releasing another free radical and a saturated molecule or reacting with another free radical and forming an alkane. Not every time a bonds is broken a molecule is evaporated. At early stages of the reaction (conversion and temperature below 40% and 300°C), most products are not short enough to evaporate. Only at higher degrees of conversion most of cleavage of bonds releases molecules small enough to evaporate.

Keywords: kinetic, municipal plastic waste, pyrolysis, random scission

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Authors: Lukasz Szymanski, Zbigniew Kolacinski, Grzegorz Raniszewski, Slawomir Wiak, Lukasz Pietrzak, Dariusz Koza, Karolina Przybylowska-Sygut, Ireneusz Majsterek, Zbigniew Kaminski, Justyna Fraczyk, Malgorzata Walczak, Beata Kolasinska, Adam Bednarek, Joanna Konka

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The aim of this work is to investigate the influence of electromagnetic field from the range of radio frequencies on the desired nanoparticles for cancer therapy. In the article, the development and demonstration of the method and the model device for hyperthermic selective destruction of cancer cells are presented. This method was based on the synthesis and functionalization of carbon nanotubes serving as ferromagnetic material nanocontainers. The methodology of the production carbon - ferromagnetic nanocontainers (FNCs) includes: The synthesis of carbon nanotubes, chemical, and physical characterization, increasing the content of a ferromagnetic material and biochemical functionalization involving the attachment of the key addresses. The ferromagnetic nanocontainers were synthesised in CVD and microwave plasma system. Biochemical functionalization of ferromagnetic nanocontainers is necessary in order to increase the binding selectively with receptors presented on the surface of tumour cells. Multi-step modification procedure was finally used to attach folic acid on the surface of ferromagnetic nanocontainers. Pristine ferromagnetic carbon nanotubes are not suitable for application in medicine and biotechnology. Appropriate functionalization of ferromagnetic carbon nanotubes allows to receiving materials useful in medicine. Finally, a product contains folic acids on the surface of FNCs. The folic acid is a ligand of folate receptors – α which is overexpressed on the surface of epithelial tumours cells. It is expected that folic acids will be recognized and selectively bound by receptors presented on the surface of tumour cells. In our research, FNCs were covalently functionalized in a multi-step procedure. Ferromagnetic carbon nanotubes were oxidated using different oxidative agents. For this purpose, strong acids such as HNO3, or mixture HNO3 and H2SO4 were used. Reactive carbonyl and carboxyl groups were formed on the open sides and at the defects on the sidewalls of FNCs. These groups allow further modification of FNCs as a reaction of amidation, reaction of introduction appropriate linkers which separate solid surface of FNCs and ligand (folic acid). In our studies, amino acid and peptide have been applied as ligands. The last step of chemical modification was reaction-condensation with folic acid. In all reaction as coupling reagents were used derivatives of 1,3,5-triazine. The first trials in the device for hyperthermal RF generator have been done. The frequency of RF generator was in the ranges from 10 to 14Mhz and from 265 to 621kHz. Obtained functionalized nanoparticles enabled to reach the temperature of denaturation tumor cells in given frequencies.

Keywords: cancer colon cells, carbon nanotubes, hyperthermia, ligands

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Authors: Wu Wei-Ting, Liu Po-Yen, Chang Chin-Tzu, Cheng Wei-Chun

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Three types of low-temperature phase transformations in an Fe-12.5 Mn-6.53 Al-1.28 C (wt %) alloy have been studied. The steel underwent solution heat treatment at 1100℃ and isothermal holding at low temperatures. γ’ phase appears in the austenite matrix in the air-cooled steel. Coherent ultra-fine particles of γ’ phase precipitated uniformly in the austenite matrix after the air-cooling process. These ultra-fine particles were very small and only could be detected by TEM through dark-field images. After short periods of isothermal holding at low temperatures these particles of γ’ phase grew and could be easily detected by TEM. A pro-eutectoid reaction happened after isothermal holding at temperatures below 875 ℃. Proeutectoid κ-carbide and ferrite appear in the austenite matrix as grain boundary precipitates and cellular precipitates. The cellular precipitates are composed of lamellar κ-carbide and austenite. The lamellar κ-carbide grains are always accompanied by layers of austenite twins. The presence of twin layers adhering to the κ-carbide plates might be attributed to the lower activation energy for the precipitation of κ-carbide plates in the austenite. The final form of phase transformation is the eutectoid reaction for the decomposition of supersaturated austenite into stable κ-carbide and ferrite phases at temperatures below 700℃. The ferrite and κ-carbide are in the form of pearlite lamellae.

Keywords: austenite, austenite twin layers, κ-carbide, twins

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Authors: Yogi Wibisono Budhi, Ferry Iskandar, Veinardi Suendo, Muhammad Fakhrudin, Neng Tresna Umi Culsum

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Oil palm empty fruit bunch (OPEFB), an abundant agro-waste in Indonesia, is being studied as raw material of Cellulose Nanocrystals (CNC) synthesis. Instead of conventional acid mineral, phosphotungstic acid (H₃PW₁₂O₄₀, HPW) was used to hydrolyze cellulose due to recycling ability and easy handling. Before hydrolysis process, dried EFB was treated by 4% NaOH solution at 90oC for 2 hours and then bleached using 2% NaClO₂ solution at 80oC for 3 hours to remove hemicellulose and lignin. Hydrolysis reaction parameters such as temperature, acid concentration, and reaction time were optimized with fixed solid-liquid ratio of 1:40. Response surface method was used for experimental design to determine the optimum condition of each parameter. HPW was extracted from the mixed solution and recycled with diethyl ether. CNC was separated from the solution by centrifuging and washing with distilled water and ethanol to remove degraded sugars and unreacted celluloses. In this study, pulp from dried EFB produced 44.8% yield of CNC. Dynamic Light Scattering (DLS) analysis showed that most of CNC equivalent diameter was 140 nm. Crystallinity index was observed at 73.3% using X-ray Diffraction (XRD) analysis. Thus, a green established process for the preparation of CNC was achieved.

Keywords: acid hydrolysis, cellulose nanocrystals, oil palm empty fruit bunch, phosphotungstic acid

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Authors: Adriana Sosa, Susana Rincon, Chérif Ben, Diana Cabañas, Juan E. Ruiz, Alejandro Zepeda

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The complex chemical composition (mixtures of ammonium and recalcitrant compounds) of the effluents from the chemical, pharmaceutical and petrochemical industries represents a challenge in their biological treatment. This treatment involves nitrification process that can suffer an inhibition due to the presence of aromatic compounds giving as a result the decrease of the process efficiency. The inhibitory effects on nitrification in the presence of aromatic compounds have already been studied; however a few studies have considered the presence of phenolic compounds in the form of mixtures, which is the form that they are present in real context. For this reason, we realized a kinetic study on the nitrifying process in the presence of different concentrations of a mixture of phenol, o-cresol, m-cresol and p-cresol (0 - 320 mg C/L) in a sequencing batch reactor (SBR). Firstly, the nitrifying process was evaluated in absence of the phenolic mixture (control 1) in a SBR with 2 L working volume and 176 mg/L of nitrogen of microbial protein. Total oxidation of initial ammonium (efficiency; ENH4+ of 100 %) to nitrate (nitrifying yield; YNO3- of 0.95) were obtained with specific rates of ammonium consumption (qN-NH4+) and nitrate production (qN-NO3-) (of 1.11 ± 0.04 h-1 and 0.67 h-1 ± 0.11 respectively. During the phase of acclimation with 40 mg C/L of the phenolic mixture, an inhibitory effect on the nitrifying process was observed, provoking a decrease in ENH4+ and YNO3- (11 and 54 % respectively) as well as in the specific rates (89 y 46 % respectively), being the ammonia oxidizing bacteria (BAO) the most affected. However, in the next cycles without the phenolic mixture (control 2), the nitrifying consortium was able to recover its nitrifying capacity (ENH4+ = 100% and YNO3-=0.98). Afterwards the SBR was fed with 10 mg C/L of the phenolic mixture, obtaining and ENH4+ of 100%, YNO3- and qN-NH4+ 0.62 ± 0.006 and 0.13 ± 0.004 respectively, while the qN-NO3- was 0.49 ± 0.007. Moreover, with the increase of the phenolic concentrations (10-160 mg C/L) and the number of cycles the nitrifying consortium was able to oxidize the ammonia with ENH4+ of 100 % and YNO3- close to 1. However a decrease in the values of the nitrification specific rates and increase in the oxidation in phenolic compounds (70 to 94%) were observed. Finally, in the presence of 320 mg C/L, the nitrifying consortium was able to simultaneously oxidize the ammonia (ENH4+= 100%) and the phenolic mixture (p-cresol>phenol>m-cresol>o-cresol) being the o-cresol the most recalcitrant compound. In all the experiments the use of a SBR allowed a respiratory adaptation of the consortium to oxidize the phenolic mixture achieving greater adaptation of the nitrite-oxidizing bacteria (NOB) than in the ammonia-oxidizing bacteria (AOB).

Keywords: cresol, inhibition, nitrification, phenol, sequencing batch reactor

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Authors: Malee Santikunaporn, Tattep Techopittayakul, Channarong Asavatesanupap

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Biofuel production especially that of biodiesel has gained tremendous attention during the last decade due to environmental concerns and shortage in petroleum oil reservoir. This research aims to investigate the influences of operating parameters, such as the alcohol-to-oil molar ratio (4:1, 6:1, and 9:1) and the amount of catalyst (1, 1.5, and 2 wt.%) on the trans esterification of refined palm oil (RPO) in a medium-scale oscillatory baffle reactor.  It has been shown that an increase in the methanol-to-oil ratio resulted in an increase in fatty acid methyl esters (FAMEs) content. The amount of catalyst has an insignificant effect on the FAMEs content. Engine testing was performed on B0 (100 v/v% diesel) and blended fuel or B50 (50 v/v% diesel). Combustion of B50 was found to give lower torque compared to pure diesel. Exhaust gas from B50 was found to contain lower concentration of CO and CO₂.

Keywords: biodiesel, palm oil, transesterification, oscillatory baffled reactor

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Authors: Ashish Kumar Singh, Mehak Gulati, Neelam Verma

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Arginine majorly acts as a substrate for the enzyme nitric oxide synthase (NOS) for the production of nitric oxide, a strong vasodilator. Current study demonstrated a novel amperometric approach for estimation of arginine using nitric oxide synthase. The enzyme was co-immobilized in carbon paste electrode with NADP+, FAD and BH4 as cofactors. The detection principle of the biosensor is enzyme NOS catalyzes the conversion of arginine into nitric oxide. The developed biosensor could able to detect up to 10-9M of arginine. The oxidation peak of NO was observed at 0.65V. The developed arginine biosensor was used to monitor arginine content in fruit juices.

Keywords: arginine, biosensor, carbon paste elctrode, nitric oxide

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Authors: Om Kalthoum Sallem, Saidakilani, Kamiliya Ounaissa, Abdelmajid Abid

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Introduction and purposes: Olive oil is the main oil used in the Mediterranean diet. Virgin olive oil is valued for its organoleptic and nutritional characteristics and is resistant to oxidation due to its high monounsaturated fatty acid content (MUFAs), and low polyunsaturates (PUFAs) and the presence of natural antioxidants such as phenols, tocopherols and carotenoids. The fatty acid composition, especially the MUFA content, and the natural antioxidants provide advantages for health. The aim of the present study was to examine the impact of method of extraction on the chemical profiles of ‘Chemchali’ olive oil variety, which is cultivated in the city of Gafsa, and to compare it with chetoui and chemchali varieties. Methods: Our study is a qualitative prospective study that deals with ‘Chemchali’ olive oil variety. Analyses were conducted during three months (from December to February) in different oil mills in the city of Gafsa. We have compared ‘Chemchali’ olive oil obtained by continuous method to this obtained by superpress method. Then we have analyzed quality index parameters, including free fatty acid content (FFA), acidity, and UV spectrophotometric characteristics and other physico-chemical data [oxidative stability, ß-carotene, and chlorophyll pigment composition]. Results: Olive oil resulting from super press method compared with continuous method is less acid(0,6120 vs. 0,9760), less oxydazible(K232:2,478 vs. 2,592)(k270:0,216 vs. 0,228), more rich in oleic acid(61,61% vs. 66.99%), less rich in linoleic acid(13,38% vs. 13,98 %), more rich in total chlorophylls pigments (6,22 ppm vs. 3,18 ppm ) and ß-carotene (3,128 mg/kg vs. 1,73 mg/kg). ‘Chemchali’ olive oil showed more equilibrated total content in fatty acids compared with the varieties ’Chemleli’ and ‘Chetoui’. Gafsa’s variety ’Chemlali’ have significantly less saturated and polyunsaturated fatty acids. Whereas it has a higher content in monounsaturated fatty acid C18:2, compared with the two other varieties. Conclusion: The use of super press method had benefic effects on general chemical characteristics of ‘Chemchali’ olive oil, maintaining the highest quality according to the ecocert legal standards. In light of the results obtained in this study, a more detailed study is required to establish whether the differences in the chemical properties of oils are mainly due to agronomic and climate variables or, to the processing employed in oil mills.

Keywords: olive oil, extraction method, fatty acids, chemchali olive oil

Procedia PDF Downloads 383

Authors: Pedro J. Rolim-Neto, Leslie R. M. Ferraz, Fabiana L. A. Santos, Pablo A. Ferreira, Ricardo T. L. Maia-Jr., Magaly A. M. Lyra, Danilo A F. Fonte, Salvana P. M. Costa, Amanda C. Q. M. Vieira, Larissa A. Rolim

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Initially developed as an antimalarial agent, hydroxychloroquine (HCQ) sulfate is often used as a slow-acting antirheumatic drug in the treatment of disorders of connective tissue. The United States Pharmacopeia (USP) 37 provides a reversed-phase HPLC method for quantification of HCQ. However, this method was not reproducible, producing asymmetric peaks in a long analysis time. The asymmetry of the peak may cause an incorrect calculation of the concentration of the sample. Furthermore, the analysis time is unacceptable, especially regarding the routine of a pharmaceutical industry. The aiming of this study was to develop a fast, easy and efficient method for quantification of HCQ sulfate by High Performance Liquid Chromatography (HPLC) based on the Quality by Design (QbD) methodology. This method was optimized in terms of peak symmetry using the surface area graphic as the Design of Experiments (DoE) and the tailing factor (TF) as an indicator to the Design Space (DS). The reference method used was that described at USP 37 to the quantification of the drug. For the optimized method, was proposed a 33 factorial design, based on the QbD concepts. The DS was created with the TF (in a range between 0.98 and 1.2) in order to demonstrate the ideal analytical conditions. Changes were made in the composition of the USP mobile-phase (USP-MP): USP-MP: Methanol (90:10 v/v, 80:20 v/v and 70:30 v/v), in the flow (0.8, 1.0 and 1.2 mL) and in the oven temperature (30, 35, and 40ºC). The USP method allowed the quantification of drug in a long time (40-50 minutes). In addition, the method uses a high flow rate (1,5 mL.min-1) which increases the consumption of expensive solvents HPLC grade. The main problem observed was the TF value (1,8) that would be accepted if the drug was not a racemic mixture, since the co-elution of the isomers can become an unreliable peak integration. Therefore, the optimization was suggested in order to reduce the analysis time, aiming a better peak resolution and TF. For the optimization method, by the analysis of the surface-response plot it was possible to confirm the ideal setting analytical condition: 45 °C, 0,8 mL.min-1 and 80:20 USP-MP: Methanol. The optimized HPLC method enabled the quantification of HCQ sulfate, with a peak of high resolution, showing a TF value of 1,17. This promotes good co-elution of isomers of the HCQ, ensuring an accurate quantification of the raw material as racemic mixture. This method also proved to be 18 times faster, approximately, compared to the reference method, using a lower flow rate, reducing even more the consumption of the solvents and, consequently, the analysis cost. Thus, an analytical method for the quantification of HCQ sulfate was optimized using QbD methodology. This method proved to be faster and more efficient than the USP method, regarding the retention time and, especially, the peak resolution. The higher resolution in the chromatogram peaks supports the implementation of the method for quantification of the drug as racemic mixture, not requiring the separation of isomers.

Keywords: analytical method, hydroxychloroquine sulfate, quality by design, surface area graphic

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Authors: Luís R. Silva, Ana C. Gonçalves, Catarina Bento, Fábio Jesus, Branca M. Silva

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Prunus avium Linnaeus, more known as sweet cherry, is one of the most appreciated fruit worldwide. Most of these quantities are produced in Fundão region, being Saco the cultivar most produced. Saco is very rich in bioactive compounds, especially phenolics, and presents great antioxidant capacity. The purpose of the present study was to investigate the chemical profile and biological potential, concerning antioxidant, anti-diabetic activity and protective effects towards erythrocytes by Saco sweet cherry collected from Fundão region (Portugal). The hydroethanolic extracts were prepared and passed through a C18 solid-phase extraction column. The phenolic profile analyzed by LC-DAD method allowed to the identification of 22 phenolic compounds, being 16 non-phenolics and 6 anthocyanins. In respect to non-coloured phenolics, 3-O-caffeoylquinic and ρ-coumaroylquinic acids were the main ones. Concerning to anthocyanins, cyanidin-3-O-rutinoside was found in higher amounts. Relatively to biological potential, Saco showed great antioxidant potential, through DPPH and NO radical assays, with IC50 =16.24 ± 0.46 µg/mL and IC50 = 176.69 ± 3.35 µg/mL for DPPH and NO, respectively. These results were similar to those obtained for ascorbic acid control (IC50 = 16.92 ± 0.69 and IC50 = 162.66 ± 1.31 μg/mL for DPPH and NO, respectively). In respect to antidiabetic potential, Saco revealed capacity to inhibit α-glucosidase in a dose-dependent manner (IC50 = 10.79 ± 0.40 µg/mL), being much active than positive control acarbose (IC50 = 306.66 ± 0.84 μg/mL). Additionally, Saco extracts revealed protective effects against ROO•-mediated toxicity generated by AAPH in human blood erythrocytes, inhibiting hemoglobin oxidation (IC50 = 38.57 ± 0.96 μg/mL) and hemolysis (IC50 = 73.03 ± 1.48 μg/mL), in a concentration-dependent manner. However, Saco extracts were less effective than quercetin control (IC50 = 3.10 μg/mL and IC50 = 0.7 μg/mL for inhibition of hemoglobin oxidation and hemolysis, respectively). The results obtained showed that Saco is an excellent source of phenolic compounds. These ones are natural antioxidant substances, which easily capture reactive species. This work presents new insights regarding sweet cherry antioxidant properties which may be useful for the future development of new therapeutic strategies for preventing or attenuating oxidative-related disorders.

Keywords: antioxidant capacity, health benefits, phenolic compounds, saco

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Authors: Wael M. Rabeh, Cesar Carrasco-Lopez, Juliana C. Ferreira, Pance Naumov

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Bioluminescence, the emission of light from a biological process, is found in various living organisms including bacteria, fireflies, beetles, fungus and different marine organisms. Luciferase is an enzyme that catalyzes a two steps oxidation of luciferin in the presence of Mg2+ and ATP to produce oxyluciferin and releases energy in the form of light. The luciferase assay is used in biological research and clinical applications for in vivo imaging, cell proliferation, and protein folding and secretion analysis. The luciferase enzyme consists of two domains, a large N-terminal domain (1-436 residues) that is connected to a small C-terminal domain (440-544) by a flexible loop that functions as a hinge for opening and closing the active site. The two domains are separated by a large cleft housing the active site that closes after binding the substrates, luciferin and ATP. Even though all insect luciferases catalyze the same chemical reaction and share 50% to 90% sequence homology and high structural similarity, they emit light of different colors from green at 560nm to red at 640 nm. Currently, the majority of the structural and biochemical studies have been conducted on green-emitting firefly luciferases. To address the color emission mechanism, we expressed and purified two luciferase enzymes with blue-shifted green and red emission from indigenous Brazilian species Amydetes fanestratus and Phrixothrix, respectively. The two enzymes naturally emit light of different colors and they are an excellent system to study the color-emission mechanism of luciferases, as the current proposed mechanisms are based on mutagenesis studies. Using a vapor-diffusion method and a high-throughput approach, we crystallized and solved the crystal structure of both enzymes, at 1.7 Å and 3.1 Å resolution respectively, using X-ray crystallography. The free enzyme adopted two open conformations in the crystallographic unit cell that are different from the previously characterized firefly luciferase. The blue-shifted green luciferase crystalized as a monomer similar to other luciferases reported in literature, while the red luciferases crystalized as an octamer and was also purified as an octomer in solution. The octomer conformation is the first of its kind for any insect’s luciferase, which might be relate to the red color emission. Structurally designed mutations confirmed the importance of the transition between the open and close conformations in the fine-tuning of the color and the characterization of other interesting mutants is underway.

Keywords: bioluminescence, enzymology, structural biology, x-ray crystallography

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Authors: Harshdeep Singh, Kuljeet Singh Anand

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Background: Cerebrovascular Accidents (CVA) cause abnormal or asymmetrical tendon reflexes contributing to motor impairments. Since the tendon reflexes are mediated by the spinal cord, their effects on cognitive performances are overlooked. This study aims to find the contributions of tendon reflexes on the performance of the Flanker task. Methods: A total population of 46 mixed subjects with movement disorders were recruited for the study. Deep tendon reflexes (DTR) of the biceps, triceps and brachioradialis were assessed for both upper extremities. Later, the Flanker task was performed on all the subjects, and the mean Reaction Time (RT) along with both the congruent and incongruent stimuli were evaluated. For the final analysis, the Kruskal Wallis test was performed to see the difference between the DTR and the performance of the Flanker Task. Results: The Kruskal Wallis test results showed a significant difference between the DTR scores, X²(2) = 11.328, p= 0.023 with the mean RT of the flanker task and X²(2) = 9.531, p= 0.049 with mean RT of the Incongruent Stimuli. Whereas the result found a non-significant difference in the mean RT of the Congruent Stimuli. Conclusion: Each DTR score is distributed differently with the mean RT of the flanker task and for the incongruent stimuli as well. Therefore, the tendon reflexes in PD may be contributing to the performance of the Flanker Task and may be an indicator of abnormal cognitive performance. Further research is needed to evaluate how the RTs are distributed with each DTR score.

Keywords: cerebrovascular accidents, deep tendon reflexes, flanker task, reaction time, congruent stimuli, incongruent stimuli

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