Search results for: oxidation activity

Authors: Supriyono, Sumardiyono, Rendy J. Pramono

Abstract:

Biodiesel is one of the alternative fuels promising for substituting petrodiesel as energy source which has an advantage as it is sustainable and eco-friendly. Due to the raw material that tends to decompose during storage, biodiesel also has the same characteristic that tends to decompose during storage. Biodiesel decomposition will form higher acid value as the result of oxidation to double bond on a fatty acid compound on biodiesel. Thus, free fatty acid value could be used to evaluate degradation of biodiesel due to the oxidation process. High free fatty acid on biodiesel could impact on the engine performance. Decomposition of biodiesel due to oxidation reaction could prevent by introducing a small amount of antioxidant. The origin of raw materials and the process for producing biodiesel will determine the effectiveness of antioxidant. Biodiesel made from high free fatty acid (FFA) crude palm oil (CPO) by using two steps esterification is vulnerable to oxidation process which is resulted in increasing on the FFA value. Tocopherol also known as vitamin E is one of the antioxidant that could improve the stability of biodiesel due to decomposition by the oxidation process. Tocopherol 0.5% concentration on palm oil biodiesel could reduce 13% of increasing FFA under temperature 80 °C and exposing time 180 minute.

Keywords: antioxidant, palm oil biodiesel, decomposition, oxidation, tocopherol

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Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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The present study reports the development of noble metal free nano catalysts for low-temperature CO oxidation and water gas shift reaction. Mn-substituted CeO2 solid solution catalysts were synthesized by co-precipitation, combustion and hydrothermal methods. The formation of solid solution was confirmed by XRD with Rietveld refinement and the percentage of carbon and nitrogen doping was ensured by CHNS analyzer. Raman spectroscopic confirmed the oxygen vacancies. The surface area, pore volume and pore size distribution confirmed by N2 physisorption analysis, whereas, UV-visible diffuse reflectance spectroscopy and XPS data confirmed the oxidation state of the Mn ion. The particle size and morphology (spherical shape) of the material was confirmed using FESEM and HRTEM analysis. Ce0.8Mn0.2O2-δ was calcined at 400 °C, 600 °C and 800 °C. Raman spectroscopy confirmed that the catalyst calcined at 400 °C has the best redox properties. The activity of the designed catalysts for CO oxidation (0.2 vol%), carried out with GHSV of 21,000 h-1 and it has been observed that co-precipitation favored the best active catalyst towards CO oxidation and water gas shift reaction, due to the high surface area, improved reducibility, oxygen mobility and highest quantity of surface oxygen species. The activation energy of low temperature CO oxidation on Ce0.8Mn0.2O2- δ (combustion) was 5.5 kcal.K-1.mole-1. The designed catalysts were tested for water gas shift reaction. The present study demonstrates that Mn ion substituted ceria at 400 °C calcination temperature prepared by co-precipitation method promise to revive a green sustainable energy production approach.

Keywords: Ce0.8Mn0.2O2-ð, CO oxidation, physicochemical characterization, water gas shift reaction (WGS)

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Authors: Minoo Tavakoli, Alireza Kiani Rashid, Abbas Afrasiabi

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An aluminum coating deposited on mild steel substrate by electric arc spray and diffused to the base steel material by diffusion treatment at 800 and 900°C for 1 and 3 hours in a static air. Alloy layers formed by diffusion at both temperatures were investigated, and their features were compared with those of pack cementation aluminized steel. High-temperature oxidation tests were carried out in air at 600 °C for 145 hours. Results indicated that the aluminide coatings obtained from this process have significantly improved the high-temperature oxidation resistance in both methods due to the Al2O3 scale formation. Furthermore, it showed that the isothermal oxidation resistance of arc spray technique is better than pack cementation method. This can be attributed to voids that formed at the intermetallic layer /Al layer interface which is increased in the pack cementation method.

Keywords: electric arc spray, pack cementation, oxidation resistance, aluminized steel

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Authors: S. Nouri

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In this study, the Si-aluminide coating was prepared on gamma-TiAl [Ti-45Al-2Nb-2Mn-1B (at. %)] via liquid-phase slurry procedure. The high temperature oxidation resistance of this diffusion coating was evaluated at 1100 °C for 400 hours. The results of the isothermal oxidation showed that the formation of Si-aluminide coating can remarkably improve the high temperature oxidation of bare gamma-TiAl alloy. The identification of oxide scale microstructure showed that the formation of protective Al₂O₃+SiO₂ mixed oxide scale along with a continuous, compact and uniform layer of Ti₅Si₃ beneath the surface oxide scale can act as an oxygen diffusion barrier during the high temperature oxidation. The other possible mechanisms related to the formation of Si-aluminide coating and oxide scales were also discussed.

Keywords: Gamma-TiAl alloy, high temperature oxidation, Si-aluminide coating, slurry procedure

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Authors: Ahmed I. Osman, Jehad K. Abu-Dahrieh, Jillian M. Thompson, David W. Rooney

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Natural gas (the main constituent is Methane 95%) is considered as an alternative to petroleum for the production of synthetics fuels. Nowadays, methane combustion at low temperature has received much attention however; it is the most difficult hydrocarbon to be combusted. Co/Mo and (4:1 wt/wt) catalysts were prepared from a range of different precursors and used for the low temperature total methane oxidation (TMO). The catalysts were characterized by, XRD, BET and H2-TPR and tested under reaction temperatures of 250-400 °C with a GHSV= 36,000 mL g-1 h-1. It was found that the combustion temperature was dependent on the type of the precursor, and that those containing chloride led to catalysts with lower activity. The optimum catalyst was Co/Mo (4:1wt/wt) where greater than 20% methane conversion was observed at 250 °C. This catalyst showed a high degree of stability for TMO, showing no deactivation during 50 hours of time on stream.

Keywords: methane low temperature total oxidation, oxygen carrier, Co/Mo, Co/Mn

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Authors: Jinge Liu, Shuyuan Min, Bingchuan Liu, Bangzhao Yin, Bo Peng, Peng Wen, Yun Tian

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WE43 magnesium alloy can be additively manufactured via laser powder bed fusion (LPBF) for biodegradable applications, but the as-built WE43 exhibits an excessively rapid corrosion rate. High-temperature oxidation (HTO) was performed on the as-built WE43 to improve its biodegradation behavior. A sandwich structure including an oxide layer at the surface, a transition layer in the middle, and the matrix was generated influenced by the oxidation reaction and diffusion of RE atoms when heated at 525 ℃for 8 hours. The oxide layer consisted of Y₂O₃ and Nd₂O₃ oxides with a thickness of 2-3 μm. The transition layer is composed of α-Mg and Y₂O₃ with a thickness of 60-70 μm, while Mg24RE5 could be observed except α-Mg and Y₂O₃. The oxide layer and transition layer appeared to have an effective passivation effect. The as-built WE43 lost 40% weight after the in vitro immersion test for three days and finally broke into debris after seven days of immersion. The high-temperature oxidation samples kept the structural integrity and lost only 6.88 % weight after 28-day immersion. The corrosion rate of HTO samples was significantly controlled, which improved the biocompatibility of the as-built WE43 at the same time. The samples after HTO had better osteogenic capability according to ALP activity. Moreover, as built WE43 performed unqualified in cell adhesion and hemolytic test due to its excessively rapid corrosion rate. While as for HTO samples, cells adhered well, and the hemolysis ratio was only 1.59%.

Keywords: laser powder bed fusion, biodegradable metal, high temperature oxidation, biodegradation behavior, WE43

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Authors: Ateeq Ur Rehman

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This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electrocatalysts. The synthesized catalysts are characterized using different physicochemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), nano particles, formic acid fuel cell

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Authors: Pisut Painmanakul, Thawatchai Chintateerachai, Supanid Lertlapwasin, Nusara Rojvilavan, Tanun Chalermsinsuwan, Nattawin Chawaloesphonsiya, Onanong Larpparisudthi

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Conventional coagulation, advance oxidation process (AOPs), and the combined process were evaluated and compared for its suitability to treat the stabilized cutting-oil wastewater. The 90% efficiency was obtained from the coagulation at Al2(SO4)3 dosage of 150 mg/L and pH 7. On the other hands, efficiencies of AOPs for 30 minutes oxidation time were 10% for acoustic oxidation, 12% for acoustic oxidation with hydrogen peroxide, 76% for Fenton, and 92% sono-Fenton processes. The highest efficiency for effective oil removal of AOPs required large amount of chemical. Therefore, AOPs were studied as a post-treatment after conventional separation process. The efficiency was considerable as the effluent COD can pass the standard required for industrial wastewater discharge with less chemical and energy consumption.

Keywords: cutting oily-wastewater, advance oxidation process, sono-fenton, combined process

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Authors: Sewon Kim, Changyeop Lee

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A new concept of in-furnace partial oxidation combustion is successfully applied in this research. The burner is designed such that liquid fuel is prevaporized in the furnace then injected into a fuel rich combustion zone so that a partial oxidation reaction occurs. The effects of equivalence ratio, thermal load, injection distance and fuel distribution ratio on the NOx and CO are experimentally investigated. This newly developed burner showed very low NOx emission level, about 15 ppm when light oil is used as a fuel.

Keywords: burner, low NOx, liquid fuel, partial oxidation

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Authors: Mohammad Ali Karimi, Hossein Tavallali, Abdolhamid Hatefi-Mehrjardi

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In this study, an electrochemical sensor based on gold nanoparticles (AuNPs) functionalized improved graphene (AuNPs-IGE) was fabricated for selective determination of L-dopa in the presence of ascorbic acid by a novel self-assembly method. The AuNP IGE modified carbon paste electrode (AuNPs-IGE/CPE) utilized for investigation of the electrochemical behavior of L-dopa in phosphate buffer solution. Compared to bare CPE, AuNPs-IGE/CPE shows novel properties towards the electrochemical redox of levodopa (L-dopa) in phosphate buffer solution at pH 4.0. The oxidation potential of L-dopa shows a significant decrease at the AuNPs-IGE/CPE. The oxidation current of L-dopa is higher than that of the unmodified CPE. AuNPs-IG/CPE shows excellent electrocatalytic activity for the oxidation of ascorbic acid (AA). Using differential pulse voltammetry (DPV) method, the oxidation current is well linear with L-dopa concentration in the range of 0.4–50 µmol L-1, with a detection limit of about 1.41 nmol L-1 (S/N = 3). Therefore, it was applied to measure L-dopa from real samples that recoveries are 94.6-106.2%. The proposed electrode can also effectively avoid the interference of ascorbic acid, making the proposed sensor suitable for the accurate determination of L-dopa in both pharmaceutical preparations and human body fluids.

Keywords: gold nanoparticles, improved graphene, L-dopa, self-assembly

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Authors: Hsien T. Hsieh, Chao R. Chen, Li C. Chuang, Chin C. Shen

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Fenton oxidation technology is the general strategy for the treatment of organic compounds-contained wastewater. However, a considerable amount of ferric sludge was produced during the Fenton process as secondary wastes, which were needed to be further removed from the effluent and treated. In this study, heterogeneous catalysts based on ferrite oxide (Cu-Fe-Ce-O) were synthesized and characterized, and their application for Fenton-like oxidation of simulated and actual radioactive organic wastewater was investigated. The results of TOC decomposition efficiency around 54% ~ 99% were obtained when the catalyst loading, H₂O₂ loading, pH, temperature, and reaction time were controlled. In this case, no secondary wastes formed and the given catalysts were able to be separated by magnetic devices and reused again.

Keywords: fenton, oxidation, heterogeneous catalyst, wastewater

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Authors: J. M. Hung, J. S. Chan, M. I. Kuo, D. S. Chan, C. P. Lu

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Wheat germ is a by-product obtained from wheat milling and it contains highly concentrated nutrients. Due to highly lipase and lipoxygenase activities, wheat germ products can easily turn into rancid flavor and cause a short life. The objective of this study is to control moisture content and retard lipid hydrolysis by fluidized-bed drying. The raw wheat germ of 2 kg was dried with a vertical batch fluidized bed with the following varying conditions, inlet air temperature of 50, 80 and 120°C, inlet air velocity of 3.62 m/s. The experiment was designed to obtain a final product at around 40°C with water activity of 0.3 ± 0.1. Changes in the moisture content, water activity, enzyme activity of dried wheat germ during storage were measured. Results showed the fluidized-bed drying was found to reduce moisture content, water activity and lipase activity of raw wheat germ. After drying wheat germ, moisture content and water activity were between 5.8% to 7.2% and 0.28 to 0.40 respectively during 12 weeks of storage. The variation range of water activity indicated to retard lipid oxidation. All drying treatments displayed inactivation of lipase, except for drying condition of 50°C which showed relative high enzyme activity. During storage, lipase activity increased slowly during the first 6 weeks of storage and reached a plateau for another 6 weeks. As a result, using a fluidized-bed dryer was found to be effective drying technique in improving storage stability of wheat germ.

Keywords: wheat germ, fluidized-bed dryer, storage, lipase, stability

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Authors: Azeem Ur Rehman, Asma Tayyaba

Abstract:

This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electro catalysts. The synthesized catalysts are characterized using different physico chemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), electro catalyst, formic acid fuel cell

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Authors: Abolfazl Kamkar

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Vegetable oils and fats are recognized as important components of our diet. They provide essential fatty acids, which are precursors of important hormones and control many physiological factors such as blood pressure, cholesterol level, and the reproductive system.Vegetable oils with higher contents of unsaturated fatty acids, especially polyunsaturated fatty acids (PUFAs) are more susceptible to oxidation.Protective effects of Sature jahortensis(SE) extracts in stabilizing soybean oil at different concentrations (200 and 400 ppm) were tested. Results showed that plant extracts could significantly (P< 0.05) lower the peroxide value and thiobarbituric acid value of oil during storage at 60 oC. The IC50 values for methanol and ethanol extracts were 31.5 ± 0.7 and 37.00 ± 0 µg/ml, respectively. In the β- carotene/linoleic acid system, methanol and ethanol extracts exhibited 87.5 ± 1.41% and 74.0 ±2.25 % inhibition against linoleic acid oxidation. The total phenolic and flavonoid contents of methanol and ethanol extracts were (101.58 ± 0. 26m g/ g) and (96.00 ± 0.027 mg/ g), (44.91 ± 0.14 m g/ g) and (14.30 ± 0.12 mg/ g) expressed in Gallic acid and Quercetin equivalents, respectively.These findings suggest that Satureja extracts may have potential application as natural antioxidants in the edible oil and food industry.

Keywords: satureja hortensis, antioxidant activity, oxidative stability, vegetable oil, extract

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Authors: R. Velvarska, A. Vrablik, M. Fiedlerova, R. Cerny

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Near-infrared spectrometry (NIR) was tested as a rapid and alternative tool for determination of biodiesel oxidation stability. A PetroOxy method is standardly used for the determination, but this method is hazardous due to the possibility of explosion and ignition of flammable fuels. The second disadvantage is time consuming. The near-infrared spectrometry served for the development of the calibration model which was composed of 133 real samples (calibration standards). The reference values of these standards were obtained by PetroOxy method. Many chemometric diagnostics were used for the development of the final NIR model with the aim to have accurate prediction of the oxidation stability. The final NIR model was validated by 30 validation standards. The repeatability was determined as well with the acceptable residual standard deviation (8.59 %). The NIR spectrometry has proved to be an accurate alternative method for the determination of biodiesel oxidation stability with advantages as the time and cost saving, non-destructive character of analyzing and the possibility of online monitoring in safe mode.

Keywords: biodiesel, fatty acid methyl ester, NIR, oxidation stability

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Authors: Ayse Demirbas, Bruce A. Welt, Yavuz Yagiz

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Oxidation of polyunsaturated fatty acids (PUFA), eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in fish causes loss of product quality. Oxidative rancidity causes loss of nutritional value and undesirable color changes. Therefore, powerful antioxidant extracts may provide a relatively low cost and natural means to reduce oxidation, resulting in longer, higher quality and higher value shelf life of foods. In this study, we measured effects of red cabbage antioxidant on lipid oxidation in fresh tilapia filets using thiobarbituric acid reactive substances (TBARS) assay, peroxide value (PV) and color assesment analysis. Extraction of red cabbage was performed using an efficient microwave method. Fresh tilapia filets were dipped in or sprayed with solutions containing different concentrations of extract. Samples were stored for up to 9 days at 4°C and analyzed every other day for color and lipid oxidation. Results showed that treated samples had lower oxidation than controls. Lipid peroxide values on treated samples showed benefits through day-7. Only slight differences were observed between spraying and dipping methods. This work shows that red cabbage antioxidant extracts may represent an inexpensive and all natural method for reducing oxidative spoilage of fresh fish.

Keywords: antioxidant, shelf life, fish, red cabbage, lipid oxidation

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Authors: Zhenghua Dai, Jianliang Xu, Fuchen Wang

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Non-catalyst partial oxidation technology has been widely used to produce syngas by reforming of hydrocarbon, including gas (natural gas, shale gas, refinery gas, coalbed gas, coke oven gas, pyrolysis gas, etc.) and liquid (residual oil, asphalt, deoiled asphalt, biomass oil, etc.). For natural gas non-catalyst partial oxidation, the H₂/CO(v/v) of syngas is about 1.8, which is agreed well with the request of FT synthesis. But for other process, such as carbonylation and glycol, the H₂/CO(v/v) should be close to 1 and 2 respectively. So the syngas composition of non-catalyst partial oxidation should be adjusted to satisfy the request of different chemical synthesis. That means a multi-reforming method by CO₂ and H₂O addition. The natural gas non-catalytic partial oxidation hot model was established. The effects of O₂/CH4 ratio, steam, and CO₂ on the syngas composition were studied. The results of the experiment indicate that the addition of CO₂ and steam into the reformer can be applied to change the syngas H₂/CO ratio. The reactor network model (RN model) was established according to the flow partition of industrial reformer and GRI-Mech 3.0. The RN model results agree well with the industrial data. The effects of steam, CO₂ on the syngas compositions were studied with the RN model.

Keywords: non-catalyst partial oxidation, natural gas, H₂/CO, CO₂ and H₂O addition, multi-reforming method

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Authors: Atena Naeimi, Asghar Amiri, Zahra Ghasemi

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A stable suspension of nanocomposite simple manganese(III) meso-tetraphenylporphyrin nanoaggregates and Ag was prepared by a host–guest procedure, in which ethanol and water are used as ‘green’ solvents. The oxidation of alcohols by tetrabutylammonium Peroxomonosulfate(TP) were efficiently enhanced with excellent selectivity under the influence of simple Mn(TPP)OAc (TPP = meso-tetraphenylporphyrin) nanoparticles. Enhanced stabilities and activities were achieved with nanostructured Mn catalysts compared to those of the individual counterparts in solution according to turnover numbers and UV/Vis studies. The title nanocatalyst facilitates a greener reaction because the reaction solvent is water and TP is safe to use. The efficiency of the oxidation system depends critically upon the steric hindrances and electronic structures of both nitrogen donor ligand sand porphyrin nanoparticles.

Keywords: oxidation, nanoaggregates, porphyrinoids, silver

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Authors: Ahmed A. Abdel-Khalek, Reham A. Mohamed

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The kinetics of oxidation of binary complex [CrIII(DMG)2(H2O)4 ]+ to Cr(VI) by periodate has been investigated spectrophotometrically where, [DMG= Dimethylglyoxime] at 370nm under pseudo first order reaction conditions in aqueous medium over 20- 40ºC range, PH 2-3, and I=0.07 mol dm-3. The reaction is first order with respect to both [IO4-] and Cr(III), and the reaction increased with PH increased. Thermodymanic activation parameters have been calculated. It is suggested that electron transfer proceeds through an inner sphere mechanism via coordination of IO4- to Cr (III). The reaction obeys the following rate law Rate= {k1 K5+ k2 K6 K2 } [Cr III (DMG)2(H2O)4 ]+ [H5IO6].

Keywords: chromium, dimethylglyoxime, kinetics, oxidation, periodate

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Authors: Lucija Pustahija, Christine Bandl, Wolfgang Kern, Christian Mitterer

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Concerning today´s ecological demands, producing reliable materials from sustainable resources is a continuously developing topic. Such an example is the production of carbon materials via pyrolysis of natural gases or biomass. The amazing properties of pyrolytic carbon are utilized in various fields, where in particular the application in building industry is a promising way towards the utilization of pyrolytic carbon and composites based on pyrolytic carbon. For many applications, surface modification of carbon is an important step in tailoring its properties. Therefore, in this paper, an investigation of different oxidation methods was performed to prepare the carbon surface before functionalizing it with organosilanes, which act as coupling agents for epoxy and polyurethane resins. Made in such a way, a building material based on carbon composites could be used as a lightweight, durable material that can be applied where water or air filtration / purification is needed. In this work, both wet and dry oxidation were investigated. Wet oxidation was first performed in solutions of nitric acid (at 120 °C and 150 °C) followed by oxidation in hydrogen peroxide (80 °C) for 3 and 6 h. Moreover, a hydrothermal method (under oxygen gas) in autoclaves was investigated. Dry oxidation was performed under plasma and corona discharges, using different power values to elaborate optimum conditions. Selected samples were then (in preliminary experiments) subjected to a silanization of the surface with amino and glycidoxy organosilanes. The functionalized surfaces were examined by X-ray photon spectroscopy and Fourier transform infrared spectroscopy spectroscopy, and by scanning electron microscopy. The results of wet and dry oxidation methods indicated that the creation of functionalities was influenced by temperature, the concentration of the reagents (and gases) and the duration of the treatment. Sequential oxidation in aq. HNO₃ and H₂O₂ results in a higher content of oxygen functionalities at lower concentrations of oxidizing agents, when compared to oxidizing the carbon with concentrated nitric acid. Plasma oxidation results in non-permanent functionalization on the carbon surface, by which it´s necessary to find adequate parameters of oxidation treatments that could enable longer stability of functionalities. Results of the functionalization of the carbon surfaces with organosilanes will be presented as well.

Keywords: building materials, dry oxidation, organosilanes, pyrolytic carbon, resins, surface functionalization, wet oxidation

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Authors: Parvin Berenjkar, Qiuyan Yuan, Richard Sparling, Stan Lozecznik

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Landfills highly contribute to anthropological global warming through CH₄ emissions. Landfills are usually capped by a conventional soil cover to control the migration of gases. Methane is consumed by CH₄-oxidizing microorganisms known as methanotrophs that naturally exist in the landfill soil cover. The growth of methanotrophs can be optimized in a bio-cover that typically consists of a gas distribution layer (GDL) to homogenize landfill gas fluxes and an overlying oxidation layer composed of suitable materials that support methanotrophic populations. Materials such as mature yard waste composts can provide an inexpensive and favourable porous support for the growth and activity of methanotrophs. In areas with seasonal cold climates, it is valuable to know if methanotrophs in a bio-cover can survive in winter until the next spring, and how deep they are active in the bio-cover to mitigate CH₄. In this study, a pilot bio-cover was constructed in a closed landfill cell in Winnipeg that has a very cold climate in Canada. The bio-cover has a surface area of 2.5 m x 3.5 m and 1.5 m of depth, filled with 50 cm of gravel as a GDL and 70 cm of biosolids compost amended with yard and leaf waste compost. The observed in situ potential of methanotrophs for CH₄ oxidation was investigated at a specific period of time from December 2016 to April 2017 as well as November 2017 to April 2018, when the transition to surface frost and thawing happens in the bio-cover. Compost samples taken from different depths of the bio-cover were incubated in the laboratory under standardized conditions; an optimal air: methane atmosphere, at 22ºC, but at in situ moisture content. Results showed that the methanotrophs were alive oxidizing methane without a lag, indicating that there was the potential for methanotrophic activity at some depths of the bio-cover.

Keywords: bio-cover, global warming, landfill, methanotrophic activity

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Authors: Ontima Yamchuti, Waruntorn Kanitpanyacharoen, Chakkaphan Sutthirat, Wantana Klysuban, Penphitcha Amonpattarakit

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Natural corundum occurs in various colors due to impurities or trace elements in its structure. Sapphire and ruby are essentially the same mineral, corundum, but valued differently due to their red and blue varieties, respectively. Color is one of the critical factors used to determine the value of natural and synthetic corundum. Despite the abundance of research on impurities in natural corundum, little is known about trace elements in synthetic corundum. This project thus aims to quantify trace elements and identify their oxidation states in synthetic corundum. A total of 15 corundum samples in red, blue, and yellow, synthesized by melt growth process, were first investigated by X-ray diffraction (XRD) analysis to determine the composition. Electron probe micro-analyzer (EPMA) was used to identify the types of trace elements. Results confirm that all synthetic corundums contain crystalline Al₂O₃ and a wide variety type of trace element, particularly Cr, Fe, and Ti. In red, yellow, and blue corundums respectively. To further determine their oxidation states, synchrotron X-ray absorption near edge structure spectrometry (XANES) was used to observe absorbing energy of each element. XANES results show that red synthetic corundum has Cr³⁺ as a major trace element (62%). The pre-edge absorption energy of Cr³⁺ is at 6001 eV. In addition, Fe²⁺ and Fe³⁺ are dominant oxidation states of yellow synthetic corundum while Ti³⁺and Ti⁴⁺ are dominant oxidation states of blue synthetic corundum. the average absorption energy of Fe and Ti is 4980 eV and 7113 eV respectively. The presence of Fe²⁺, Fe³⁺, Cr³⁺, Ti³⁺, and Ti⁴⁺ in synthetic corundums in this study is governed by comparison absorption energy edge with standard transition. The results of oxidation states in this study conform with natural corundum. However yellow synthetic corundums show difference oxidation state of trace element compared with synthetic in electron spin resonance spectrometer method which found that Ni³⁺ is a dominant oxidation state.

Keywords: corundum, trace element, oxidation state, XANES technique

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Authors: Sahana Selladurai, Christine DeWolf

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Lung surfactant comprises a lipid-protein film that coats the alveolar surface and serves to prevent alveolar collapse upon repeated breathing cycles. Exposure of lung surfactant to high concentrations of airborne pollutants, for example tropospheric ozone in smog, can chemically modify the lipid and protein components. These chemical changes can impact the film functionality by decreasing the film’s collapse pressure (minimum surface tension attainable), altering it is mechanical and flow properties and modifying lipid reservoir formation essential for re-spreading of the film during the inhalation process. In this study, we use Langmuir monolayers spread at the air-water interface as model membranes where the compression and expansion of the film mimics the breathing cycle. The impact of ozone exposure on model lung surfactant films is measured using a Langmuir film balance, Brewster angle microscopy and a pendant drop tensiometer as a function of film and sub-phase composition. The oxidized films are analyzed using mass spectrometry where lipid and protein oxidation products are observed. Oxidation is shown to reduce surface activity, alter line tension (and film morphology) and in some cases visibly reduce the viscoelastic properties of the film when compared to controls. These reductions in functionality of the films are highly dependent on film and sub-phase composition, where for example, the effect of oxidation is more pronounced when using a physiologically relevant buffer as opposed to water as the sub-phase. These findings can lead to a better understanding on the impact of continuous exposure to high levels of ozone on the mechanical process of breathing, as well as understanding the roles of certain lung surfactant components in this process.

Keywords: lung surfactant, oxidation, ozone, viscoelasticity

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Authors: Khaled S. Al Salhen

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Aldehyde oxidase (AO) and xanthine oxidoreductase (XOR) catalyze the oxidation of many different N-heterocyclic compounds as well as aliphatic and aromatic aldehydes to their corresponding lactam and carboxylic acids respectively. The present study examines the oxidation of dimethylamino-cinnamaldehyde (DMAC), vanillin and phenanthridine by AO and xanthine by XOR from Drosophila cytosol. Therefore, the results obtained in the present study showed the DMAC, vanillin and phenanthridine substrates used were found to be good substrates of Drosophila AO and xanthine is the preferred substrate for Drosophila XOR. Km values of AO substrates were observed with DMAC (50±5.4 µM), phenanthridine (80±9.1 µM) and vanillin (303±11.7 µM) respectively for Drosophila cytosol. The Km values for DMAC and phenanthridine were ~6 and ~4 fold lower than that for vanillin as a substrate. The Km for XOR with xanthine using NAD+ as an electron acceptor was 27±4.1 µM. Relatively low Vmax values were obtained with phenanthridine (1.78±0.38 nmol/min/mg protein) and DMAC (1.80±0.35 nmol/min/mg protein). The highest Vmax was obtained from Drosophila cytosol with vanillin (7.58±2.11 nmol/min/mg protein). It is concluded these results that AO and XOR in Drosophila were able to catalyse the biotransformation of numerous substrates of the well-characterised mammalian AO and XOR. The kinetic parameters have indicated that the activity of AO of Drosophila may be a significant factor the oxidation of aromatic aldehyde compounds.

Keywords: aldehyde oxidase, xanthine oxidoreductase, dimethylamino-cinnamaldehyde, vanillin, phenanthridine, Drosophila melanogaster

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Authors: Chin-Yuan Hsu, Yu-Lung Chuang

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The expression, concentration, and activity of mitochondrial energy-utilized molecules and cellular energy-regulated molecules decreased with age in the trophocytes and oenocytes of honeybees (Apis mellifera), but those of cellular energy-metabolized molecules is unknown. In this study, the expression, concentration, and activity of cellular energy-metabolized molecules were assayed in the trophocytes and fat cells of young and old worker bees by using the techniques of cell and biochemistry. The results showed that (i) the •-hydroxylacyl-coenzyme A dehydrogenase (HOAD) activity/citrate synthase (CS) activity ratio, non-esterified fatty acids concentrations, the expression of eukaryotic initiation factor 4E, and the expression of phosphorylated eIF4E binding protein 1 decreased with age; (ii) fat and glycogen accumulation increased with age; and (iii) the pyruvate dehydrogenase (PDH) activity/citrate synthase (CS) activity ratio was not correlated with age. These finding indicated that •-oxidation (HOAD/CS) and protein synthsis decreased with age. Glycolysis (PDH/CS) was unchanged with age. The most likely reason is that sugars are the vital food of worker bees. Taken together these data reveal that young workers have higher cellular energy metabolism than old workers and that aging results in a decline in the cellular energy metabolism in worker honeybees.

Keywords: aging, energy, honeybee, metabolism

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Authors: S. Trafela, X. Xua, K. Zuzek Rozmana

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In this study, we used an accurate and precise method to measure the electrochemically active surface areas (Aecsa) of nickel electrodes. Calculated Aecsa is really important for the evaluation of an electro-catalyst’s activity in electrochemical reaction of different organic compounds. The method involves the electrochemical formation of Ni(OH)₂ and NiOOH in the presence of adsorbed oxalate in alkaline media. The studies were carried out using cyclic voltammetry with polycrystalline nickel as a reference material and electrodeposited nickel nanowires, homogeneous and heterogeneous nickel films. From cyclic voltammograms, the charge (Q) values for the formation of Ni(OH)₂ and NiOOH surface oxides were calculated under various conditions. At sufficiently fast potential scan rates (200 mV s⁻¹), the adsorbed oxalate limits the growth of the surface hydroxides to a monolayer. Although the Ni(OH)₂/NiOOH oxidation peak overlaps with the oxygen evolution reaction, in the reverse scan, the NiOOH/ Ni(OH)₂ reduction peak is well-separated from other electrochemical processes and can be easily integrated. The values of these integrals were used to correlate experimentally measured charge density with an electrochemically active surface layer. The Aecsa of the nickel nanowires, homogeneous and heterogeneous nickel films were calculated to be Aecsa-NiNWs = 4.2066 ± 0.0472 cm², Aecsa-homNi = 1.7175 ± 0.0503 cm² and Aecsa-hetNi = 2.1862 ± 0.0154 cm². These valuable results were expanded and used in electrochemical studies of formaldehyde oxidation. As mentioned nickel nanowires, heterogeneous and homogeneous nickel films were used as simple and efficient sensor for formaldehyde detection. For this purpose, electrodeposited nickel electrodes were modified in 0.1 mol L⁻¹ solution of KOH in order to expect electrochemical activity towards formaldehyde. The investigation of the electrochemical behavior of formaldehyde oxidation in 0.1 mol L⁻¹ NaOH solution at the surface of modified nickel nanowires, homogeneous and heterogeneous nickel films were carried out by means of electrochemical techniques such as cyclic voltammetric and chronoamperometric methods. From investigations of effect of different formaldehyde concentrations (from 0.001 to 0.1 mol L⁻¹) on electrochemical signal - current we provided catalysis mechanism of formaldehyde oxidation, detection limit and sensitivity of nickel electrodes. The results indicated that nickel electrodes participate directly in the electrocatalytic oxidation of formaldehyde. In the overall reaction, formaldehyde in alkaline aqueous solution exists predominantly in form of CH₂(OH)O⁻, which is oxidized to CH₂(O)O⁻. Taking into account the determined (Aecsa) values we have been able to calculate the sensitivities: 7 mA mol L⁻¹ cm⁻² for nickel nanowires, 3.5 mA mol L⁻¹ cm⁻² for heterogeneous nickel film and 2 mA mol L⁻¹ cm⁻² for heterogeneous nickel film. The detection limit was 0.2 mM for nickel nanowires, 0.5 mM for porous Ni film and 0.8 mM for homogeneous Ni film. All of these results make nickel electrodes capable for further applications.

Keywords: electrochemically active surface areas, nickel electrodes, formaldehyde, electrocatalytic oxidation

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Authors: Chandrashekar, R. T. Radhika, B. M. Venkatesha, S. Ananda, Shivalingegowda, T. S. Shashikumar, H. Ramachandra

Abstract:

The kinetics of the oxidation of amitriptyline (AT) by sodium N-bromotoluene sulphonamide (C₆H₅SO₂NBrNa) has been studied in an acidic buffer medium of pH 1.2 at 303 K. The oxidation reaction of AT was followed spectrophotometrically at maximum wavelength, 410 nm. The reaction rate shows a first order dependence each on concentration of AT and concentration of sodium N-bromotoluene sulphonamide. The reaction also shows an inverse fractional order dependence at low or high concentration of HCl. The dielectric constant of the solvent shows negative effect on the rate of reaction. The addition of halide ions and the reduction product of BAT have no significant effect on the rate. The rate is unchanged with the variation in the ionic strength (NaClO₄) of the medium. Addition of reaction mixtures to be aqueous acrylamide solution did not initiate polymerization, indicating the absence of free radical species. The stoichiometry of the reaction was found to be 1:1 and oxidation product of AT is identified. The Michaelis-Menton type of kinetics has been proposed. The CH₃C₆H₅SO₂NHBr has been assumed to be the reactive oxidizing species. Thermodynamical parameters were computed by studying the reactions at different temperatures. A mechanism consistent with observed kinetics is presented.

Keywords: amitriptyline, bromamine-T, kinetics, oxidation

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Authors: Folorunso Omoniyi, Peter Olubambi, Rotimi Sadiku

Abstract:

Thermal barrier coating (TBC) system is used in both aero engines and other gas turbines to offer oxidation protection to superalloy substrate component. In the present work, it shows the ability of a new fabrication technique to develop rapidly new coating composition and microstructure. The compact powders were prepared by Powder Metallurgy method involving powder mixing and the bond coat was synthesized through the application of Spark Plasma Sintering (SPS) at 10500C to produce a fully dense (97%) NiCrAl bulk samples. The influence of sintering temperature on the hardness of NiCrAl, done by Micro Vickers hardness tester, was investigated. And Oxidation test was carried out at 1100oC for 20h, 40h, and 100h. The resulting coat was characterized with optical microscopy, scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDAX) and x-ray diffraction (XRD). Micro XRD analysis after the oxidation test revealed the formation of protective oxides and non-protective oxides.

Keywords: high-temperature oxidation, powder metallurgy, spark plasma sintering, thermal barrier coating

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Authors: Marzieh Joda, Narges Fallah, Neda Afsham

Abstract:

Graphite-supported two different of morphology α and β -Ni (OH)₂ electrodes were prepared by electrochemical deposition at appropriate potentials with regard to Ni (II)/Ni (III) redox couple under alkaline and acidic conditions, respectively, for selective oxidation of ammonia to nitrogen in the direct electro-oxidation process. Cyclic voltammetry (CV) of the electrolyte containing NH₃ indicated mediation of electron transfer by Ni (OH)₂ and the electrode surface was analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectrometer (RS), and X-ray photoelectron spectroscopy (XPS). Results of surface characterization indicated the presence of α polymorphs which is the stable phase of Ni (OH)₂ /Graphite. Cyclic voltammograms gave information on the nature of electron transfer between nitrogen species and working electrode and revealed that the potential has depended on both nature ammonia oxidation and that of concentration. The mechanism of selective ammonia conversion to nitrogen and byproducts, namely NO₂- and NO₃- was established by Cyclic voltammograms and current efficiency. The removal efficiency and selective conversion of ammonia (0.1 M KNO₃ + 0.01 M Ni(NO₃)₂, pH 11, 250°C) on Nickel Oxide-hydroxide /Graphite was determined based on potential controlled experiments.

Keywords: Electro deposition, Nickel oxide-hydroxide, Nitrogen selectivity, Ammonia oxidation

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Authors: Ali Bahri Lubis

Abstract:

Tryptophan oxidation by Heme-dioxygenase enzyme is the initial rate-limiting step in the kynurenine pathway, which leads to the formation of NADH and dangerous metabolites, implicating several severe diseases such as Parkinson’s Disease, Huntington's Disease, poliomyelitis and cataract. This oxidation, generally, allows tryptophan to convert to N-Formylkynurenine (NFK). Observing the catalytic mechanism of Heme dioxygenase in tryptophan oxidation has been a debatably scientific interest since no one has yet proven the mechanism obviously. In this research we have attempted to prove mechanistic steps of tryptophan oxidation via human indoleamine dioxygenase (h-IDO) utilising various substrates: L-tryptophan, L-tryptophan (indole-ring-2-¹³C), L-fully-labelled¹³C-tryptophan, L-N-methyl-tryptophan, L-tryptophanol and 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid. All enzyme assay experiments were measured using a UV-Vis spectrophotometer, LC-MS, 1H-NMR and HSQC. We also successfully synthesised enzyme products as our control in NMR measurements. The result exhibited that all substrates produced N-formyl kynurenine (NFK), and a side, the minor product of hydroxypyrrolloindoleamine carboxylic acid (HPIC) in cis and trans isomer, except 1-methyl tryptophan only generating cis HPIC. Interestingly, L- tryptophanol was oxidised to form HPIC derivative as a major product and 5-hydroxy tryptophan was converted to NFK derivative instead without any HPIC derivative. The bizarre result of oxidation underwent in 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid, which produced epoxide cyclic. Those phenomena have been explainable in our research based on the proposed mechanism of how tryptophan is oxidised by human indoleamine dioxygenase.

Keywords: tryptophan oxidation, heme-dioxygenases, human indoleamine dioxygenases, N-formylkynurenine, hydroxypyrroloindoleamine carboxylic acid

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