Search results for: carbonylative Suzuki cross-coupling reaction
Commenced in January 2007
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Edition: International
Paper Count: 2501

Search results for: carbonylative Suzuki cross-coupling reaction

221 Nitrate Photoremoval in Water Using Nanocatalysts Based on Ag / Pt over TiO2

Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

Abstract:

Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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220 Garnet-based Bilayer Hybrid Solid Electrolyte for High-Voltage Cathode Material Modified with Composite Interface Enabler on Lithium-Metal Batteries

Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

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219 Influence of a Cationic Membrane in a Double Compartment Filter-Press Reactor on the Atenolol Electro-Oxidation

Authors: Alan N. A. Heberle, Salatiel W. Da Silva, Valentin Perez-Herranz, Andrea M. Bernardes

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Contaminants of emerging concern are substances widely used, such as pharmaceutical products. These compounds represent risk for both wild and human life since they are not completely removed from wastewater by conventional wastewater treatment plants. In the environment, they can be harm even in low concentration (µ or ng/L), causing bacterial resistance, endocrine disruption, cancer, among other harmful effects. One of the most common taken medicine to treat cardiocirculatory diseases is the Atenolol (ATL), a β-Blocker, which is toxic to aquatic life. In this way, it is necessary to implement a methodology, which is capable to promote the degradation of the ATL, to avoid the environmental detriment. A very promising technology is the advanced electrochemical oxidation (AEO), which mechanisms are based on the electrogeneration of reactive radicals (mediated oxidation) and/or on the direct substance discharge by electron transfer from contaminant to electrode surface (direct oxidation). The hydroxyl (HO•) and sulfate (SO₄•⁻) radicals can be generated, depending on the reactional medium. Besides that, at some condition, the peroxydisulfate (S₂O₈²⁻) ion is also generated from the SO₄• reaction in pairs. Both radicals, ion, and the direct contaminant discharge can break down the molecule, resulting in the degradation and/or mineralization. However, ATL molecule and byproducts can still remain in the treated solution. On this wise, some efforts can be done to implement the AEO process, being one of them the use of a cationic membrane to separate the cathodic (reduction) from the anodic (oxidation) reactor compartment. The aim of this study is investigate the influence of the implementation of a cationic membrane (Nafion®-117) to separate both cathodic and anodic, AEO reactor compartments. The studied reactor was a filter-press, with bath recirculation mode, flow 60 L/h. The anode was an Nb/BDD2500 and the cathode a stainless steel, both bidimensional, geometric surface area 100 cm². The solution feeding the anodic compartment was prepared with ATL 100 mg/L using Na₂SO₄ 4 g/L as support electrolyte. In the cathodic compartment, it was used a solution containing Na₂SO₄ 71 g/L. Between both solutions was placed the membrane. The applied currents densities (iₐₚₚ) of 5, 20 and 40 mA/cm² were studied over 240 minutes treatment time. Besides that, the ATL decay was analyzed by ultraviolet spectroscopy (UV/Vis). The mineralization was determined performing total organic carbon (TOC) in TOC-L CPH Shimadzu. In the cases without membrane, the iₐₚₚ 5, 20 and 40 mA/cm² resulted in 55, 87 and 98 % ATL degradation at the end of treatment time, respectively. However, with membrane, the degradation, for the same iₐₚₚ, was 90, 100 and 100 %, spending 240, 120, 40 min for the maximum degradation, respectively. The mineralization, without membrane, for the same studied iₐₚₚ, was 40, 55 and 72 %, respectively at 240 min, but with membrane, all tested iₐₚₚ reached 80 % of mineralization, differing only in the time spent, 240, 150 and 120 min, for the maximum mineralization, respectively. The membrane increased the ATL oxidation, probably due to avoid oxidant ions (S₂O₈²⁻) reduction on the cathode surface.

Keywords: contaminants of emerging concern, advanced electrochemical oxidation, atenolol, cationic membrane, double compartment reactor

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218 Expression of Selected miRNAs in Placenta of the Intrauterine Restricted Growth Fetuses in Cattle

Authors: Karolina Rutkowska, Hubert Pausch, Jolanta Oprzadek, Krzysztof Flisikowski

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The placenta is one of the most important organs that plays a crucial role in the fetal growth and development. Placenta dysfunction is one of the primary cause of the intrauterine growth restriction (IUGR). Cattle have the cotyledonary placenta which consists of two anatomical parts: fetal and maternal. In the case of cattle during the first months of pregnancy, it is very easy to separate maternal caruncle from fetal cotyledon tissue, easier in fact than removing an ordinary glove from one's hand. Which in fact make easier to conduct tissue-specific molecular studies. Typically, animal models for the study of IUGR are created using surgical methods and malnutrition of the pregnant mother or in the case of mice by genetic modifications. However, proposed cattle model with MIMT1Del/WT deletion is unique because it was created without any surgical methods what significantly distinguish it from the other animal models. The primary objective of the study was to identify differential expression of selected miRNAs in the placenta from normal and intrauterine growth restricted fetuses. There was examined the expression of miRNA in the fetal and maternal part of the placenta from 24 fetuses (12 samples from the fetal part of the placenta and 12 samples from maternal part of the placenta). In the study, there was done miRNAs sequencing in the placenta of MIMT1Del/WT fetuses and MIMT1WT/WT fetuses. Then, there were selected miRNAs that are involved in fetal growth and development. Analysis of miRNAs expression was conducted on ABI7500 machine. miRNAs expression was analyzed by reverse-transcription polymerase chain reaction (RT-PCR). As the reference gene was used SNORD47. The results were expressed as 2ΔΔCt: ΔΔCt = (Ctij − CtSNORD47j) − (Cti1 − CtSNORD471). Where Ctij and CtSNORD47j are the Ct values for gene i and for SNORD47 in a sample (named j); Cti1 and CtSNORD471 are the Ct values in sample 1. Differences between groups were evaluated with analysis of variance by using One-Way ANOVA. Bonferroni’s tests were used for interpretation of the data. All normalised miRNA expression values are expressed on a value of natural logarithm. The data were expressed as least squares mean with standard errors. Significance was declared when P < 0.05. The study shows that miRNAs expression depends on the part of the placenta where they origin (fetal or maternal) and on the genotype of the animal. miRNAs offer a particularly new approach to study IUGR. Corresponding tissue samples were collected according to the standard veterinary protocols according to the European Union Normative for Care and Use of Experimental Animals. All animal experiments were approved by the Animal Ethics Committee of the State Provincial Office of Southern Finland (ESAVI-2010-08583/YM-23).

Keywords: placenta, intrauterine growth restriction, miRNA, cattle

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217 Synthesis of Methanol through Photocatalytic Conversion of CO₂: A Green Chemistry Approach

Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

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216 In-Situ Formation of Particle Reinforced Aluminium Matrix Composites by Laser Powder Bed Fusion of Fe₂O₃/AlSi12 Powder Mixture Using Consecutive Laser Melting+Remelting Strategy

Authors: Qimin Shi, Yi Sun, Constantinus Politis, Shoufeng Yang

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In-situ preparation of particle-reinforced aluminium matrix composites (PRAMCs) by laser powder bed fusion (LPBF) additive manufacturing is a promising strategy to strengthen traditional Al-based alloys. The laser-driven thermite reaction can be a practical mechanism to in-situ synthesize PRAMCs. However, introducing oxygen elements through adding Fe₂O₃ makes the powder mixture highly sensitive to form porosity and Al₂O₃ film during LPBF, bringing challenges to producing dense Al-based materials. Therefore, this work develops a processing strategy combined with consecutive high-energy laser melting scanning and low-energy laser remelting scanning to prepare PRAMCs from a Fe₂O₃/AlSi12 powder mixture. The powder mixture consists of 5 wt% Fe₂O₃ and the remainder AlSi12 powder. The addition of 5 wt% Fe₂O₃ aims to achieve balanced strength and ductility. A high relative density (98.2 ± 0.55 %) was successfully obtained by optimizing laser melting (Emelting) and laser remelting surface energy density (Eremelting) to Emelting = 35 J/mm² and Eremelting = 5 J/mm². Results further reveal the necessity of increasing Emelting, to improve metal liquid’s spreading/wetting by breaking up the Al₂O₃ films surrounding the molten pools; however, the high-energy laser melting produced much porosity, including H₂₋, O₂₋ and keyhole-induced pores. The subsequent low-energy laser remelting could close the resulting internal pores, backfill open gaps and smoothen solidified surfaces. As a result, the material was densified by repeating laser melting and laser remelting layer by layer. Although with two-times laser scanning, the microstructure still shows fine cellular Si networks with Al grains inside (grain size of about 370 nm) and in-situ nano-precipitates (Al₂O₃, Si, and Al-Fe(-Si) intermetallics). Finally, the fine microstructure, nano-structured dispersion strengthening, and high-level densification strengthened the in-situ PRAMCs, reaching yield strength of 426 ± 4 MPa and tensile strength of 473 ± 6 MPa. Furthermore, the results can expect to provide valuable information to process other powder mixtures with severe porosity/oxide-film formation potential, considering the evidenced contribution of laser melting/remelting strategy to densify material and obtain good mechanical properties during LPBF.

Keywords: densification, laser powder bed fusion, metal matrix composites, microstructures, mechanical properties

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215 The Highly Dispersed WO3-x Photocatalyst over the Confinement Effect of Mesoporous SBA-15 Molecular Sieves for Photocatalytic Nitrogen Reduction

Authors: Xiaoling Ren, Guidong Yang

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

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

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214 Investigation of Xanthomonas euvesicatoria on Seed Germination and Seed to Seedling Transmission in Tomato

Authors: H. Mayton, X. Yan, A. G. Taylor

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Infested tomato seeds were used to investigate the influence of Xanthomonas euvesicatoria on germination and seed to seedling transmission in a controlled environment and greenhouse assays in an effort to develop effective seed treatments and characterize seed borne transmission of bacterial leaf spot of tomato. Bacterial leaf spot of tomato, caused by four distinct Xanthomonas species, X. euvesicatoria, X. gardneri, X. perforans, and X. vesicatoria, is a serious disease worldwide. In the United States, disease prevention is expensive for commercial growers in warm, humid regions of the country, and crop losses can be devastating. In this study, four different infested tomato seed lots were extracted from tomato fruits infected with bacterial leaf spot from a field in New York State in 2017 that had been inoculated with X. euvesicatoria. In addition, vacuum infiltration at 61 kilopascals for 1, 5, 10, and 15 minutes and seed soaking for 5, 10, 15, and 30 minutes with different bacterial concentrations were used to artificially infest seed in the laboratory. For controlled environment assays, infested tomato seeds from the field and laboratory were placed othe n moistened blue blotter in square plastic boxes (10 cm x 10 cm) and incubated at 20/30 ˚C with an 8/16 hour light cycle, respectively. Infested tomato seeds from the field and laboratory were also planted in small plastic trays in soil (peat-lite medium) and placed in the greenhouse with 24/18 ˚C day and night temperatures, respectively, with a 14-hour photoperiod. Seed germination was assessed after eight days in the laboratory and 14 days in the greenhouse. Polymerase chain reaction (PCR) using the hrpB7 primers (RST65 [5’- GTCGTCGTTACGGCAAGGTGGTG-3’] and RST69 [5’-TCGCCCAGCGTCATCAGGCCATC-3’]) was performed to confirm presence or absence of the bacterial pathogen in seed lots collected from the field and in germinating seedlings in all experiments. For infested seed lots from the field, germination was lowest (84%) in the seed lot with the highest level of bacterial infestation (55%) and ranged from 84-98%. No adverse effect on germination was observed from artificially infested seeds for any bacterial concentration and method of infiltration when compared to a non-infested control. Germination in laboratory assays for artificially infested seeds ranged from 82-100%. In controlled environment assays, 2.5 % were PCR positive for the pathogen, and in the greenhouse assays, no infected seedlings were detected. From these experiments, X. euvesicatoria does not appear to adversely influence germination. The lowest rate of germination from field collected seed may be due to contamination with multiple pathogens and saprophytic organisms as no effect of artificial bacterial seed infestation in the laboratory on germination was observed. No evidence of systemic movement from seed to seedling was observed in the greenhouse assays; however, in the controlled environment assays, some seedlings were PCR positive. Additional experiments are underway with green fluorescent protein-expressing isolates to further characterize seed to seedling transmission of the bacterial leaf spot pathogen in tomato.

Keywords: bacterial leaf spot, seed germination, tomato, Xanthomonas euvesicatoria

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213 Synthesis of Functionalized-2-Aryl-2, 3-Dihydroquinoline-4(1H)-Ones via Fries Rearrangement of Azetidin-2-Ones

Authors: Parvesh Singh, Vipan Kumar, Vishu Mehra

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Quinoline-4-ones represent an important class of heterocyclic scaffolds that have attracted significant interest due to their various biological and pharmacological activities. This heterocyclic unit also constitutes an integral component in drugs used for the treatment of neurodegenerative diseases, sleep disorders and in antibiotics viz. norfloxacin and ciprofloxacin. The synthetic accessibility and possibility of fictionalization at varied positions in quinoline-4-ones exemplifies an elegant platform for the designing of combinatorial libraries of functionally enriched scaffolds with a range of pharmacological profles. They are also considered to be attractive precursors for the synthesis of medicinally imperative molecules such as non-steroidal androgen receptor antagonists, antimalarial drug Chloroquine and martinellines with antibacterial activity. 2-Aryl-2,3-dihydroquinolin-4(1H)-ones are present in many natural and non-natural compounds and are considered to be the aza-analogs of favanones. The β-lactam class of antibiotics is generally recognized to be a cornerstone of human health care due to the unparalleled clinical efficacy and safety of this type of antibacterial compound. In addition to their biological relevance as potential antibiotics, β-lactams have also acquired a prominent place in organic chemistry as synthons and provide highly efficient routes to a variety of non-protein amino acids, such as oligopeptides, peptidomimetics, nitrogen-heterocycles, as well as biologically active natural and unnatural products of medicinal interest such as indolizidine alkaloids, paclitaxel, docetaxel, taxoids, cyptophycins, lankacidins, etc. A straight forward route toward the synthesis of quinoline-4-ones via the triflic acid assisted Fries rearrangement of N-aryl-βlactams has been reported by Tepe and co-workers. The ring expansion observed in this case was solely attributed to the inherent ring strain in β-lactam ring because -lactam failed to undergo rearrangement under reaction conditions. Theabovementioned protocol has been recently extended by our group for the synthesis of benzo[b]-azocinon-6-ones via a tandem Michael addition–Fries rearrangement of sorbyl anilides as well as for the single-pot synthesis of 2-aryl-quinolin-4(3H)-ones through the Fries rearrangement of 3-dienyl-βlactams. In continuation with our synthetic endeavours with the β-lactam ring and in view of the lack of convenient approaches for the synthesis of C-3 functionalized quinolin-4(1H)-ones, the present work describes the single-pot synthesis of C-3 functionalized quinolin-4(1H)-ones via the trific acid promoted Fries rearrangement of C-3 vinyl/isopropenyl substituted β-lactams. In addition, DFT calculations and MD simulations were performed to investigate the stability profles of synthetic compounds.

Keywords: dihydroquinoline, fries rearrangement, azetidin-2-ones, quinoline-4-ones

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212 Modeling Sorption and Permeation in the Separation of Benzene/ Cyclohexane Mixtures through Styrene-Butadiene Rubber Crosslinked Membranes

Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay

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Pervaporation (PV), a membrane-based separation technology, has gained much attention because of its energy saving capability and low-cost, especially for separation of azeotropic or close-boiling liquid mixtures. There are two crucial issues for industrial application of pervaporation process. The first is developing membrane material and tailoring membrane structure to obtain high pervaporation performances. The second is modeling pervaporation transport to better understand of the above-mentioned structure–pervaporation relationship. Many models were proposed to predict the mass transfer process, among them, solution-diffusion model is most widely used in describing pervaporation transport including preferential sorption, diffusion and evaporation steps. For modeling pervaporation transport, the permeation flux, which depends on the solubility and diffusivity of components in the membrane, should be obtained first. Traditionally, the solubility was calculated according to the Flory–Huggins theory. Separation of the benzene (Bz)/cyclohexane (Cx) mixture is industrially significant. Numerous papers have been focused on the Bz/Cx system to assess the PV properties of membrane materials. Membranes with both high permeability and selectivity are desirable for practical application. Several new polymers have been prepared to get both high permeability and selectivity. Styrene-butadiene rubbers (SBR), dense membranes cross-linked by chloromethylation were used in the separation of benzene/cyclohexane mixtures. The impact of chloromethylation reaction as a new method of cross-linking SBR on the pervaporation performance have been reported. In contrast to the vulcanization with sulfur, the cross-linking takes places on styrene units of polymeric chains via a methylene bridge. The partial pervaporative (PV) fluxes of benzene/cyclohexane mixtures in styrene-butadiene rubber (SBR) were predicted using Fick's first law. The predicted partial fluxes and the PV separation factor agreed well with the experimental data by integrating Fick's law over the benzene concentration. The effects of feed concentration and operating temperature on the predicted permeation flux by this proposed model are investigated. The predicted permeation fluxes are in good agreement with experimental data at lower benzene concentration in feed, but at higher benzene concentration, the model overestimated permeation flux. The predicted and experimental permeation fluxes all increase with operating temperature increasing. Solvent sorption levels for benzene/ cyclohexane mixtures in a SBR membrane were determined experimentally. The results showed that the solvent sorption levels were strongly affected by the feed composition. The Flory- Huggins equation generates higher R-square coefficient for the sorption selectivity.

Keywords: benzene, cyclohexane, pervaporation, permeation, sorption modeling, SBR

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211 Obtaining Composite Cotton Fabric by Cyclodextrin Grafting

Authors: U. K. Sahin, N. Erdumlu, C. Saricam, I. Gocek, M. H. Arslan, H. Acikgoz-Tufan, B. Kalav

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Finishing is an important part of fabric processing with which a wide range of features are imparted to greige or colored fabrics for various end-uses. Especially, by the addition or impartation of nano-scaled particles to the fabric structure composite fabrics, a kind of composite materials can be acquired. Composite materials, generally shortened as composites or in other words composition materials, are engineered or naturally occurring materials made from two or more component materials with significantly different physical, mechanical or chemical characteristics remaining separate and distinctive at the macroscopic or microscopic scale within the end product structure. Therefore, the technique finishing which is one of the fundamental methods to be applied on fabrics for obtainment of composite fabrics with many functionalities was used in the current study with the same purpose. However, regardless of the finishing materials applied, the efficient life of finished product on offering desired feature is low, since the durability of finishes on the material is limited. Any increase in durability of these finishes on textiles would enhance the life of use for textiles, which will result in happier users. Therefore, in this study, since higher durability was desired for the finishing materials fixed on the fabrics, nano-scaled hollow structured cyclodextrins were chemically imparted by grafting to the structure of conventional cotton fabrics by the help of finishing technique in order to be fixed permanently. By this way, a processed and functionalized base fabric having potential to be treated in the subsequent processes with many different finishing agents and nanomaterials could be obtained. Henceforth, this fabric can be used as a multi-functional fabric due to the encapturing ability of cyclodextrins to molecules/particles via physical/chemical means. In this study, scoured and rinsed woven bleached plain weave 100% cotton fabrics were utilized because textiles made of cotton are the most demanded textile products in the textile market by the textile consumers in daily life. Cotton fabric samples were immersed in treating baths containing β-cyclodextrin and 1,2,3,4-butanetetracarboxylic acid and to reduce the curing temperature the catalyst sodium hypophosphite monohydrate was used. All impregnated fabric samples were pre-dried. The reaction of grafting was performed in dry state. The treated and cured fabric samples were rinsed with warm distilled water and dried. The samples were dried for 4 h and weighed before and after finishing and rinsing. Stability and durability of β-cyclodextrins on fabric surface against external factors such as washing as well as strength of functionalized fabric in terms of tensile and tear strength were tested. Presence and homogeneity of distribution of β-cyclodextrins on fabric surface were characterized.

Keywords: cotton fabric, cyclodextrine, improved durability, multifunctional composite textile

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210 Pathogenic Escherichia Coli Strains and Their Antibiotic Susceptibility Profiles in Cases of Child Diarrhea at Addis Ababa University, College of Health Sciences, Tikur Anbessa Specialized Hospital, Addis Ababa, Ethiopia

Authors: Benyam Zenebe, Tesfaye Sisay, Gurja Belay, Workabeba Abebe

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Background: The prevalence and antibiogram of pathogenic E. coli strains, which cause diarrhea vary from region to region, and even within countries in the same geographical area. In Ethiopia, diagnostic approaches to E. coli induced diarrhea in children less than five years of age are not standardized. The aim of this study was to determine the involvement of pathogenic E. coli strains in child diarrhea and determine the antibiograms of the isolates in children less than 5 years of age with diarrhea at Addis Ababa University College of Health Sciences TikurAnbessa Specialized Hospital, Addis Ababa, Ethiopia. Methods: A purposive study that included 98 diarrheic children less than five years of age was conducted at Addis Ababa University College of Health Sciences, TikurAnbessa Specialized Hospital, Addis Ababa, Ethiopia to detect pathogenic E. coli biotypes. Stool culture was used to identify presumptive E. coliisolates. Presumptive isolates were confirmed by biochemical tests, and antimicrobial susceptibility tests were performed on confirmed E. coli isolates by the disk diffusion method. DNA was extracted from confirmed isolates by a heating method and subjected to Polymerase Chain Reaction or the presence of virulence genes. Amplified PCR products were analyzed by agarose gel electrophoresis. Data were collected on child demographics and clinical conditions using administered questionnaires. The prevalence of E. coli strains from the total diarrheic children, and the prevalence of pathogenic strains from total E. coli isolates along with their susceptibility profiles; the distribution of pathogenic E.coli biotypes among different age groups and between the sexes were determined by using descriptive statistics. Result: Out of 98 stool specimens collected from diarrheic children less than 5 years of age, 75 presumptive E. coli isolates were identified by culture; further confirmation by biochemical tests showed that only 56 of the isolates were E. coli; 29 of the isolates were found in male children and 27 of them in female children. Out of the 58 isolates of E. coli, 25 pathotypes belonging to different classes of pathogenic strains: STEC, EPEC, EHEC, EAEC were detected by using the PCR technique. Pathogenic E. coli exhibited high rates of antibiotic resistance to many of the antibiotics tested. Moreover, they exhibited multiple drug resistance. Conclusion: This study found that the isolation rate of E. coli and the involvement of antibiotic-resistant pathogenic E. coli in diarrheic children is prominent, and hence focus should be given on the diagnosis and antimicrobial sensitivity testing of pathogenic E. coli at Addis Ababa University College of Health Sciences TikurAnbessa Specialized Hospital. Among antibiotics tested, Cefotitan could be a drug of choice to treat E. coli.

Keywords: antibiotic susceptibility profile, children, diarrhea, E. coli, pathogenic

Procedia PDF Downloads 234
209 Evaluation of the Cytotoxicity and Cellular Uptake of a Cyclodextrin-Based Drug Delivery System for Cancer Therapy

Authors: Caroline Mendes, Mary McNamara, Orla Howe

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Drug delivery systems are proposed for use in cancer treatment to specifically target cancer cells and deliver a therapeutic dose without affecting normal cells. For that purpose, the use of folate receptors (FR) can be considered a key strategy, since they are commonly over-expressed in cancer cells. In this study, cyclodextrins (CD) have being used as vehicles to target FR and deliver the chemotherapeutic drug, methotrexate (MTX). CDs have the ability to form inclusion complexes, in which molecules of suitable dimensions are included within their cavities. Here, β-CD has been modified using folic acid so as to specifically target the FR. Thus, this drug delivery system consists of β-CD, folic acid and MTX (CDEnFA:MTX). Cellular uptake of folic acid is mediated with high affinity by folate receptors while the cellular uptake of antifolates, such as MTX, is mediated with high affinity by the reduced folate carriers (RFCs). This study addresses the gene (mRNA) and protein expression levels of FRs and RFCs in the cancer cell lines CaCo-2, SKOV-3, HeLa, MCF-7, A549 and the normal cell line BEAS-2B, quantified by real-time polymerase chain reaction (real-time PCR) and flow cytometry, respectively. From that, four cell lines with different levels of FRs, were chosen for cytotoxicity assays of MTX and CDEnFA:MTX using the MTT assay. Real-time PCR and flow cytometry data demonstrated that all cell lines ubiquitously express moderate levels of RFC. These experiments have also shown that levels of FR protein in CaCo-2 cells are high, while levels in SKOV-3, HeLa and MCF-7 cells are moderate. A549 and BEAS-2B cells express low levels of FR protein. FRs are highly expressed in all the cancer cell lines analysed when compared to the normal cell line BEAS-2B. The cell lines CaCo-2, MCF-7, A549 and BEAS-2B were used in the cell viability assays. 48 hours treatment with the free drug and the complex resulted in IC50 values of 93.9 µM ± 15.2 and 56.0 µM ± 4.0 for CaCo-2 for free MTX and CDEnFA:MTX respectively, 118.2 µM ± 16.8 and 97.8 µM ± 12.3 for MCF-7, 36.4 µM ± 6.9 and 75.0 µM ± 10.5 for A549 and 132.6 µM ± 16.1 and 288.1 µM ± 26.3 for BEAS-2B. These results demonstrate that free MTX is more toxic towards cell lines expressing low levels of FR, such as the BEAS-2B. More importantly, these results demonstrate that the inclusion complex CDEnFA:MTX showed greater cytotoxicity than the free drug towards the high FR expressing CaCo-2 cells, indicating that it has potential to target this receptor, enhancing the specificity and the efficiency of the drug. The use of cell imaging by confocal microscopy has allowed visualisation of FR targeting in cancer cells, as well as the identification of the interlisation pathway of the drug. Hence, the cellular uptake and internalisation process of this drug delivery system is being addressed.

Keywords: cancer treatment, cyclodextrins, drug delivery, folate receptors, reduced folate carriers

Procedia PDF Downloads 311
208 Carbonyl Iron Particles Modified with Pyrrole-Based Polymer and Electric and Magnetic Performance of Their Composites

Authors: Miroslav Mrlik, Marketa Ilcikova, Martin Cvek, Josef Osicka, Michal Sedlacik, Vladimir Pavlinek, Jaroslav Mosnacek

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Magnetorheological elastomers (MREs) are a unique type of materials consisting of two components, magnetic filler, and elastomeric matrix. Their properties can be tailored upon application of an external magnetic field strength. In this case, the change of the viscoelastic properties (viscoelastic moduli, complex viscosity) are influenced by two crucial factors. The first one is magnetic performance of the particles and the second one is off-state stiffness of the elastomeric matrix. The former factor strongly depends on the intended applications; however general rule is that higher magnetic performance of the particles provides higher MR performance of the MRE. Since magnetic particles possess low stability properties against temperature and acidic environment, several methods how to improve these drawbacks have been developed. In the most cases, the preparation of the core-shell structures was employed as a suitable method for preservation of the magnetic particles against thermal and chemical oxidations. However, if the shell material is not single-layer substance, but polymer material, the magnetic performance is significantly suppressed, due to the in situ polymerization technique, when it is very difficult to control the polymerization rate and the polymer shell is too thick. The second factor is the off-state stiffness of the elastomeric matrix. Since the MR effectivity is calculated as the relative value of the elastic modulus upon magnetic field application divided by elastic modulus in the absence of the external field, also the tuneability of the cross-linking reaction is highly desired. Therefore, this study is focused on the controllable modification of magnetic particles using a novel monomeric system based on 2-(1H-pyrrol-1-yl)ethyl methacrylate. In this case, the short polymer chains of different chain lengths and low polydispersity index will be prepared, and thus tailorable stability properties can be achieved. Since the relatively thin polymer chains will be grafted on the surface of magnetic particles, their magnetic performance will be affected only slightly. Furthermore, also the cross-linking density will be affected, due to the presence of the short polymer chains. From the application point of view, such MREs can be utilized for, magneto-resistors, piezoresistors or pressure sensors especially, when the conducting shell on the magnetic particles will be created. Therefore, the selection of the pyrrole-based monomer is very crucial and controllably thin layer of conducting polymer can be prepared. Finally, such composite particle consisting of magnetic core and conducting shell dispersed in elastomeric matrix can find also the utilization in shielding application of electromagnetic waves.

Keywords: atom transfer radical polymerization, core-shell, particle modification, electromagnetic waves shielding

Procedia PDF Downloads 211
207 Effect of Maturation on the Characteristics and Physicochemical Properties of Banana and Its Starch

Authors: Chien-Chun Huang, P. W. Yuan

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Banana is one of the important fruits which constitute a valuable source of energy, vitamins and minerals and an important food component throughout the world. The fruit ripening and maturity standards vary from country to country depending on the expected shelf life of market. During ripening there are changes in appearance, texture and chemical composition of banana. The changes of component of banana during ethylene-induced ripening are categorized as nutritive values and commercial utilization. The objectives of this study were to investigate the changes of chemical composition and physicochemical properties of banana during ethylene-induced ripening. Green bananas were harvested and ripened by ethylene gas at low temperature (15℃) for seven stages. At each stage, banana was sliced and freeze-dried for banana flour preparation. The changes of total starch, resistant starch, chemical compositions, physicochemical properties, activity of amylase, polyphenolic oxidase (PPO) and phenylalanine ammonia lyase (PAL) of banana were analyzed each stage during ripening. The banana starch was isolated and analyzed for gelatinization properties, pasting properties and microscopic appearance each stage of ripening. The results indicated that the highest total starch and resistant starch content of green banana were 76.2% and 34.6%, respectively at the harvest stage. Both total starch and resistant starch content were significantly declined to 25.3% and 8.8%, respectively at the seventh stage. Soluble sugars content of banana increased from 1.21% at harvest stage to 37.72% at seventh stage during ethylene-induced ripening. Swelling power of banana flour decreased with the progress of ripening stage, but solubility increased. These results strongly related with the decreases of starch content of banana flour during ethylene-induced ripening. Both water insoluble and alcohol insoluble solids of banana flour decreased with the progress of ripening stage. Both activity of PPO and PAL increased, but the total free phenolics content decreased, with the increases of ripening stages. As ripening stage extended, the gelatinization enthalpy of banana starch significantly decreased from 15.31 J/g at the harvest stage to 10.55 J/g at the seventh stage. The peak viscosity and setback increased with the progress of ripening stages in the pasting properties of banana starch. The highest final viscosity, 5701 RVU, of banana starch slurry was found at the seventh stage. The scanning electron micrograph of banana starch showed the shapes of banana starch appeared to be round and elongated forms, ranging in 10-50 μm at the harvest stage. As the banana closed to ripe status, some parallel striations were observed on the surface of banana starch granular which could be caused by enzyme reaction during ripening. These results inferred that the highest resistant starch was found in the green banana could be considered as a potential application of healthy foods. The changes of chemical composition and physicochemical properties of banana could be caused by the hydrolysis of enzymes during the ethylene-induced ripening treatment.

Keywords: maturation of banana, appearance, texture, soluble sugars, resistant starch, enzyme activities, physicochemical properties of banana starch

Procedia PDF Downloads 319
206 Assessment of the Properties of Microcapsules with Different Polymeric Shells Containing a Reactive Agent for their Suitability in Thermoplastic Self-healing Materials

Authors: Małgorzata Golonka, Jadwiga Laska

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Self-healing polymers are one of the most investigated groups of smart materials. As materials engineering has recently focused on the design, production and research of modern materials and future technologies, researchers are looking for innovations in structural, construction and coating materials. Based on available scientific articles, it can be concluded that most of the research focuses on the self-healing of cement, concrete, asphalt and anticorrosion resin coatings. In our study, a method of obtaining and testing the properties of several types of microcapsules for use in self-healing polymer materials was developed. A method to obtain microcapsules exhibiting various mechanical properties, especially compressive strength was developed. The effect was achieved by using various polymer materials to build the shell: urea-formaldehyde resin (UFR), melamine-formaldehyde resin (MFR), melamine-urea-formaldehyde resin (MUFR). Dicyclopentadiene (DCPD) was used as the core material due to the possibility of its polymerization according to the ring-opening olefin metathesis (ROMP) mechanism in the presence of a solid Grubbs catalyst showing relatively high chemical and thermal stability. The ROMP of dicyclopentadiene leads to a polymer with high impact strength, high thermal resistance, good adhesion to other materials and good chemical and environmental resistance, so it is potentially a very promising candidate for the self-healing of materials. The capsules were obtained by condensation polymerization of formaldehyde with urea, melamine or copolymerization with urea and melamine in situ in water dispersion, with different molar ratios of formaldehyde, urea and melamine. The fineness of the organic phase dispersed in water, and consequently the size of the microcapsules, was regulated by the stirring speed. In all cases, to establish such synthesis conditions as to obtain capsules with appropriate mechanical strength. The microcapsules were characterized by determining the diameters and their distribution and measuring the shell thickness using digital optical microscopy and scanning electron microscopy, as well as confirming the presence of the active substance in the core by FTIR and SEM. Compression tests were performed to determine mechanical strength of the microcapsules. The highest repeatability of microcapsule properties was obtained for UFR resin, while the MFR resin had the best mechanical properties. The encapsulation efficiency of MFR was much lower compared to UFR, though. Therefore, capsules with a MUFR shell may be the optimal solution. The chemical reaction between the active substance present in the capsule core and the catalyst placed outside the capsules was confirmed by FTIR spectroscopy. The obtained autonomous repair systems (microcapsules + catalyst) were introduced into polyethylene in the extrusion process and tested for the self-repair of the material.

Keywords: autonomic self-healing system, dicyclopentadiene, melamine-urea-formaldehyde resin, microcapsules, thermoplastic materials

Procedia PDF Downloads 47
205 Development and Total Error Concept Validation of Common Analytical Method for Quantification of All Residual Solvents Present in Amino Acids by Gas Chromatography-Head Space

Authors: A. Ramachandra Reddy, V. Murugan, Prema Kumari

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Residual solvents in Pharmaceutical samples are monitored using gas chromatography with headspace (GC-HS). Based on current regulatory and compendial requirements, measuring the residual solvents are mandatory for all release testing of active pharmaceutical ingredients (API). Generally, isopropyl alcohol is used as the residual solvent in proline and tryptophan; methanol in cysteine monohydrate hydrochloride, glycine, methionine and serine; ethanol in glycine and lysine monohydrate; acetic acid in methionine. In order to have a single method for determining these residual solvents (isopropyl alcohol, ethanol, methanol and acetic acid) in all these 7 amino acids a sensitive and simple method was developed by using gas chromatography headspace technique with flame ionization detection. During development, no reproducibility, retention time variation and bad peak shape of acetic acid peaks were identified due to the reaction of acetic acid with the stationary phase (cyanopropyl dimethyl polysiloxane phase) of column and dissociation of acetic acid with water (if diluent) while applying temperature gradient. Therefore, dimethyl sulfoxide was used as diluent to avoid these issues. But most the methods published for acetic acid quantification by GC-HS uses derivatisation technique to protect acetic acid. As per compendia, risk-based approach was selected as appropriate to determine the degree and extent of the validation process to assure the fitness of the procedure. Therefore, Total error concept was selected to validate the analytical procedure. An accuracy profile of ±40% was selected for lower level (quantitation limit level) and for other levels ±30% with 95% confidence interval (risk profile 5%). The method was developed using DB-Waxetr column manufactured by Agilent contains 530 µm internal diameter, thickness: 2.0 µm, and length: 30 m. A constant flow of 6.0 mL/min. with constant make up mode of Helium gas was selected as a carrier gas. The present method is simple, rapid, and accurate, which is suitable for rapid analysis of isopropyl alcohol, ethanol, methanol and acetic acid in amino acids. The range of the method for isopropyl alcohol is 50ppm to 200ppm, ethanol is 50ppm to 3000ppm, methanol is 50ppm to 400ppm and acetic acid 100ppm to 400ppm, which covers the specification limits provided in European pharmacopeia. The accuracy profile and risk profile generated as part of validation were found to be satisfactory. Therefore, this method can be used for testing of residual solvents in amino acids drug substances.

Keywords: amino acid, head space, gas chromatography, total error

Procedia PDF Downloads 150
204 Fuel Cells Not Only for Cars: Technological Development in Railways

Authors: Marita Pigłowska, Beata Kurc, Paweł Daszkiewicz

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Railway vehicles are divided into two groups: traction (powered) vehicles and wagons. The traction vehicles include locomotives (line and shunting), railcars (sometimes referred to as railbuses), and multiple units (electric and diesel), consisting of several or a dozen carriages. In vehicles with diesel traction, fuel energy (petrol, diesel, or compressed gas) is converted into mechanical energy directly in the internal combustion engine or via electricity. In the latter case, the combustion engine generator produces electricity that is then used to drive the vehicle (diesel-electric drive or electric transmission). In Poland, such a solution dominates both in heavy linear and shunting locomotives. The classic diesel drive is available for the lightest shunting locomotives, railcars, and passenger diesel multiple units. Vehicles with electric traction do not have their own source of energy -they use pantographs to obtain electricity from the traction network. To determine the competitiveness of the hydrogen propulsion system, it is essential to understand how it works. The basic elements of the construction of a railway vehicle drive system that uses hydrogen as a source of traction force are fuel cells, batteries, fuel tanks, traction motors as well as main and auxiliary converters. The compressed hydrogen is stored in tanks usually located on the roof of the vehicle. This resource is supplemented with the use of specialized infrastructure while the vehicle is stationary. Hydrogen is supplied to the fuel cell, where it oxidizes. The effect of this chemical reaction is electricity and water (in two forms -liquid and water vapor). Electricity is stored in batteries (so far, lithium-ion batteries are used). Electricity stored in this way is used to drive traction motors and supply onboard equipment. The current generated by the fuel cell passes through the main converter, whose task is to adjust it to the values required by the consumers, i.e., batteries and the traction motor. The work will attempt to construct a fuel cell with unique electrodes. This research is a trend that connects industry with science. The first goal will be to obtain hydrogen on a large scale in tube furnaces, to thoroughly analyze the obtained structures (IR), and to apply the method in fuel cells. The second goal is to create low-energy energy storage and distribution station for hydrogen and electric vehicles. The scope of the research includes obtaining a carbon variety and obtaining oxide systems on a large scale using a tubular furnace and then supplying vehicles. Acknowledgments: This work is supported by the Polish Ministry of Science and Education, project "The best of the best! 4.0", number 0911/MNSW/4968 – M.P. and grant 0911/SBAD/2102—B.K.

Keywords: railway, hydrogen, fuel cells, hybrid vehicles

Procedia PDF Downloads 189
203 Innovative Food Related Modification of the Day-Night Task Demonstrates Impaired Inhibitory Control among Patients with Binge-Purge Eating Disorder

Authors: Sigal Gat-Lazer, Ronny Geva, Dan Ramon, Eitan Gur, Daniel Stein

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Introduction: Eating disorders (ED) are common psychopathologies which involve distorted body image and eating disturbances. Binge-purge eating disorders (B/P ED) are characterized by repetitive events of binge eating followed by purges. Patients with B/P ED behavior may be seen as impulsive especially when relate to food stimulation and affective conditions. The current study included innovative modification of the day-night task targeted to assess inhibitory control among patients with B/P ED. Methods: This prospective study included 50 patients with B/P ED during acute phase of illness (T1) upon their admission to specialized ED department in tertiary center. 34 patients repeated the study towards discharge to ambulatory care (T2). Treatment effect was evaluated by BMI and emotional questionnaires regarding depression and anxiety by the Beck Depression Inventory and State Trait Anxiety Inventory questionnaires. Control group included 36 healthy controls with matched demographic parameters who performed both T1 and T2 assessments. The current modification is based on the emotional day-night task (EDNT) which involves five emotional stimulation added to the sun and moon pictures presented to participants. In the current study, we designed the food-emotional modification day night task (F-EDNT) food stimulations of egg and banana which resemble the sun and moon, respectively, in five emotional states (angry, sad, happy, scrambled and neutral). During this computerized task, participants were instructed to push on “day” bottom in response to moon and banana stimulations and on “night” bottom when sun and egg were presented. Accuracy (A) and reaction time (RT) were evaluated and compared between EDNT and F-EDNT as a reflection of participants’ inhibitory control. Results: Patients with B/P ED had significantly improved BMI, depression and anxiety scores on T2 compared to T1 (all p<0.001). Task performance was similar among patients and controls in the EDNT without significant A or RT differences in both T1 and T2. On F-EDNT during T1, B/P ED patients had significantly reduced accuracy in 4/5 emotional stimulation compared to controls: angry (73±25% vs. 84±15%, respectively), sad (69±25% vs. 80±18%, respectively), happy (73±24% vs. 82±18%, respectively) and scrambled (74±24% vs. 84±13%, respectively, all p<0.05). Additionally, patients’ RT to food stimuli was significantly faster compared to neutral ones, in both cry and neutral emotional stimulations (356±146 vs. 400±141 and 378±124 vs. 412±116 msec, respectively, p<0.05). These significant differences between groups as a function of stimulus type were diminished on T2. Conclusion: Having to process food related content, in particular in emotional context seems to be impaired in patients with B/P ED during the acute phase of their illness and elicits greater impulsivity. Innovative modification using such procedures seem to be sensitive to patients’ illness phase and thus may be implemented during screening and follow up through the clinical management of these patients.

Keywords: binge purge eating disorders, day night task modification, eating disorders, food related stimulations

Procedia PDF Downloads 382
202 Physical Contact Modulation of Macrophage-Mediated Anti-Inflammatory Response in Osteoimmune Microenvironment by Pollen-Like Nanoparticles

Authors: Qing Zhang, Janak L. Pathak, Macro N. Helder, Richard T. Jaspers, Yin Xiao

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Introduction: Nanomaterial-based bone regeneration is greatly influenced by the immune microenvironment. Tissue-engineered nanomaterials mediate the inflammatory response of macrophages to regulate bone regeneration. Silica nanoparticles have been widely used in tissue engineering-related preclinical studies. However, the effect of topological features on the surface of silica nanoparticles on the immune response of macrophages remains unknown. Purposes: The aims of this research are to compare the influences of normal and pollen-like silica nano-surface topography on macrophage immune responses and to obtain insight into their potential regulatory mechanisms. Method: Macrophages (RAW 264.7 cells) were exposed to mesoporous silica nanoparticles with normal morphology (MSNs) and pollen-like morphology (PMSNs). RNA-seq, RT-qPCR, and LSCM were used to assess the changes in expression levels of immune response-related genes and proteins. SEM and TEM were executed to evaluate the contact and adherence of silica nanoparticles by macrophages. For the assessment of the immunomodulation-mediated osteogenic potential, BMSCs were cultured with conditioned medium (CM) from LPS pre-stimulated macrophage cultures treated with MSNs or PMSNs. Osteoimmunomodulatory potential of MSNs and PMSNs in vivo was tested in a mouse cranial bone osteolysis model. Results: The results of the RNA-seq, RT-qPCR, and LSCM assays showed that PMSNs inhibited the expression of pro-inflammatory genes and proteins in macrophages. SEM images showed distinct macrophage membrane surface binding patterns of MSNs and PMSNs. MSNs were more evenly dispersed across the macrophage cell membrane, while PMSNs were aggregated. PMSNs-induced macrophage anti-inflammatory response was associated with upregulation of the cell surface receptor CD28 and inhibition of ERK phosphorylation. TEM images showed that both MSNs and PMSNs could be phagocytosed by macrophages, and inhibiting nanoparticle phagocytosis did not affect the expression of anti-inflammatory genes and proteins. Moreover, PMSNs-induced conditioned medium from macrophages enhanced BMP-2 expression and osteogenic differentiation mBMSCs. Similarly, PMSNs prevented LPS-induced bone resorption via downregulation of inflammatory reaction. Conclusions: PMSNs can promote bone regeneration by modulating osteoimmunological processes through surface topography. The study offers insights into how surface physical contact cues can modulate the regulation of osteoimmunology and provides a basis for the application of nanoparticles with pollen-like morphology to affect immunomodulation in bone tissue engineering and regeneration.

Keywords: physical contact, osteoimmunology, macrophages, silica nanoparticles, surface morphology, membrane receptor, osteogenesis, inflammation

Procedia PDF Downloads 61
201 Study of the Kinetics of Formation of Carboxylic Acids Using Ion Chromatography during Oxidation Induced by Rancimat of the Oleic Acid, Linoleic Acid, Linolenic Acid, and Biodiesel

Authors: Patrícia T. Souza, Marina Ansolin, Eduardo A. C. Batista, Antonio J. A. Meirelles, Matthieu Tubino

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Lipid oxidation is a major cause of the deterioration of the quality of the biodiesel, because the waste generated damages the engines. Among the main undesirable effects are the increase of viscosity and acidity, leading to the formation of insoluble gums and sediments which cause the blockage of fuel filters. The auto-oxidation is defined as the spontaneous reaction of atmospheric oxygen with lipids. Unsaturated fatty acids are usually the components affected by such reactions. They are present as free fatty acids, fatty esters and glycerides. To determine the oxidative stability of biodiesels, through the induction period, IP, the Rancimat method is used, which allows continuous monitoring of the induced oxidation process of the samples. During the oxidation of the lipids, volatile organic acids are produced as byproducts, in addition, other byproducts, including alcohols and carbonyl compounds, may be further oxidized to carboxylic acids. By the methodology developed in this work using ion chromatography, IC, analyzing the water contained in the conductimetric vessel, were quantified organic anions of carboxylic acids in samples subjected to oxidation induced by Rancimat. The optimized chromatographic conditions were: eluent water:acetone (80:20 v/v) with 0.5 mM sulfuric acid; flow rate 0.4 mL min-1; injection volume 20 µL; eluent suppressor 20 mM LiCl; analytical curve from 1 to 400 ppm. The samples studied were methyl biodiesel from soybean oil and unsaturated fatty acids standards: oleic, linoleic and linolenic. The induced oxidation kinetics curves were constructed by analyzing the water contained in the conductimetric vessels which were removed, each one, from the Rancimat apparatus at prefixed intervals of time. About 3 g of sample were used under the conditions of 110 °C and air flow rate of 10 L h-1. The water of each conductimetric Rancimat measuring vessel, where the volatile compounds were collected, was filtered through a 0.45 µm filter and analyzed by IC. Through the kinetic data of the formation of the organic anions of carboxylic acids, the formation rates of the same were calculated. The observed order of the rates of formation of the anions was: formate >>> acetate > hexanoate > valerate for the oleic acid; formate > hexanoate > acetate > valerate for the linoleic acid; formate >>> valerate > acetate > propionate > butyrate for the linolenic acid. It is possible to suppose that propionate and butyrate are obtained mainly from linolenic acid and that hexanoate is originated from oleic and linoleic acid. For the methyl biodiesel the order of formation of anions was: formate >>> acetate > valerate > hexanoate > propionate. According to the total rate of formation these anions produced during the induced degradation of the fatty acids can be assigned the order of reactivity: linolenic acid > linoleic acid >>> oleic acid.

Keywords: anions of carboxylic acids, biodiesel, ion chromatography, oxidation

Procedia PDF Downloads 475
200 3D Nanostructured Assembly of 2D Transition Metal Chalcogenide/Graphene as High Performance Electrocatalysts

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

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Design and development of highly efficient, inexpensive, and long-term stable earth-abundant electrocatalysts hold tremendous promise for hydrogen evolution reaction (HER) in water electrolysis. The 2D transition metal dichalcogenides, especially molybdenum disulfide attracted a great deal of interests due to its high electrocatalytic activity. However, due to its poor electrical conductivity and limited exposed active sites, the performance of these catalysts is limited. In this context, a facile and scalable synthesis method for fabrication nanostructured electrocatalysts composed 3D graphene porous aerogels supported with MoS₂ and WS₂ is highly desired. Here we developed a highly active and stable electrocatalyst catalyst for the HER by growing it into a 3D porous architecture on conducting graphene. The resulting nanohybrids were thoroughly investigated by means of several characterization techniques to understand structure and properties. Moreover, the HER performance of these 3D catalysts is expected to greatly improve in compared to other, well-known catalysts which mainly benefits from the improved electrical conductivity of the by graphene and porous structures of the support. This technologically scalable process can afford efficient electrocatalysts for hydrogen evolution reactions (HER) and hydrodesulfurization catalysts for sulfur-rich petroleum fuels. Owing to the lower cost and higher performance, the resulting materials holds high potential for various energy and catalysis applications. In typical hydrothermal method, sonicated GO aqueous dispersion (5 mg mL⁻¹) was mixed with ammonium tetrathiomolybdate (ATTM) and tungsten molybdate was treated in a sealed Teflon autoclave at 200 ◦C for 4h. After cooling, a black solid macroporous hydrogel was recovered washed under running de-ionized water to remove any by products and metal ions. The obtained hydrogels were then freeze-dried for 24 h and was further subjected to thermal annealing driven crystallization at 600 ◦C for 2h to ensure complete thermal reduction of RGO into graphene and formation of highly crystalline MoS₂ and WoS₂ phases. The resulting 3D nanohybrids were characterized to understand the structure and properties. The SEM-EDS clearly reveals the formation of highly porous material with a uniform distribution of MoS₂ and WS₂ phases. In conclusion, a novice strategy for fabrication of 3D nanostructured MoS₂-WS₂/graphene is presented. The characterizations revealed that the in-situ formed promoters uniformly dispersed on to few layered MoS₂¬-WS₂ nanosheets that are well-supported on graphene surface. The resulting 3D hybrids hold high promise as potential electrocatalyst and hydrodesulfurization catalyst.

Keywords: electrocatalysts, graphene, transition metal chalcogenide, 3D assembly

Procedia PDF Downloads 138
199 Inhibition of the Activity of Polyphenol Oxidase Enzyme Present in Annona muricata and Musa acuminata by the Experimentally Identified Natural Anti-Browning Agents

Authors: Michelle Belinda S. Weerawardana, Gobika Thiripuranathar, Priyani A. Paranagama

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Most of fresh vegetables and fruits available in the retail markets undergo a physiological disorder in its appearance and coloration, which indeed discourages consumer purchase. A loss of millions of dollars yearly to the food industry had been due to this pronounced color reaction called Enzymatic Browning which is driven due to the catalytic activity by an oxidoreductase enzyme, polyphenol oxidase (PPO). The enzyme oxidizes the phenolic compounds which are abundantly available in fruits and vegetables as substrates into quinones, which could react with proteins in its surrounding to generate black pigments, called melanins, which are highly UV-active compounds. Annona muricata (Katu anoda) and Musa acuminata (Ash plantains) is a fruit and a vegetable consumed by Sri Lankans widely due to their high nutritional values, medicinal properties and economical importance. The objective of the present study was to evaluate and determine the effective natural anti-browning inhibitors that could prevent PPO activity in the selected fruit and vegetable. Enzyme extracts from Annona muricata (Katu anoda) and Musa acuminata (Ash plantains), were prepared by homogenizing with analytical grade acetone, and pH of each enzyme extract was maintained at 7.0 using a phosphate buffer. The extracts of inhibitors were prepared using powdered ginger rhizomes and essential oil from the bark of Cinnamomum zeylanicum. Water extracts of ginger were prepared and the essential oil from Ceylon cinnamon bark was extracted using steam distillation method. Since the essential oil is not soluble in water, 0.1µl of cinnamon bark oil was mixed with 0.1µl of Triton X-100 emulsifier and 5.00 ml of water. The effect of each inhibitor on the PPO activity was investigated using catechol (0.1 mol dm-3) as the substrate and two samples of enzyme extracts prepared. The dosages of the prepared Cinnamon bark oil, and ginger (2 samples) which were used to measure the activity were 0.0035 g/ml, 0.091 g/ml and 0.087 g/ml respectively. The measurements of the inhibitory activity were obtained at a wavelength of 525 nm using the UV-visible spectrophotometer. The results evaluated thus revealed that % inhibition observed with cinnamon bark oil, and ginger for Annona muricata was 51.97%, and 60.90% respectively. The effects of cinnamon bark oil, and ginger extract on PPO activity of Musa acuminata were 49.51%, and 48.10%. The experimental findings thus revealed that Cinnamomum zeylanicum bark oil was a more effective inhibitor for PPO enzyme present in Musa acuminata and ginger was effective for PPO enzyme present in Annona muricata. Overall both the inhibitors were proven to be more effective towards the activities of PPO enzyme present in both samples. These inhibitors can thus be corroborated as effective, natural, non-toxic, anti-browning extracts, which when added to the above fruit and vegetable will increase the shelf life and also the acceptance of the product by the consumers.

Keywords: anti-browning agent, enzymatic browning, inhibitory activity, polyphenol oxidase

Procedia PDF Downloads 276
198 Synergy Surface Modification for High Performance Li-Rich Cathode

Authors: Aipeng Zhu, Yun Zhang

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The growing grievous environment problems together with the exhaustion of energy resources put urgent demands for developing high energy density. Considering the factors including capacity, resource and environment, Manganese-based lithium-rich layer-structured cathode materials xLi₂MnO₃⋅(1-x)LiMO₂ (M = Ni, Co, Mn, and other metals) are drawing increasing attention due to their high reversible capacities, high discharge potentials, and low cost. They are expected to be one type of the most promising cathode materials for the next-generation Li-ion batteries (LIBs) with higher energy densities. Unfortunately, their commercial applications are hindered with crucial drawbacks such as poor rate performance, limited cycle life and continuous falling of the discharge potential. With decades of extensive studies, significant achievements have been obtained in improving their cyclability and rate performances, but they cannot meet the requirement of commercial utilization till now. One major problem for lithium-rich layer-structured cathode materials (LLOs) is the side reaction during cycling, which leads to severe surface degradation. In this process, the metal ions can dissolve in the electrolyte, and the surface phase change can hinder the intercalation/deintercalation of Li ions and resulting in low capacity retention and low working voltage. To optimize the LLOs cathode material, the surface coating is an efficient method. Considering the price and stability, Al₂O₃ was used as a coating material in the research. Meanwhile, due to the low initial Coulombic efficiency (ICE), the pristine LLOs was pretreated by KMnO₄ to increase the ICE. The precursor was prepared by a facile coprecipitation method. The as-prepared precursor was then thoroughly mixed with Li₂CO₃ and calcined in air at 500℃ for 5h and 900℃ for 12h to produce Li₁.₂[Ni₀.₂Mn₀.₆]O₂ (LNMO). The LNMO was then put into 0.1ml/g KMnO₄ solution stirring for 3h. The resultant was filtered and washed with water, and dried in an oven. The LLOs obtained was dispersed in Al(NO₃)₃ solution. The mixture was lyophilized to confer the Al(NO₃)₃ was uniformly coated on LLOs. After lyophilization, the LLOs was calcined at 500℃ for 3h to obtain LNMO@LMO@ALO. The working electrodes were prepared by casting the mixture of active material, acetylene black, and binder (polyvinglidene fluoride) dissolved in N-methyl-2-pyrrolidone with a mass ratio of 80: 15: 5 onto an aluminum foil. The electrochemical performance tests showed that the multiple surface modified materials had a higher initial Coulombic efficiency (84%) and better capacity retention (91% after 100 cycles) compared with that of pristine LNMO (76% and 80%, respectively). The modified material suggests that the KMnO₄ pretreat and Al₂O₃ coating can increase the ICE and cycling stability.

Keywords: Li-rich materials, surface coating, lithium ion batteries, Al₂O₃

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197 Exploring the Motivations That Drive Paper Use in Clinical Practice Post-Electronic Health Record Adoption: A Nursing Perspective

Authors: Sinead Impey, Gaye Stephens, Lucy Hederman, Declan O'Sullivan

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Continued paper use in the clinical area post-Electronic Health Record (EHR) adoption is regularly linked to hardware and software usability challenges. Although paper is used as a workaround to circumvent challenges, including limited availability of a computer, this perspective does not consider the important role paper, such as the nurses’ handover sheet, play in practice. The purpose of this study is to confirm the hypothesis that paper use post-EHR adoption continues as paper provides both a cognitive tool (that assists with workflow) and a compensation tool (to circumvent usability challenges). Distinguishing the different motivations for continued paper-use could assist future evaluations of electronic record systems. Methods: Qualitative data were collected from three clinical care environments (ICU, general ward and specialist day-care) who used an electronic record for at least 12 months. Data were collected through semi-structured interviews with 22 nurses. Data were transcribed, themes extracted using an inductive bottom-up coding approach and a thematic index constructed. Findings: All nurses interviewed continued to use paper post-EHR adoption. While two distinct motivations for paper use post-EHR adoption were confirmed by the data - paper as a cognitive tool and paper as a compensation tool - further finding was that there was an overlap between the two uses. That is, paper used as a compensation tool could also be adapted to function as a cognitive aid due to its nature (easy to access and annotate) or vice versa. Rather than present paper persistence as having two distinctive motivations, it is more useful to describe it as presenting on a continuum with compensation tool and cognitive tool at either pole. Paper as a cognitive tool referred to pages such as nurses’ handover sheet. These did not form part of the patient’s record, although information could be transcribed from one to the other. Findings suggest that although the patient record was digitised, handover sheets did not fall within this remit. These personal pages continued to be useful post-EHR adoption for capturing personal notes or patient information and so continued to be incorporated into the nurses’ work. Comparatively, the paper used as a compensation tool, such as pre-printed care plans which were stored in the patient's record, appears to have been instigated in reaction to usability challenges. In these instances, it is expected that paper use could reduce or cease when the underlying problem is addressed. There is a danger that as paper affords nurses a temporary information platform that is mobile, easy to access and annotate, its use could become embedded in clinical practice. Conclusion: Paper presents a utility to nursing, either as a cognitive or compensation tool or combination of both. By fully understanding its utility and nuances, organisations can avoid evaluating all incidences of paper use (post-EHR adoption) as arising from usability challenges. Instead, suitable remedies for paper-persistence can be targeted at the root cause.

Keywords: cognitive tool, compensation tool, electronic record, handover sheet, nurse, paper persistence

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196 Development of Bilayer Coating System for Mitigating Corrosion of Offshore Wind Turbines

Authors: Adamantini Loukodimou, David Weston, Shiladitya Paul

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Offshore structures are subjected to harsh environments. It is documented that carbon steel needs protection from corrosion. The combined effect of UV radiation, seawater splash, and fluctuating temperatures diminish the integrity of these structures. In addition, the possibility of damage caused by floating ice, seaborne debris, and maintenance boats make them even more vulnerable. Their inspection and maintenance when far out in the sea are difficult, risky, and expensive. The most known method of mitigating corrosion of offshore structures is the use of cathodic protection. There are several zones in an offshore wind turbine. In the atmospheric zone, due to the lack of a continuous electrolyte (seawater) layer between the structure and the anode at all times, this method proves inefficient. Thus, the use of protective coatings becomes indispensable. This research focuses on the atmospheric zone. The conversion of commercially available and conventional paint (epoxy) system to an autonomous self-healing paint system via the addition of suitable encapsulated healing agents and catalyst is investigated in this work. These coating systems, which can self-heal when damaged, can provide a cost-effective engineering solution to corrosion and related problems. When the damage of the paint coating occurs, the microcapsules are designed to rupture and release the self-healing liquid (monomer), which then will react in the presence of the catalyst and solidify (polymerization), resulting in healing. The catalyst should be compatible with the system because otherwise, the self-healing process will not occur. The carbon steel substrate will be exposed to a corrosive environment, so the use of a sacrificial layer of Zn is also investigated. More specifically, the first layer of this new coating system will be TSZA (Thermally Sprayed Zn85/Al15) and will be applied on carbon steel samples with dimensions 100 x 150 mm after being blasted with alumina (size F24) as part of the surface preparation. Based on the literature, it corrodes readily, so one additional paint layer enriched with microcapsules will be added. Also, the reaction and the curing time are of high importance in order for this bilayer system of coating to work successfully. For the first experiments, polystyrene microcapsules loaded with 3-octanoyltio-1-propyltriethoxysilane were conducted. Electrochemical experiments such as Electrochemical Impedance Spectroscopy (EIS) confirmed the corrosion inhibiting properties of the silane. The diameter of the microcapsules was about 150-200 microns. Further experiments were conducted with different reagents and methods in order to obtain diameters of about 50 microns, and their self-healing properties were tested in synthetic seawater using electrochemical techniques. The use of combined paint/electrodeposited coatings allows for further novel development of composite coating systems. The potential for the application of these coatings in offshore structures will be discussed.

Keywords: corrosion mitigation, microcapsules, offshore wind turbines, self-healing

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195 Predicting Long-Term Performance of Concrete under Sulfate Attack

Authors: Elakneswaran Yogarajah, Toyoharu Nawa, Eiji Owaki

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Cement-based materials have been using in various reinforced concrete structural components as well as in nuclear waste repositories. The sulfate attack has been an environmental issue for cement-based materials exposed to sulfate bearing groundwater or soils, and it plays an important role in the durability of concrete structures. The reaction between penetrating sulfate ions and cement hydrates can result in swelling, spalling and cracking of cement matrix in concrete. These processes induce a reduction of mechanical properties and a decrease of service life of an affected structure. It has been identified that the precipitation of secondary sulfate bearing phases such as ettringite, gypsum, and thaumasite can cause the damage. Furthermore, crystallization of soluble salts such as sodium sulfate crystals induces degradation due to formation and phase changes. Crystallization of mirabilite (Na₂SO₄:10H₂O) and thenardite (Na₂SO₄) or their phase changes (mirabilite to thenardite or vice versa) due to temperature or sodium sulfate concentration do not involve any chemical interaction with cement hydrates. Over the past couple of decades, an intensive work has been carried out on sulfate attack in cement-based materials. However, there are several uncertainties still exist regarding the mechanism for the damage of concrete in sulfate environments. In this study, modelling work has been conducted to investigate the chemical degradation of cementitious materials in various sulfate environments. Both internal and external sulfate attack are considered for the simulation. In the internal sulfate attack, hydrate assemblage and pore solution chemistry of co-hydrating Portland cement (PC) and slag mixing with sodium sulfate solution are calculated to determine the degradation of the PC and slag-blended cementitious materials. Pitzer interactions coefficients were used to calculate the activity coefficients of solution chemistry at high ionic strength. The deterioration mechanism of co-hydrating cementitious materials with 25% of Na₂SO₄ by weight is the formation of mirabilite crystals and ettringite. Their formation strongly depends on sodium sulfate concentration and temperature. For the external sulfate attack, the deterioration of various types of cementitious materials under external sulfate ingress is simulated through reactive transport model. The reactive transport model is verified with experimental data in terms of phase assemblage of various cementitious materials with spatial distribution for different sulfate solution. Finally, the reactive transport model is used to predict the long-term performance of cementitious materials exposed to 10% of Na₂SO₄ for 1000 years. The dissolution of cement hydrates and secondary formation of sulfate-bearing products mainly ettringite are the dominant degradation mechanisms, but not the sodium sulfate crystallization.

Keywords: thermodynamic calculations, reactive transport, radioactive waste disposal, PHREEQC

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194 Rt-Pcr Negative COVID-19 Infection in a Bodybuilding Competitor Using Anabolic Steroids: A Case Report

Authors: Mariana Branco, Nahida Sobrino, Cristina Neves, Márcia Santos, Afonso Granja, João Rosa Oliveira, Joana Costa, Luísa Castro Leite

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This case reports a COVID-19 infection in an unvaccinated adult man with no history of COVID-19 and no relevant clinical history besides anabolic steroid use, undergoing weaning with tamoxifen after a bodybuilding competition. The patient presented a 4cm cervical mass 3 weeks after COVID-19 infection in his cohabitants. He was otherwise asymptomatic and tested negative to multiple RT-PCR tests. Nevertheless, the IgG COVID-19 antibody was positive, suggesting the previous infection. This report raises a potential link between anabolic steroid use and atypical COVID-19 onset. Objectives: The goals of this paper are to raise a potential link between anabolic steroid use and atypical COVID-19 onset but also to report an uncommon case of COVID-19 infection with consecutive negative gold standard tests. Methodology: The authors used CARE guidelines for case report writing. Introduction: This case reports a COVID-19 infection case in an unvaccinated adult man, with multiple serial negative reverse transcription polymerase chain reaction (RT-PCR) test results, presenting with single cervical lymphadenopathy. Although the association between COVID-19 and lymphadenopathy is well established, there are no cases with this presentation, and consistently negative RT-PCR tests have been reported. Methodologies: The authors used CARE guidelines for case report writing. Case presentation: This case reports a 28-year-old Caucasian man with no previous history of COVID-19 infection or vaccination and no relevant clinical history besides anabolic steroid use undergoing weaning with tamoxifendue to participation in a bodybuilding competition. He visits his primary care physician because of a large (4 cm) cervical lump, present for 3 days prior to the consultation. There was a positive family history for COVID-19 infection 3 weeks prior to the visit, during which the patient cohabited with the infected family members. The patient never had any previous clinical manifestation of COVID-19 infection and, despite multiple consecutive RT-PCR testing, never tested positive. The patient was treated with an NSAID and a broad-spectrum antibiotic, with little to no effect. Imagiological testing was performed via a cervical ultrasound, followed by a needle biopsy for histologic analysis. Serologic testing for COVID-19 immunity was conducted, revealing a positive Anti-SARS-CoV-2 IgG (Spike S1) antibody, suggesting the previous infection, given the unvaccinated status of our patient Conclusion: In patients with a positive epidemiologic context and cervical lymphadenopathy, physicians should still consider COVID-19 infection as a differential diagnosis, despite negative PCR testing. This case also raises a potential link between anabolic steroid use and atypical COVID-19 onset, never before reported in scientific literature.

Keywords: COVID-19, cervical lymphadenopathy, anabolic steroids, primary care

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193 Tuberculosis (TB) and Lung Cancer

Authors: Asghar Arif

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Lung cancer has been recognized as one of the greatest common cancers, causing the annual mortality rate of about 1.2 million people in the world. Lung cancer is the most prevalent cancer in men and the third-most common cancer among women (after breast and digestive cancers).Recent evidences have shown the inflammatory process as one of the potential factors of cancer. Tuberculosis (TB), pneumonia, and chronic bronchitis are among the most important inflammation-inducing factors in the lungs, among which TB has a more profound role in the emergence of cancer.TB is one of the important mortality factors throughout the world, and 205,000 death cases are reported annually due to this disease. Chronic inflammation and fibrosis due to TB can induce genetic mutation and alternations. Parenchyma tissue of lung is involved in both diseases of TB and lung cancer, and continuous cough in lung cancer, morphological vascular variations, lymphocytosis processes, and generation of immune system mediators such as interleukins, are all among the factors leading to the hypothesis regarding the role of TB in lung cancer Some reports have shown that the induction of necrosis and apoptosis or TB reactivation, especially in patients with immune-deficiency, may result in increasing IL-17 and TNF_α, which will either decrease P53 activity or increase the expression of Bcl-2, decrease Bax-T, and cause the inhibition of caspase-3 expression due to decreasing the expression of mitochondria cytochrome oxidase. It has been also indicated that following the injection of BCG vaccine, the host immune system will be reinforced, and in particular, the rates of gamma interferon, nitric oxide, and interleukin-2 are increased. Therefore, CD4 + lymphocyte function will be improved, and the person will be immune against cancer.Numerous prospective studies have so far been conducted on the role of TB in lung cancer, and it seems that this disease is effective in that particular cancer.One of the main challenges of lung cancer is its correct and timely diagnosis. Unfortunately, clinical symptoms (such as continuous cough, hemoptysis, weight loss, fever, chest pain, dyspnea, and loss of appetite) and radiological images are similar in TB and lung cancer. Therefore, anti-TB drugs are routinely prescribed for the patients in the countries with high prevalence of TB, like Pakistan. Regarding the similarity in clinical symptoms and radiological findings of lung cancer, proper diagnosis is necessary for TB and respiratory infections due to nontuberculousmycobacteria (NTM). Some of the drug resistive TB cases are, in fact, lung cancer or NTM lung infections. Acid-fast staining and histological study of phlegm and bronchial washing, culturing and polymerase chain reaction TB are among the most important solutions for differential diagnosis of these diseases. Briefly, it is assumed that TB is one of the risk factors for cancer. Numerous studies have been conducted in this regard throughout the world, and it has been observed that there is a significant relationship between previous TB infection and lung cancer. However, to prove this hypothesis, further and more extensive studies are required. In addition, as the clinical symptoms and radiological findings of TB, lung cancer, and non-TB mycobacteria lung infections are similar, they can be misdiagnosed as TB.

Keywords: TB and lung cancer, TB people, TB servivers, TB and HIV aids

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192 Cytotoxic Effects of Ag/TiO2 Nanoparticles on the Unicellular Organism Paramecium tetraurelia

Authors: Juan Bernal-Martinez, Zoe Quinones-Jurado, Miguel Waldo-Mendoza, Elias Perez

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Introduction and Objective: Ag-TiO2 nanoparticles (NP) have been characterized as effective antibacterial compounds against E. aureous, E. coli, Salmonella and others. Because these nanoparticles have been used in plastic-food containers, there is a concern about the toxicity of Ag-TiO2 NP for higher organisms from protozoan, invertebrates, and mammals. The objective of this study is to evaluate the cytotoxic effect of Ag-TiO2 NP on the survival and swimming behavior of the unicellular organism Paramecium tetraurelia. Material and Methods: Preparation of metallic silver on TiO2 surface was based on chemical reduction route of AgNO3. Aqueous suspension of TiO2 nanoparticles was preparing by adding 5 g of TiO2 to 250 ml of deionized water and followed by sonication for 10 min. The required amount of AgNO3 solutions was added to TiO2 suspension, maintaining heating and stirring. Silver concentration was 0.5, 1.5, 5.0, 25, 35 and 45 % w/w versus TiO2. Paramecium tetraurelia (Carolina Biological, Cat. # 131560) was used as a biological preparation. It was cultured in artificial culture media made as follows: Stigmasterol 5 mg/ml of ethanol, Caseaminoacids 0.3 gr/lt.; KCl 4mM; CaCl2 1mM; MgCl2 100uM and MOPS 1mM, pH 7.3. This media was inoculated with Enterobacter-sp. Paramecium was concentrated after 24 hours of incubation by centrifugation. The pellet of cells was resuspended in 4.1.1 solution prepared as follows (in mM): KCl, 4 mM; CaCl2, 1mM and Trizma, 1mM; pH 7.3. Transmission electron microscopy (TEM) studies were performed to evaluate the appropriate dispersion and topographic distribution AgNPs deposited on TiO2. The experimental solutions were prepared as follows: 50 mg of Polyvinyhlpirolidone were added to 5 ml of 4.1.1. solution. Then, 50 mg of powder 25-Ag-TiO2 was added, mixing for 10 min and sonicated for 60 min. Survival of Paramecium and possible toxic effects after 25-Ag-TiO2 treatment was observed through an inverted microscope. The Paramecium swimming behavior and possible dead cells were recorded for periods of approximately 20-50 seconds by using a digital USB camera adapted to the microscope. Results and Discussion: TEM micrographs demonstrated the topographic distribution of AgNPs deposited on TiO2. 25Ag-TiO2 NP was efficiently dissolved and dispersed in 4.1.1 solution at concentrations from 0.1, 1 and 10 mg/ml. When Paramecium were treated with 25Ag-TiO2 NP at 100 ug/ml, it was observed that cells started swimming backwards. This backward swimming behavior is the typical avoiding reaction of the ciliate in response to a noxious stimulus. After 10 min of incubation, it was observed that Paramecium stopped swimming backwards and exploited. We can argue that this toxic effect of 25Ag-TiO2 NP is probably due to the calcium influx and calcium accumulation during the long-lasting swimming backwards. Conclusions: Here we have demonstrated that 25Ag-TiO2 NP has a specific toxic effect on an organism higher than bacteria such as the protozoan Paremecium. Probably these toxic phenomena could be expected to be observed in a higher organism such as invertebrates and mammals.

Keywords: Ag-TiO2, calcium permeability, cytotoxicity, paramecium

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