Search results for: tryptophan oxidation

Authors: Phakamani Xaba, Robert Huberts, Bilainu Oboirien

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The present study was aimed at developing & comparing two neural-network-based predictive models to predict shelf-life/product age of South African margarine using free fatty acid (FFA), water droplet size (D3.3), water droplet distribution (e-sigma), moisture content, peroxide value (PV), anisidine valve (AnV) and total oxidation (totox) value as input variables to the model. Brick margarine products which had varying ages ranging from fresh i.e. week 0 to week 47 were sourced. The brick margarine products which had been stored at 10 & 25 °C and were characterized. JMP and MATLAB models to predict shelf-life/ margarine age were developed and their performances were compared. The key performance indicators to evaluate the model performances were correlation coefficient (CC), root mean square error (RMSE), and mean absolute percentage error (MAPE) relative to the actual data. The MATLAB-developed model showed a better performance in all three performance indicators. The correlation coefficient of the MATLAB model was 99.86% versus 99.74% for the JMP model, the RMSE was 0.720 compared to 1.005 and the MAPE was 7.4% compared to 8.571%. The MATLAB model was selected to be the most accurate, and then, the number of hidden neurons/ nodes was optimized to develop a single predictive model. The optimized MATLAB with 10 neurons showed a better performance compared to the models with 1 & 5 hidden neurons. The developed models can be used by margarine manufacturers, food research institutions, researchers etc, to predict shelf-life/ margarine product age, optimize addition of antioxidants, extend shelf-life of products and proactively troubleshoot for problems related to changes which have an impact on shelf-life of margarine without conducting expensive trials.

Keywords: margarine shelf-life, predictive modelling, neural networks, oil oxidation

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Authors: Vishnu V. Pillai, Sunil P. Lonkar, Akhil M. Abraham, Saeed M. Alhassan

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An effectual technology for wastewater treatment is a great demand now in order to encounter the water pollution caused by organic pollutants. Photocatalytic oxidation technology is widely used in removal of such unsafe contaminants. Among the semi-conducting metal oxides, robust and thermally stable TiO2 has emerged as a fascinating material for photocatalysis. Enhanced catalytic activity was observed for nanostructured TiO2 due to its higher surface, chemical stability and higher oxidation ability. However, higher charge carrier recombination and wide band gap of TiO2 limits its use as a photocatalyst in the UV region. It is desirable to develop a photocatalyst that can efficiently absorb the visible light, which occupies the main part of the solar spectrum. Hence, in order to extend its photocatalytic efficiency under visible light, TiO2 nanoparticles are often doped with metallic or non-metallic elements. Non-metallic doping of TiO2 has attracted much attention due to the low thermal stability and enhanced recombination of charge carriers endowed by metallic doping of TiO2. Amongst, sulfur doped TiO2 is most widely used photocatalyst in environmental purification. However, the most of S-TiO2 synthesis technique uses toxic chemicals and complex procedures. Hence, a facile, scalable and environmentally benign preparation process for S-TiO2 is highly desirable. In present work, we have demonstrated new and facile solid-state reaction method for S-TiO2 synthesis that uses abundant elemental sulfur as S source and moderate temperatures. The resulting nano-sized S-TiO2 has been successfully employed as visible light photocatalyst in methylene blue dye removal from aqueous media.

Keywords: ecofriendly, nanomaterials, methylene blue, photocatalysts

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Authors: Ana M. T. Mata, Alexiane Ligneul

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Textile effluents are usually heavily loaded with organic carbon and color compounds, the latter being azo dyes in an estimated 70% of the case effluent posing a major challenge in environmental protection. In this study, the ecotoxicity of simulated textile effluent after biological treatment with anaerobic and aerobic phase (aerobic granular sludge, AGS) and after advanced oxidation processes (AOP) namely ozonation and UV irradiation as post-treatment, were tested to evaluate the fitness of this treatments for ecotoxicity abatement. AGS treatment achieved an 80% removal in both COD and color. AOP was applied with the intention to mineralize the metabolites resulting from biodecolorization of the azo dye Acid Red 14, especially the stable aromatic amine (4-amino-1-naphthalenesulfonic acid, 4A1NS). The ecotoxicity evaluation was based on growth inhibition of the algae Pseudokirchneriella subcapitata following OECD TG 201 except regarding the medium, MBL medium was used instead. Five replicate control cultures and samples were performed with an average STD of 2.7% regarding specific algae growth rate determination. It was found that untreated textile effluent holds an inhibition of specific growth rate of 82%. AGS treatment by itself is able to lower ecotoxicity to 53%. This is probably due to the high color removal of the treatment. AOP post-treatment with Ozone and UV irradiation improves the ecotoxicity abatment to 49 and 43% inhibition respectively, less significantly than previously thought. Since over 85% of 4A1NS was removed by either of the AOP (followed by HPLC), an individual ecotoxicity test of 4A1NS was performed showing that 4A1NS does not inhibit algae growth (0% inhibition). It was concluded that AGS treatment is able by itself to achieve a significant ecotoxicity abatement of textile effluent. The cost-benefit of AOP as a post-treatment have to be better accessed since their application resulted in an improvement of only 10% regarding ecotoxicity effluent removal. It was also found that the 4A1NS amine had no apparent effect on ecotoxicity. Further studies will be conducted to study where ecotoxicity is coming from after AGS biological treatment and how to eliminate it.

Keywords: textile wastewate, ecotoxicity, aerobic granular sludge, AOP

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Authors: Karen G. Bastidas Gomez, Hugo R. Zea Ramirez, Manuel F. Ribeiro Pereira, Cesar A. Sierra Avila, Juan A. Clavijo Morales

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The contamination of water sources with heavy metals such as mercury has been an environmental problem; it has generated a high impact on the environment and human health. In countries such as Colombia, mercury contamination due to mining has reached levels much higher than the world average. This work proposes the use of fique fibers as adsorbent in mercury removal. The evaluation of the material was carried out under five different conditions (raw, pretreated by organosolv, functionalized by TEMPO oxidation, fiber functionalized plus MOF-199 and fiber functionalized plus MOF-199-SH). All the materials were characterized using FTIR, SEM, EDX, XRD, and TGA. Regarding the mercury removal, it was done under room pressure and temperature, also pH = 7 for all materials presentations, followed by Atomic Absorption Spectroscopy. The high cellulose content in fique is the main particularity of this lignocellulosic biomass since the degree of oxidation depends on the number of hydroxyl groups on the surface capable of oxidizing into carboxylic acids, a functional group capable of increasing ion exchange with mercury in solution. It was also expected that the impregnation of the MOF would increase the mercury removal; however, it was found that the functionalized fique achieved a greater percentage of removal, resulting in 81.33% of removal, 44% for the fique with the MOF-199 and 72% for the MOF-199-SH with. The pretreated fiber and raw also showed 74% and 56%, respectively, which indicates that fique does not require considerable modifications in its structure to achieve good performances. Even so, the functionalized fiber increases the percentage of removal considerably compared to the pretreated fique, which suggests that the functionalization process is a feasible procedure to apply with the purpose of improving the removal percentage. In addition, this is a procedure that follows a green approach since the reagents involved have low environmental impact, and the contribution to the remediation of natural resources is high.

Keywords: biomass, nanotechnology, science materials, wastewater treatment

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Authors: Arámbula-Villa Gerónimo, García-Lara Kenia Y., Figueroa-Cárdenas J. D., Pérez-Robles J. F., Jiménez-Sandoval S., Salazar-López R., Herrera-Corredor J. A.

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The nixtamalization process (thermal-alkaline method) improves the nutritional part of the corn grain. In this process, the using of Ca(OH)₂ is basic, although the chemical mechanisms between this alkali and the carbohydrates (starch), proteins, lipids, and fiber have not been fully identified. In this study, the native corn starch was taken as a model, and it was subjected to cooking with different concentrations of lime (nixtamalization process) and specific studies of FTIR and XRD were carried out to identify the formation of chemical compounds, and the physical, physicochemical, rheological (paste) and structural properties of material obtained were determined. The FTIR spectra showed the formation of calcium-starch complexes. The treatments with Ca(OH)₂ showed a band shift towards 1675 cm⁻¹ and a band in 1436 cm⁻¹ (COO⁻), indicating the oxidation of starch. Three bands were identified (1575, 1550, and 1540 cm⁻¹) characteristics of carboxylic acid salts for three types of coordinated structures: monodentate, pseudo-bridged, and bidentate. The XRD spectra of starch treated with Ca(OH)₂ showed a peak corresponding to CaCO₃ (29.40°). The oxidation of starch was favored with low concentrations of Ca(OH)₂, producing carboxyl and carbonyl groups and increasing the residual CaCO₃. The increased concentration of Ca(OH)₂ showed the formation of calcium carboxylates, with a decrease in relative crystallinity and residual CaCO₃. Samples with low concentrations of Ca(OH)₂ slowed the onset of gelatinization and increased the swelling of the granules and the peak viscosity. The higher concentrations of Ca(OH)₂ difficulted the water absorption and decreased the viscosity rate and peak viscosity. These results can be used to improve the quality characteristics of the dough and tortillas and to get better acceptance by consumers.

Keywords: maize starch, nixtamalization, gelatinization, calcium carboxylates

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Authors: Gelu Varghese, Khizer Saeed

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Biodiesel is as a mixture of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats. Recent studies in the literature suggest that end property of biodiesel such as its oxidative stability (OS) is highly influenced by the structure and composition of its alkyl esters than by environmental conditions. The structure and composition of these long chain fatty acid components have been also associated with trends in Cetane number, heat of combustion, cold flow properties viscosity, and lubricity. In the present work, detailed investigation has been carried out to decouple and correlate the fatty acid structure indices of biodiesel such as degree of unsaturation, chain length, double bond orientation, and composition with its oxidative stability. Measurements were taken using the EN14214 established Rancimat oxidative stability test method (EN141120). Firstly, effects of the degree of unsaturation, chain length and bond orientation were tested for the pure fatty acids to establish their oxidative stability. Results for pure Fatty acid show that Saturated FAs are more stable than unsaturated ones to oxidation; superior oxidative stability can be achieved by blending biodiesel fuels with relatively high in saturated fatty acid contents. A lower oxidative stability is noticed when a greater quantity of double bonds is present in the methyl ester. A strong inverse relationship with the number of double bonds and the Rancimat IP values can be identified. Trans isomer Methyl elaidate shows superior stability to oxidation than its cis isomer methyl oleate (7.2 vs. 2.3). Secondly, the effects of the variation in the composition of the biodiesel were investigated and established. Finally, biodiesels with varying structure and composition were investigated and correlated.

Keywords: biodiesel, fame, oxidative stability, fatty acid structure, acid composition

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Authors: Jigar Shaileshumar Halpati, Aravind Kumar Chandiran

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Vacancy ordered double perovskites (VOPs) have been significantly attracting researchers due to their chemical structure diversity and interesting optoelectronic properties. Some VOPs have been recently reported to be suitable photoelectrodes for photoelectrochemical water-splitting reactions due to their high stability and panchromatic absorption. In this work, we systematically synthesized mixed tetravalent VOPs based on Cs₂RuₘPt₁-ₘX₆ (X = Cl-, Br-) and reported their structural, optical, electrochemical and photoelectrochemical properties. The structural characterization confirms that the mixed tetravalent site intermediates formed their own phases. The parent materials, as well as their intermediates, were found to be stable in ambient conditions for over 1 year and also showed incredible stability in harsh pH media ranging from pH 1 to pH 11. Moreover, these materials showed panchromatic absorption with onset up to 1000 nm depending upon the mixture stoichiometry. The extraordinary stability and excellent absorption properties make them suitable materials for photoelectrochemical water-splitting applications. PEC studies of these series of materials showed a high water oxidation photocurrent of 0.56 mA cm-² for Cs₂Ru₀.₅Pt₀.₅Cl₆. Fundamental investigation from photoelectrochemical reactions revealed that the intrinsic ruthenium-based VOP showed enhanced hole transfer to the electrolyte, while the intrinsic platinum-based VOP showed higher photovoltage. The mix of these end members at the tetravalent site showed a synergic effect of reduced charge transfer resistance from the material to the electrolyte and increased photovoltage, which led to increased PEC performance of the intermediate materials.

Keywords: solar water splitting, photo electrochemistry, photo absorbers, material characterization, device characterization, green hydrogen

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Authors: Martin Grootveld, Benita Percival, Sarah Moumtaz, Kerry L. Grootveld

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Objectives/Hypotheses: The adverse health effect potential of dietary lipid oxidation products (LOPs) has evoked much clinical interest. Therefore, we employed a ¹H NMR-linked Principal Component Regression (PCR) chemometrics modelling strategy to explore relationships between data matrices comprising (1) aldehydic LOP concentrations generated in culinary oils/fats when exposed to laboratory-simulated shallow frying practices, and (2) the prior saturated (SFA), monounsaturated (MUFA) and polyunsaturated fatty acid (PUFA) contents of such frying media (FM), together with their heating time-points at a standard frying temperature (180 ^oC). Methods: Corn, sunflower, extra virgin olive, rapeseed, linseed, canola, coconut and MUFA-rich algae frying oils, together with butter and lard, were heated according to laboratory-simulated shallow-frying episodes at 180 ^oC, and FM samples were collected at time-points of 0, 5, 10, 20, 30, 60, and 90 min. (n = 6 replicates per sample). Aldehydes were determined by ¹H NMR analysis (Bruker AV 400 MHz spectrometer). The first (dependent output variable) PCR data matrix comprised aldehyde concentration scores vectors (PC1* and PC2*), whilst the second (predictor) one incorporated those from the fatty acid content/heating time variables (PC1-PC4) and their first-order interactions. Results: Structurally complex trans,trans- and cis,trans-alka-2,4-dienals, 4,5-epxy-trans-2-alkenals and 4-hydroxy-/4-hydroperoxy-trans-2-alkenals (group I aldehydes predominantly arising from PUFA peroxidation) strongly and positively loaded on PC1*, whereas n-alkanals and trans-2-alkenals (group II aldehydes derived from both MUFA and PUFA hydroperoxides) strongly and positively loaded on PC2*. PCR analysis of these scores vectors (SVs) demonstrated that PCs 1 (positively-loaded linoleoylglycerols and [linoleoylglycerol]:[SFA] content ratio), 2 (positively-loaded oleoylglycerols and negatively-loaded SFAs), 3 (positively-loaded linolenoylglycerols and [PUFA]:[SFA] content ratios), and 4 (exclusively orthogonal sampling time-points) all powerfully contributed to aldehydic PC1* SVs (p 10^-3 to < 10^-9), as did all PC1-3 x PC4 interaction ones (p 10^-5 to < 10^-9). PC2* was also markedly dependent on all the above PC SVs (PC2 > PC1 and PC3), and the interactions of PC1 and PC2 with PC4 (p < 10^-9 in each case), but not the PC3 x PC4 contribution. Conclusions: NMR-linked PCR analysis is a valuable strategy for (1) modelling the generation of aldehydic LOPs in heated cooking oils and other FM, and (2) tracking their unsaturated fatty acid (UFA) triacylglycerol sources therein.

Keywords: frying oils, lipid oxidation products, frying episodes, chemometrics, principal component regression, NMR Analysis, cytotoxic/genotoxic aldehydes

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Authors: Lakshmikanth Reddy, Bhavin Desai, Chandrakala Kari, Sanjay Sarkar, Pradeep Binu

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The sulphur dioxide gases generated as a by-product of smelting and converting operations of copper concentrate contain selenium apart from zinc, lead, copper, cadmium, bismuth, antimony, and arsenic. The gaseous stream is treated in waste heat boiler, electrostatic precipitator and scrubbers to remove coarse particulate matter in order to produce commercial grade sulfuric acid. The gas cleaning section of the acid plant uses water to scrub the smelting gases. After scrubbing, the sludge settled at the bottom of the scrubber, was analyzed in present investigation. It was found to contain 30 to 40 wt% copper and selenium up to 40 wt% selenium. The sludge collected during blow-down is directly recycled to the smelter for copper recovery. However, the selenium is expected to again vaporize due to high oxidation potential during smelting and converting, causing accumulation of selenium in sludge. In present investigation, a roasting process has been developed to recover the selenium before the copper recovery from the sludge at smelter. Selenium is associated with copper in sludge as copper selenide, as determined by X-ray diffraction and electron microscopy. The thermodynamic and thermos-gravimetry study revealed that the copper selenide phase present in the sludge was amenable to oxidation at 600°C forming oxides of copper and selenium (Cu-Se-O). However, the dissociation of selenium from the copper oxide was made possible by sulfatation using sulfur dioxide between 450 to 600°C, resulting into the formation of CuSO₄ (s) and SeO₂ (g). Lab scale trials were carried out in vertical tubular furnace to determine the optimum roasting conditions with respect to roasting time, temperature and molar ratio of O₂:SO₂. Using these optimum conditions, selenium up to 90 wt% in the form of SeO₂ vapors could be recovered from the sludge in a large-scale commercial roaster. Roasted sludge free from the selenium and containing oxides and sulfates of copper could now be recycled in the smelter for copper recovery.

Keywords: copper, selenium, copper selenide, sludge, roasting, SeO₂

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Authors: M. Ardelean, F. Manea, A. Pop, J. Schoonman

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The presence of pharmaceuticals in the environment and especially in water has gained increasing attention. They are included in emerging class of pollutants, and for most of them, legal limits have not been set-up due to their impact on human health and ecosystem was not determined and/or there is not the advanced analytical method for their quantification. In this context, the development of various advanced analytical methods for the quantification of pharmaceuticals in water is required. The electrochemical methods are known to exhibit the great potential for high-performance analytical methods but their performance is in direct relation to the electrode material and the operating techniques. In this study, two types of carbon-based electrodes materials, i.e., boron-doped diamond (BDD) and carbon nanofiber (CNF)-epoxy composite electrodes have been investigated through voltammetric techniques for the detection of naproxen in water. The comparative electrochemical behavior of naproxen (NPX) on both BDD and CNF electrodes was studied by cyclic voltammetry, and the well-defined peak corresponding to NPX oxidation was found for each electrode. NPX oxidation occurred on BDD electrode at the potential value of about +1.4 V/SCE (saturated calomel electrode) and at about +1.2 V/SCE for CNF electrode. The sensitivities for NPX detection were similar for both carbon-based electrode and thus, CNF electrode exhibited superiority in relation to the detection potential. Differential-pulsed voltammetry (DPV) and square-wave voltammetry (SWV) techniques were exploited to improve the electroanalytical performance for the NPX detection, and the best results related to the sensitivity of 9.959 µA·µM^-1 were achieved using DPV. In addition, the simultaneous detection of NPX and fluoxetine -a very common antidepressive drug, also present in water, was studied using CNF electrode and very good results were obtained. The detection potential values that allowed a good separation of the detection signals together with the good sensitivities were appropriate for the simultaneous detection of both tested pharmaceuticals. These results reclaim CNF electrode as a valuable tool for the individual/simultaneous detection of pharmaceuticals in water.

Keywords: boron-doped diamond electrode, carbon nanofiber-epoxy composite electrode, emerging pollutans, pharmaceuticals

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Authors: Mariana-Dana Damaceanu

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Electrochemical oxidation is one of the most convenient ways to obtain conjugated polymer films as polypyrrole, polyaniline, polythiophene or polycarbazole. The research in the field has been mainly directed to the study of electrical conduction properties of the materials obtained by electropolymerization, often the main reason being their use as electroconducting electrodes, and very little attention has been paid to the morphological and optical quality of the films electrodeposited on flat surfaces. Electropolymerization of the monomer solution was scarcely used in the past to manufacture polymer-based light-emitting diodes (PLED), most probably due to the difficulty of obtaining defectless polymer films with good mechanical and optical properties, or conductive polymers with well controlled molecular weights. Here we report our attempts in using electrochemical deposition as appropriate method for preparing ultrathin films of fluorene-based polymers for PLED applications. The properties of these films were evaluated in terms of structural morphology, optical properties, and electrochemical conduction. Thus, electropolymerization of 4,4'-(9-fluorenylidene)-dianiline was performed in dichloromethane solution, at a concentration of 10-2 M, using 0.1 M tetrabutylammonium tetrafluoroborate as electrolyte salt. The potential was scanned between 0 and 1.3 V on the one hand, and 0 - 2 V on the other hand, when polymer films with different structures and properties were obtained. Indium tin oxide-coated glass substrate of different size was used as working electrode, platinum wire as counter electrode and calomel electrode as reference. For each potential range 100 cycles were recorded at a scan rate of 100 mV/s. The film obtained in the potential range from 0 to 1.3 V, namely poly(FDA-NH), is visible to the naked eye, being light brown, transparent and fluorescent, and displays an amorphous morphology. Instead, the electrogrowth poly(FDA) film in the potential range of 0 - 2 V is yellowish-brown and opaque, presenting a self-assembled structure in aggregates of irregular shape and size. The polymers structure was identified by FTIR spectroscopy, which shows the presence of broad bands specific to a polymer, the band centered at approx. 3443 cm-1 being ascribed to the secondary amine. The two polymer films display two absorption maxima, at 434-436 nm assigned to π-π* transitions of polymers, and another at 832 and 880 nm assigned to polaron transitions. The fluorescence spectra indicated the presence of emission bands in the blue domain, with two peaks at 422 and 488 nm for poly (FDA-NH), and four narrow peaks at 422, 447, 460 and 484 nm for poly(FDA), peaks originating from fluorene-containing segments of varying degrees of conjugation. Poly(FDA-NH) exhibited two oxidation peaks in the anodic region and the HOMO energy value of 5.41 eV, whereas poly(FDA) showed only one oxidation peak and the HOMO level localized at 5.29 eV. The electrochemical data are discussed in close correlation with the proposed chemical structure of the electrogrowth films. Further research will be carried out to study their use and performance in light-emitting devices.

Keywords: electrogrowth polymer films, fluorene, morphology, optical properties

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Authors: Indu Barwal, Shloka Thakur, Subhash C. Yadav

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The plant virus capsid protein based nanoparticles are extensively studied for their application in biomedical research for development of nanomedicines and drug delivery systems. We have developed a chimeric drug delivery system by controlled in vitro assembly of separately bioconjugated fluorescent dye (as reporting molecule), folic acid (as receptor binding biomolecule for targeted delivery) and doxorubicin (as anticancer drug) using modified EDC NHS chemistry on heterologously overexpressed (E. coli) capsid proteins of cowpea chlorotic mottle virus (CCMV). This chimeric vehicle was further encapsidated on gold nanoparticles (20nm) coated with 5≠ thiolated DNA probe to neutralize the positive charge of capsid proteins. This facilitates the in vitro assembly of modified capsid subunits on the gold nanoparticles to develop chimeric GNPs encapsidated targeted drug delivery system. The bioconjugation of functionalities, number of functionality on capsid subunits as well as virus like nanoparticles, structural stability and in vitro assembly were confirmed by SDS PAGE, relative absorbance, MALDI TOF, ESI-MS, Circular dichroism, intrinsic tryptophan fluorescence, zeta particle size analyzer and TEM imaging. This vehicle was stable at pH 4.0 to 8.0 suitable for many organelles targeting. This in vitro assembled chimeric plant virus like particles could be suitable for ideal drug delivery vehicles for subcutaneous cancer treatment and could be further modified for other type of cancer treatment by conjugating other functionalities (targeting, drug) on capsids.

Keywords: chimeric drug delivery vehicles, bioconjugated plant, virus, capsid

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Authors: Reza Vakili, Xiaolei Fan, Alex Walton

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The first near ambient pressure (NAP)-XPS study of CO oxidation over Pt nanoparticles (NPs) incorporated into Zr-based UiO (UiO for Universitetet i Oslo) MOFs was carried out. For this purpose, the MOF-based Catalysts were prepared by wetness impregnation (WI-PtNPs@UiO-67) and linker design (LD-PtNPs@UiO-67) methods along with PtNPs@ZrO₂ as the control catalyst. Firstly, the as-synthesized catalysts were reduced in situ prior to the operando XPS analysis. The existence of Pt(II) species was proved in UiO-67 by observing Pt 4f core level peaks at a high binding energy of 72.6 ± 0.1 eV. However, by heating the WI-PtNPs@UiO-67 catalyst in situ to 200 °C under vacuum, the higher BE components disappear, leaving only the metallic Pt 4f doublet, confirming the formation of Pt NPs. The complete reduction of LD-PtNPs@UiO-67 is achieved at 250 °C and 1 mbar H₂. To understand the chemical state of Pt NPs in UiO-67 during catalytic turnover, we analyzed the Pt 4f region using operando NAP-XPS in the temperature-programmed measurements (100-260 °C) with reference to PtNPs@ZrO₂ catalyst. CO conversion during NAP-XPS experiments with the stoichiometric mixture shows that LD-PtNPs@UiO-67 has a better CO turnover frequency (TOF, 0.066 s⁻¹ at 260 °C) than the other two (ca. 0.055 s⁻¹). Pt 4f peaks only show one chemical species present at all temperatures, but the core level BE shifts change as a function of reaction temperature, i.e., Pt 4f peak from 71.8 eV at T < 200 °C to 71.2 eV at T > 200 °C. As this higher BE state of 71.8 eV was not observed after in situ reductions of the catalysts and only once the CO/O₂ mixture was introduced, we attribute it to the surface saturation of Pt NPs with adsorbed CO. In general, the quantitative analysis of Pt 4f data from the operando NAP-XPS experiments shows that the surface chemistry of the Pt active phase in the two PtNPs@UiO-67 catalysts is the same, comparable to that of PtNPs@ZrO₂. The observed difference in the catalytic activity can be attributed to the particle sizes of Pt NPs, as well as the dispersion of active phase in the support, which are different in the three catalysts.

Keywords: CO oxidation, heterogeneous catalysis, MOFs, Metal Organic Frameworks, NAP-XPS, Near Ambient Pressure X-ray Photoelectron Spectroscopy

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Authors: Deena Ramful-Baboolall, Eshana B. N. Bhatoo

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Morinda citrifolia L., commonly known as noni fruit, is rich in phytochemicals. This study investigated the phytophenolics content and antioxidant activity of green, mature green and ripe noni fruits. The vitamin C content ranged from 41.12 ± 0.083 to 143.63 ± 0.146 mg / 100 ml in fresh noni fruits. Ripe fruits contained the highest level of ascorbic acid followed by mature green and green fruits (p < 0.05). The total phenol content ranged from 0.909 (green) to 2.305 (ripe) mg / g of FW whilst the total flavonoid content ranged from 1.054 (green) to 2.116 (ripe) mg/g of FW. The in vitro antioxidant activity of the Morinda citrifolia L. extracts was also analysed using FRAP and TEAC assays. The reducing power of the fruit extracts as assessed by the FRAP assay decreased in the following order: ripe > mature green > green (p < 0.05). The TEAC values ranged from 0.2631 to 0.8921 µmol / g FW, with extracts of fruits at the mature green stage having highest values followed by fruits at the ripe and green stage respectively (p < 0.05). High correlation values were obtained between total phenolics, total flavonoids, ascorbic acid contents and the TEAC and FRAP assays (r > 0.8). Noni fruit extracts (0.2 and 0.4 % m / m) were compared with BHT (0.02 % m / m) on their ability to protect canola oil and mayonnaise, prepared with canola oil, against lipid oxidation during storage at 40°C. Mature green and ripe extracts, at both concentrations, were more effective than BHT in retarding oxidation in both food systems as evidenced by peroxide value and conjugated diene value determinations. Noni extracts were also very effective in inhibiting lipid peroxidation in tuna fish homogenates, assessed using TBARS assay. Noni fruits at the mature green and ripe stages represent a potential source of natural antioxidants for use a food additive.

Keywords: antioxidant, canola oil, mayonnaise, Morinda citrifolia L. fruit extracts, total flavonoids, total phenol

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Authors: Radhika Jain, Sangeeta Goomer

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In the present study an attempt has been made to re-engineer traditional wadi into wholesome ready-to-use cereal-pulse-based chunks rich in protein quality and fibre content. Chunks were made using extrusion-dehydration combination. Two formulations i.e., whole green gram dhal with instant oats and washed green gram dhal with whole oats were formulated. These chunks are versatile in nature as they can be easily incorporated in day-to-day home-made preparations such as pulao, potato curry and kadhi. Cereal-pulse ratio was calculated using NDpCal%. Limiting amino acids such as lysine, tryptophan, methionine, cysteine and threonine were calculated for maximum amino acid profile in cereal-pulse combination. Time-temperature combination for extrusion at 130^oC and dehydration at 65^oC for 7 hours and 15 minutes were standardized to obtain maximum protein and fibre content. Proximate analysis such as moisture, fat and ash content were analyzed. Protein content of formulation was 62.10% and 68.50% respectively. Fibre content of formulations was 2.99% and 2.45%, respectively. Using a 5-point hedonic scale, consumer preference trials of 102 consumers were conducted and analyzed. Evaluation of chunks prepared in potato curry, kadi and pulao showed preferences for colour 82%, 87%, 86%, texture and consistency 80%, 81%, 88%, flavour and aroma 74%, 82%, 86%, after taste 70%, 75%, 86% and overall acceptability 77%, 75%, 88% respectively. High temperature inactivates antinutritional compounds such as trypsin inhibitors, lectins, saponins etc. Hence, availability of protein content was increased. Developed products were palatable and easy to prepare.

Keywords: extrusion, NDpCal%, protein quality, wadi

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Authors: Faisal Nouroz, Mukaramin Mukaramin

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Of the transposable elements (TEs), the retrotransposons are the most copious elements identified from many sequenced genomes. They have played a major role in genome evolution, rearrangement, and expansions based on their copy and paste mode of proliferation. They are further divided into LTR and Non-LTR retrotransposons. The purpose of the current study was to identify the LTR REs in sequenced Phoenix dactylifera genome and to study their structural diversity. A total of 150 P. dactylifera BAC sequences with > 60kb sizes were randomly retrieved from National Center for Biotechnology Information (NCBI) database and screened for the presence of LTR retrotransposons. Seven bacterial artificial chromosomes (BAC) sequences showed full-length LTR Retrotransposons with 4 Copia and 3 Gypsy families having variable copy numbers in respective families. Reverse transcriptase (RT) domain was found as the most conserved domain among Copia and Gypsy superfamilies and was used to deduce evolutionary analysis. The amino acid residues among various RT sequences showed variability in their percentages indicating post divergence evolution. Amino acid Leucine was found in highest proportions followed by Lysine, while Methionine and Tryptophan were in lowest percentages. The phylogenetic analysis based on RT domains confirmed that although having most conserved RT regions, several evolutionary events occurred causing nucleotide polymorphisms and hence clustering of Gypsy and Copia superfamilies into their respective lineages. The study will be helpful in identification and annotation of these elements in other species and genera and their distribution patterns on chromosomes by fluorescent in situ hybridization techniques.

Keywords: transposable elements, Phoenix dactylifera, retrotransposons, phylogenetic analysis

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Authors: Harshit Mahandra, Rashmi Singh, Bina Gupta

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Molybdenum is widely used in thermocouples, anticathode of X-ray tubes and in the production of alloys of steels. Molybdenum compounds are extensively used as a catalyst in petroleum-refining industries for hydrodesulphurization. Activity of the catalysts decreases gradually with time and are dumped as hazardous waste due to contamination with toxic materials during the process. These spent catalysts can serve as a secondary source for metal recovery and help to sort out environmental and economical issues. In present study, extraction and separation of molybdenum from a Mo-Co spent catalyst leach liquor containing 0.870 g L⁻¹ Mo, 0.341 g L⁻¹ Co, 0.422 ×10⁻¹ g L⁻¹ Fe and 0.508 g L⁻¹ Al in 3 mol L⁻¹ HCl has been investigated using solvent extraction technique. The extracted molybdenum has been finally recovered as molybdenum trioxide. Leaching conditions used were- 3 mol L⁻¹ HCl, 90°C temperature, solid to liquid ratio (w/v) of 1.25% and reaction time of 60 minutes. 96.45% molybdenum was leached under these conditions. For the extraction of molybdenum from leach liquor, Cyphos IL 104 [trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate] in toluene was used as an extractant. Around 91% molybdenum was extracted with 0.02 mol L⁻¹ Cyphos IL 104, and 75% of molybdenum was stripped from the loaded organic phase with 2 mol L⁻¹ HNO₃ at A/O=1/1. McCabe Thiele diagrams were drawn to determine the number of stages required for the extraction and stripping of molybdenum. According to McCabe Thiele plots, two stages are required for both extraction and stripping of molybdenum at A/O=1/1 which were also confirmed by countercurrent simulation studies. Around 98% molybdenum was extracted in two countercurrent extraction stages with no co-extraction of cobalt and aluminum. Iron was removed from the loaded organic phase by scrubbing with 0.01 mol L⁻¹ HCl. Quantitative recovery of molybdenum is achieved in three countercurrent stripping stages at A/O=1/1. Trioxide of molybdenum was obtained from strip solution and was characterized by XRD, FE-SEM and EDX techniques. Molybdenum trioxide due to its distinctive electrochromic, thermochromic and photochromic properties is used as a smart material for sensors, lubricants, and Li-ion batteries. Molybdenum trioxide finds application in various processes such as methanol oxidation, metathesis, propane oxidation and in hydrodesulphurization. It can also be used as a precursor for the synthesis of MoS₂ and MoSe₂.

Keywords: Cyphos IL 104, molybdenum, spent Mo-Co catalyst, recovery

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Authors: V. Konjik, J. Schwartz, R. Sandhoff, M. Mack

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The rising number of multi-resistant pathogens demands the development of new antibiotics in order to reduce the lethal risk of infections. Here, we investigate roseoflavin, a vitamin B2 analogue which is produced by Streptomyces davawensis and Streptomyces cinnabarinus. We consider roseoflavin to be a 'Trojan horse' compound. Its chemical structure is very similar to riboflavin but in fact it is a toxin. Furthermore, it is a clever strategy with regard to the delivery of an antibiotic to its site of action but also with regard to the production of this chemical: The producer cell has only to convert a vitamin (which is already present in the cytoplasm) into a vitamin analog. Roseoflavin inhibits the activity of Flavin depending proteins, which makes up to 3.5 % of predicted proteins in organisms sequenced so far. We sequentially knocked out gene clusters and later on single genes in order to find the ones which are involved in the roseoflavin biosynthesis. Consequently, we identified the gene rosB, coding for the protein carrying out the first step of roseoflavin biosynthesis, starting form Flavin mononucleotide. Here we show, that the protein RosB has so far unknown features. It is per se an oxidoreductase, a decarboxylase and an aminotransferase, all rolled into one enzyme. A screen of cofactors revealed needs of oxygen, NAD+, thiamine and glutamic acid to carry out its function. Surprisingly, thiamine is not only needed for the decaboxylation step, but also for the oxidation of 8-demethyl-8-formyl Flavin mononucleotide. We had managed to isolate three different Flavin intermediates with different oxidation states, which gave us a mechanistic insight of RosB functionality. Our work points to a so far new function of thiamine in Streptomyces davawensis. Additionally, RosB could be extremely useful for chemical synthesis. Careful engineering of RosB may allow the site-specific replacement of methyl groups by amino groups in polyaromatic compounds of commercial interest. Finally, the complete clarification of the roseoflavin biosynthesis opens the possibility of engineering cost-effective roseoflavin producing strains.

Keywords: antibiotic, flavin analogue, roseoflavin biosynthesis, vitamin B2

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Authors: Yatimah Alias, Tilagam Marimuthu, M. R. Mahmoudian, Sharifah Mohamad

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The rapid growth of science and technology in energy and environmental fields has enlightened the substantial importance of the conducting polymer and metal composite materials engineered at nano-scale. In this study, polypyrrole-cobalt composites (PPy-Co Cs) and polypyrrole-nickel oxide composites (PPy-NiO Cs) were prepared by a simple and facile chemical polymerization method with an aqueous solution of pyrrole monomer in the presence of metal salt. These composites then fabricated into non-enzymatic hydrogen peroxide (H2O2) and glucose sensor. The morphology and composition of the composites are characterized by the Field Emission Scanning Electron Microscope, Fourier Transform Infrared Spectrum and X-ray Powder Diffraction. The obtained results were compared with the pure PPy and metal oxide particles. The structural and morphology properties of synthesized composites are different from those of pure PPy and metal oxide particles, which were attributed to the strong interaction between the PPy and the metal particles. Besides, a favorable micro-environment for the electrochemical oxidation of H2O2 and glucose was achieved on the modified glassy carbon electrode (GCE) coated with PPy-Co Cs and PPy-NiO Cs respectively, resulting in an enhanced amperometric response. Both PPy-Co/GCE and PPy-NiO/GCE give high response towards target analyte at optimum condition of 500 μl pyrrole monomer content. Furthermore, the presence of pyrrole monomer greatly increases the sensitivity of the respective modified electrode. The PPy-Co/GCE could detect H2O2 in a linear range of 20 μM to 80 mM with two linear segments (low and high concentration of H2O2) and the detection limit for both ranges is 2.05 μM and 19.64 μM, respectively. Besides, PPy-NiO/GCE exhibited good electrocatalytic behavior towards glucose oxidation in alkaline medium and could detect glucose in linear ranges of 0.01 mM to 0.50 mM and 1 mM to 20 mM with detection limit of 0.33 and 5.77 μM, respectively. The ease of modifying and the long-term stability of this sensor have made it superior to enzymatic sensors, which must kept in a critical environment.

Keywords: metal oxide, composite, non-enzymatic sensor, polypyrrole

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Authors: Satyananda Behera, Ritwik Sarkar

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In iron and steel industries, MgO–C refractories are widely used in basic oxygen furnaces, electric arc furnaces and steel ladles due to their excellent corrosion resistance, thermal shock resistance, and other excellent hot properties. Conventionally magnesia carbon refractories contain about 8-20 wt% of carbon but the use of carbon is also associate with disadvantages like oxidation, low fracture strength, high heat loss and higher carbon pick up in steel. So, MgO-C refractory having low carbon content without compromising the beneficial properties is the challenge. Nano carbon, having finer particles, can mix and distribute within the entire matrix uniformly and can result in improved mechanical, thermo-mechanical, corrosion and other refractory properties. Previous experiences with the use of nano carbon in low carbon MgO-C refractory have indicated an optimum range of use of nano carbon around 1 wt%. This optimum nano carbon content was used in MgO-C compositions with flaky graphite followed by aluminum and silicon metal powder as an anti-oxidant. These low carbon MgO-C refractory compositions were prepared by conventional manufacturing techniques. At the same time 16 wt. % flaky graphite containing conventional MgO-C refractory was also prepared parallel under similar conditions. The developed products were characterized for various refractory related properties. Nano carbon containing compositions showed better mechanical, thermo-mechanical properties, and oxidation resistance compared to that of conventional composition. Improvement in the properties is associated with the formation of in-situ ceramic phase-like aluminum carbide, silicon carbide, and magnesium aluminum spinel. Higher surface area and higher reactivity of N220 nano carbon black resulted in greater formation in-situ ceramic phases, even at a much lower amount. Nano carbon containing compositions were found to have improved properties in MgO-C refractories compared to that of the conventional ones at much lower total carbon content.

Keywords: N220nano carbon black, refractory properties, conventionally manufacturing techniques, conventional magnesia carbon refractories

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Authors: Othman Saoudi

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In this work, we have interested in the investigation of the chemical denaturants and synthesized ionic liquids effects on the fluorescence properties of the laccase from Trametes versicolor. The fluorescence properties of the laccase result from the presence of Tryptophan, which has an aromatic core responsible for the absorption in ultra violet domain and the emission of the photons of fluorescence. The effect Pyrrolidinuim Formate ([pyrr][F]) and Morpholinium Formate ([morph][F]) ionic liquids on the laccase behavior for various volumetric fractions are studied. We have shown that the fluorescence spectrum relative to the [pyrr][F] presents a single band with a maximum around 340 nm and a secondary peak at 361 nm for a volumetric fraction of 20% v/v. For concentration superiors to 40%, the fluorescence intensity decreases and a displacement of the peaks toward higher wavelengths has occurred. For the [morph][F], the fluorescence spectrum showed a single band around 340 nm. The intensity of the principal peak decreases for concentration superiors to 20% v/v. From the plot representing the variation of the λₘₐₓ versus the volumetric concentration, we have determined the concentration of the half-transitions C1/2. These concentrations are equal to 42.62% and 40.91% v/v in the presence of [pyrr][F] and [morph][F] respectively. For the chemical denaturation, we have shown that the fluorescence intensity decreases with increasing denaturant concentrations where the maximum of the wavelength of emission shifts toward the higher wavelengths. We have also determined from the spectrum relative to the urea and GdmCl, the unfolding energy, ∆GD. The results show that the variation of the unfolding energy as a function of the denaturant concentrations varies according to the linear regression model. We have demonstrated also that the half-transitions C1/2 have occurred for urea and GdmCl denaturants concentrations around 3.06 and 3.17 M respectively.

Keywords: laccase, fluorescence, ionic liquids, chemical denaturants

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Authors: Joanna Cabaj, Sylwia Baluta, Karol Malecha, Kamila Drzozga

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Catecholamines are the principal neurotransmitters that mediate a variety of the central nervous system functions, such as motor control, cognition, emotion, memory processing, and endocrine modulation. Dysfunctions in catecholamine neurotransmission are induced in some neurologic and neuropsychiatric diseases. Changeable neurotransmitters level in biological fluids can be a marker of several neurological disorders. Because of its significance in analytical techniques and diagnostics, sensitive and selective detection of neurotransmitters is increasingly attracting a lot of attention in different areas of bio-analysis or biomedical research. Recently, fluorescent techniques for detection of catecholamines have attracted interests due to their reasonable cost, convenient control, as well as maneuverability in biological environments. Nevertheless, with the observed need for a sensitive and selective catecholamines sensor, the development of a convenient method for this neurotransmitter is still at its basic level. The manipulation of nanostructured materials in conjunction with biological molecules has led to the development of a new class of hybrid modified biosensors in which both enhancement of charge transport and biological activity preservation may be obtained. Immobilization of biomaterials on electrode surfaces is the crucial step in fabricating electrochemical as well as optical biosensors and bioelectronic devices. Continuing systematic investigation in the manufacturing of enzyme–conducting sensitive systems, here is presented a convenient fluorescence sensing strategy for catecholamines detection based on FRET (fluorescence resonance energy transfer) phenomena observed for, i.e., complexes of Fe²⁺ and epinephrine. The biosensor was constructed using low temperature co-fired ceramics technology (LTCC). This sensing system used the catalytical oxidation of catecholamines and quench of the strong luminescence of obtained complexes due to FRET. The detection process was based on the oxidation of substrate in the presence of the enzyme–laccase/tyrosinase.

Keywords: biosensor, conducting polymer, enzyme, FRET, LTCC

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Authors: Ling Ai, Ziyu Zhao, Zeyu Zhou, Xiaochen Yang, Heng Zhai, Stuart Holmes

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Optimizing the catalyst layer structure is crucial for enhancing the performance of proton exchange membrane fuel cells (PEMFCs) with low Platinum (Pt) loading. Current works focused on the utilization, durability, and site activity of Pt particles on support, and performance enhancement has been achieved by loading Pt onto porous support with different morphology, such as graphene, carbon fiber, and carbon black. Some schemes have also incorporated cost considerations to achieve lower Pt loading. However, the design of the catalyst layer (CL) structure in the membrane electrode assembly (MEA) must consider the interactions between the layers. Addressing the crucial aspects of water management, low contact resistance, and the establishment of effective three-phase boundary for MEA, multi-walled carbon nanotubes (MWCNTs) are promising CL support due to their intrinsically high hydrophobicity, high axial electrical conductivity, and potential for ordered alignment. However, the drawbacks of MWCNTs, such as strong agglomeration, wall surface chemical inertness, and unopened ends, are unfavorable for Pt nanoparticle loading, which is detrimental to MEA processing and leads to inhomogeneous CL surfaces. This further deteriorates the utilization of Pt and increases the contact resistance. Robust chemical oxidation or nitrogen doping can introduce polar functional groups onto the surface of MWCNTs, facilitating the creation of open tube ends and inducing defects in tube walls. This improves dispersibility and load capacity but reduces length and conductivity. Consequently, a trade-off exists between maintaining the intrinsic properties and the degree of functionalization of MWCNTs. In this work, MWCNTs were modified based on the operational requirements of the MEA from the viewpoint of interlayer interactions, including the search for the optimal degree of oxidation, N-doping, and micro-arrangement. MWCNT were functionalized by oxidizing, N-doping, as well as micro-alignment to achieve lower contact resistance between CL and proton exchange membrane (PEM), better hydrophobicity, and enhanced performance. Furthermore, this work expects to construct a more continuously distributed three-phase boundary by aligning MWCNT to form a locally ordered structure, which is essential for the efficient utilization of Pt active sites. Different from other chemical oxidation schemes that used HNO3:H2SO4 (1:3) mixed acid to strongly oxidize MWCNT, this scheme adopted pure HNO3 to partially oxidize MWCNT at a lower reflux temperature (80 ℃) and a shorter treatment time (0 to 10 h) to preserve the morphology and intrinsic conductivity of MWCNT. The maximum power density of 979.81 mw cm-2 was achieved by Pt loading on 6h MWCNT oxidation time (Pt-MWCNT6h). This represented a 59.53% improvement over the commercial Pt/C catalyst of 614.17 (mw cm-2). In addition, due to the stronger electrical conductivity, the charge transfer resistance of Pt-MWCNT6h in the electrochemical impedance spectroscopy (EIS) test was 0.09 Ohm cm-2, which was 48.86% lower than that of Pt/C. This study will discuss the developed catalysts and their efficacy in a working fuel cell system. This research will validate the impact of low-functionalization modification of MWCNTs on the performance of PEMFC, which simplifies the preparation challenges of CL and contributing for the widespread commercial application of PEMFCs on a larger scale.

Keywords: carbon nanotubes, electrocatalyst, membrane electrode assembly, proton exchange membrane fuel cell

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Authors: W. Jahouach-Rabai, J. Aribi, Z. Azzouz-Berriche, R. Lahsni, F. Hosni

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Gamma irradiation applied in removing pharmaceutical contaminants from wastewater is an effective advanced oxidation process (AOP), considered as an alternative to conventional water treatment technologies. In this purpose, the degradation efficiency of several detected contaminants under gamma irradiation was evaluated. In fact, radiolysis of organic pollutants in aqueous solutions produces powerful reactive species, essentially hydroxyl radical ( ·OH), able to destroy recalcitrant pollutants in water. Pharmaceuticals considered in this study are aqueous solutions of paracetamol, ibuprofen, and diclofenac at different concentrations 0.1-1 mmol/L, which were treated with irradiation doses from 3 to 15 kGy. The catalytic oxidation of these compounds by gamma irradiation was investigated using hydrogen peroxide (H₂O₂) as a convenient oxidant. Optimization of the main parameters influencing irradiation process, namely irradiation doses, initial concentration and oxidant volume (H₂O₂) were investigated, in the aim to release high degradation efficiency of considered pharmaceuticals. Significant modifications attributed to these parameters appeared in the variation of degradation efficiency, chemical oxygen demand removal (COD) and concentration of radio-induced radicals, confirming them synergistic effect to attempt total mineralization. Pseudo-first-order reaction kinetics could be used to depict the degradation process of these compounds. A sophisticated analytical study was released to quantify the detected radio-induced radicals (electron paramagnetic resonance spectroscopy (EPR) and high performance liquid chromatography (HPLC)). All results showed that this process is effective for the degradation of many pharmaceutical products in aqueous solutions due to strong oxidative properties of generated radicals mainly hydroxyl radical. Furthermore, the addition of an optimal amount of H₂O₂ was efficient to improve the oxidative degradation and contribute to the high performance of this process at very low doses (0.5 and 1 kGy).

Keywords: AOP, COD, hydroxyl radical, EPR, gamma irradiation, HPLC, pharmaceuticals

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Authors: Ivan P. Pozdnyakov, Alexey A. Melnikov, Nikolai V. Tkachenko

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Photochemical reactions with participation of iron (III) carboxylates are important for environmental photochemistry and have a great potential of application in water purification (Advanced Oxidation Processes, photo-Fenton and Fenton-like processes). In spite of this information about excited states and primary intermediates in photochemistry of Fe(III) complexes with carboxylic acids is scarce. This talk presents and discusses the results of several recent authors' publications in a field of ultra fast spectroscopy of natural Fe(III) carboxylates.

Keywords: carboxylates, iron complexes, photochemistry, radical complexes, ultrafast processes

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Authors: Belal Bakheet, John Beardall, Xiwang Zhang, David McCarthy

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The potential risks associated with toxic cyanobacteria have raised growing environmental and public health concerns leading to an increasing effort into researching ways to bring about their removal from water, together with destruction of their associated cyanotoxins. A variety of toxins are synthesized by cyanobacteria and include hepatotoxins, neurotoxins, and cytotoxins which can cause a range of symptoms in humans from skin irritation to serious liver and nerve damage. Therefore drinking water treatment processes should ensure the consumers’ safety by removing both cyanobacterial cells, and cyanotoxins from the water. Cyanobacterial cells and cyanotoxins presented challenges to the conventional water treatment systems; their accumulation within drinking water treatment plants has been reported leading to plants shut down. Thus, innovative and effective water purification systems to tackle cyanobacterial pollution are required. In recent years there has been increasing attention to the electrochemical oxidation process as a feasible alternative disinfection method which is able to generate in situ a variety of oxidants that would achieve synergistic effects in the water disinfection process and toxin degradation. By utilizing only electric current, the electrochemical process through electrolysis can produce reactive oxygen species such as hydroxyl radicals from the water, or other oxidants such as chlorine from chloride ions present in the water. From extensive physiological and morphological investigation of cyanobacterial cells during electrolysis, our results show that these oxidants have significant impact on cell inactivation, simultaneously with cyanotoxins removal without the need for chemicals addition. Our research aimed to optimize existing electrochemical oxidation systems and develop new systems to treat water containing toxic cyanobacteria and cyanotoxins. The research covers detailed mechanism study on oxidants production and cell inactivation in the treatment under environmental conditions. Overall, our study suggests that the electrochemical treatment process e is an effective method for removal of toxic cyanobacteria and cyanotoxins.

Keywords: toxic cyanobacteria, cyanotoxins, electrochemical process, oxidants

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Authors: M. El Hajji, A. Hallaoui, L. Bazzi, A. Benlhachemi, O. Jbara, A. Tara, B. Bakiz, L. Bazzi, M. Hilali

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The objective of this study was the development of zinc-copper binary oxide "Cu2O-ZnO" thin films by the electrochemical method "cathodic electrodeposition" and their uses for the degradation of a basic dye "Congo Red" by direct anodic oxidation. The anode materials synthesized were characterized by X-ray diffraction "XRD" and by scanning electron microscopy "SEM" coupled to EDS.

Keywords: Cu2O-ZnO thin films, cathodic electrodeposition, electrodegradation, Congo Red, BDD

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Authors: Komal Rathore, Kiesha Pierre, Kyle Cogswell, Aaron Driscoll, Andres Tejada Martinez, Gita Iranipour, Luke Mulford, Aydin Sunol

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Modeling of Biological Wastewater Treatment Plants requires several parameters for kinetic rate expressions, thermo-physical properties, and hydrodynamic behavior. The kinetics and associated mechanisms become complex due to several biological processes taking place in wastewater treatment plants at varying times and spatial scales. A dynamic process model that incorporated the complex model for activated sludge kinetics was developed using the BioWin software platform for an Advanced Wastewater Treatment Plant in Valrico, Florida. Due to the extensive number of tunable parameters, an experimental design was employed for judicious selection of the most influential parameter sets and their bounds. The model was tuned using both the influent and effluent plant data to reconcile and rectify the forecasted results from the BioWin Model. Amount of mixed liquor suspended solids in the oxidation ditch, aeration rates and recycle rates were adjusted accordingly. The experimental analysis and plant SCADA data were used to predict influent wastewater rates and composition profiles as a function of time for extended periods. The lumped dynamic model development process was coupled with Computational Fluid Dynamics (CFD) modeling of the key units such as oxidation ditches in the plant. Several CFD models that incorporate the nitrification-denitrification kinetics, as well as, hydrodynamics was developed and being tested using ANSYS Fluent software platform. These realistic and verified models developed using BioWin and ANSYS were used to plan beforehand the operating policies and control strategies for the biological wastewater plant accordingly that further allows regulatory compliance at minimum operational cost. These models, with a little bit of tuning, can be used for other biological wastewater treatment plants as well. The BioWin model mimics the existing performance of the Valrico Plant which allowed the operators and engineers to predict effluent behavior and take control actions to meet the discharge limits of the plant. Also, with the help of this model, we were able to find out the key kinetic and stoichiometric parameters which are significantly more important for modeling of biological wastewater treatment plants. One of the other important findings from this model were the effects of mixed liquor suspended solids and recycle ratios on the effluent concentration of various parameters such as total nitrogen, ammonia, nitrate, nitrite, etc. The ANSYS model allowed the abstraction of information such as the formation of dead zones increases through the length of the oxidation ditches as compared to near the aerators. These profiles were also very useful in studying the behavior of mixing patterns, effect of aerator speed, and use of baffles which in turn helps in optimizing the plant performance.

Keywords: computational fluid dynamics, flow-sheet simulation, kinetic modeling, process dynamics

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Authors: P. M. G. Pathiraja, P. Egodawatta, A. Goonetilleke, V. S. J. Te'o

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The production and use of Polychlorinated biphenyls (PCBs), a group of synthetic halogenated hydrocarbons have been restricted worldwide due to its toxicity and categorized as one of the twelve priority persistent organic pollutants (POP) by the Stockholm Convention. Low reactivity and high chemical stability of PCBs have made them highly persistent in the environment and bio-concentration and bio-magnification along the food chain contribute to multiple health impacts in humans and animals. Remediating environments contaminated with PCBs is a challenging task for decades. Use of microorganisms for remediation of PCB contaminated soils and sediments have been widely investigated due to the potential of breakdown these complex contaminants with minimum environmental impacts. To achieve an effective bioremediation of polychlorinated biphenyls (PCBs) contaminated environments, microbes were sourced from environmental samples and tested for their ability to hydrolyze PCBs under different conditions. Comparison of PCB degradation efficiencies of four naturally occurring facultative bacterial cultures isolated through selective enrichment under aerobic and anaerobic conditions were simultaneously investigated in minimal salt medium using 50 mg/L Aroclor 1260, a commonly used commercial PCB mixture as the sole source of carbon. The results of a six-week study demonstrated that all the tested facultative Achromobacter, Ochrobactrum, Lysinibacillus and Pseudomonas strains are capable of degrading PCBs under both anaerobic and aerobic conditions while assisting hydrophobic PCBs to make solubilize in the aqueous minimal medium. Overall, the results suggest that some facultative bacteria are capable of effective in degrading PCBs under anaerobic conditions through reductive dechlorination and under aerobic conditions through oxidation. Therefore, use of suitable facultative microorganisms under combined anaerobic-aerobic conditions and combination of such strains capable of solubilization and breakdown of PCBs has high potential in achieving higher PCB removal rates.

Keywords: bioremediation, combined anaerobic-aerobic degradation, facultative microorganisms, polychlorinated biphenyls

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Authors: Medhanie Gebremedhin Gebru, Alex Schechter

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Dimethyl ether (DME) possesses several advantages over other small organic molecules such as methanol, ethanol, and ammonia in terms of providing higher energy density, being less toxic, and having lower Nafion membrane crossover. However, the absence of an active and stable catalyst has been the bottleneck that hindered the commercialization of direct DME fuel cells. A Vulcan XC72 carbon-supported ternary metal catalyst, Pt₃Pd₃Sn₂/C is reported to have yielded the highest specific power density (90 mW mg-¹PGM) as compared to other catalysts tested fordirect DME fuel cell (DDMEFC). However, the micropores and sulfur groups present in Vulcan XC72 hinder the fuel utilization by causing Pt agglomeration and sulfur poisoning. Vulcan XC72 having a high carbon sp³ hybridization content, is also prone to corrosion. Therefore, carbon supports such as multi-walled carbon nanotube (MWCNT), black pearl 2000 (BP2000), and their cold N2 plasma-treated counterpartswere tested to further enhance the activity of the catalyst, and the outputs with these carbons were compared with the originally used support. Detailed characterization of the pristine and carbon supports was conducted. Electrochemical measurements in three-electrode cells and laboratory prototype fuel cells were conducted.Pt₃Pd₃Sn₂/BP2000 exhibited excellent performance in terms of electrochemical active surface area (ECSA), peak current density (jp), and DME oxidation charge (Qoxi). The effect of the plasma activation on the activity improvement was observed only in the case of MWCNT while having little or no effect on the other carbons. A Pt₃Pd₃Sn₂ supported on the optimized mixture of carbons containing 75% plasma-activated MWCNT and 25% BP2000 (Pt₃Pd₃Sn₂/75M25B) provided the highest reported power density of 117 mW mg-1PGM using an anode loading of1.55 mgPGMcm⁻².

Keywords: DME, DDMEFC, ternary metal catalyst, carbon support, plasma activation

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