Search results for: sensory and chemical and microbiological analyses
Commenced in January 2007
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Edition: International
Paper Count: 8166

Search results for: sensory and chemical and microbiological analyses

156 A Brief Review on Doping in Sports and Performance-Enhancing Drugs

Authors: Zahra Mohajer, Afsaneh Soltani

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Doping is a major issue in competitive sports and is favored by vast groups of athletes. The feeling of being higher-ranking than others and gaining fame has caused many athletes to misuse drugs. The definition of doping is to use prohibited substances and/or methods that help physical or mental performances or both. Doping counts as the illegal use of chemical substances or drugs, excessive amounts of physiological substances to increase the performance at or out of competition or even the use of inappropriate medications to treat an injury to gain the ability to participate in a competition. The International Olympic Committee (IOC) and World Anti-Doping Agency (WADA) have forbidden these substances to ensure fair and equal competition and also the health of the competitors. As of 2004 WADA has published an international list of illegal substances used for doping, which is updated annually. In the process of the Genome Project scientists have gained the ability to treat numerous diseases by gene therapy, which may result in bodily performance increase and therefore a potential opportunity to misuse by some athletes. Gene doping is defined as the non-therapeutic direct and indirect genetic modifications using genetic materials that can improve the performances in sports events. Biosynthetic drugs are a form of indirect genetic engineering. The method can be performed in three ways such as injecting the DNA directly into the muscle, inserting the genetically engineered cells, or transferring the DNA using a virus as a vector. Erythropoietin is a hormone majorly released by the kidney and in small amounts by the liver. Its function is to stimulate the erythropoiesis and therefore the more production of red blood cells (RBC) which causes an increase in Hemoglobin (Hb). During this process, the oxygen delivery to muscles will increase, which will improve athletic performance and postpone exhaustion. There are ways to increase the oxygen transferred to muscles such as blood transfusion, stimulating the production of red blood cells by using Erythropoietin (EPO), and also using allosteric effectors of Hemoglobin. EPO can either be injected as a protein or can be inserted into the cells as the gene which encodes EPO. Adeno-associated viruses have been employed to deliver the EPO gene to the cells. Employing the genes that naturally exist in the human body such as the EPO gene can reduce the risk of detecting gene doping. The first research about blood doping was conducted in 1947. The study has shown that an increase in hematocrit (HCT) up to 55% following homologous transfusion makes it more unchallenging for the body to perform the exercise at the altitude. Thereafter athletes’ attraction to blood infusion escalated. Also, a study has demonstrated that by reinfusing their own blood 4 weeks after being drawn, three men have shown a rise in Hb level which improved the oxygen uptake, and a delay in exhaustion. The list of performance-enhancing drugs is published by WADA annually and includes the following drugs: anabolic agents, hormones, Beta-2 agonists, Beta-blockers, Diuretics, Stimulants, narcotics, cannabinoids, and corticosteroids.

Keywords: doping, PEDs, sports, WADA

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155 Polymer Composites Containing Gold Nanoparticles for Biomedical Use

Authors: Bozena Tyliszczak, Anna Drabczyk, Sonia Kudlacik-Kramarczyk, Agnieszka Sobczak-Kupiec

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Introduction: Nanomaterials become one of the leading materials in the synthesis of various compounds. This is a reason for the fact that nano-size materials exhibit other properties compared to their macroscopic equivalents. Such a change in size is reflected in a change in optical, electric or mechanical properties. Among nanomaterials, particular attention is currently directed into gold nanoparticles. They find application in a wide range of areas including cosmetology or pharmacy. Additionally, nanogold may be a component of modern wound dressings, which antibacterial activity is beneficial in the viewpoint of the wound healing process. Specific properties of this type of nanomaterials result in the fact that they may also be applied in cancer treatment. Studies on the development of new techniques of the delivery of drugs are currently an important research subject of many scientists. This is due to the fact that along with the development of such fields of science as medicine or pharmacy, the need for better and more effective methods of administering drugs is constantly growing. The solution may be the use of drug carriers. These are materials that combine with the active substance and lead it directly to the desired place. A role of such a carrier may be played by gold nanoparticles that are able to covalently bond with many organic substances. This allows the combination of nanoparticles with active substances. Therefore gold nanoparticles are widely used in the preparation of nanocomposites that may be used for medical purposes with special emphasis on drug delivery. Methodology: As part of the presented research, synthesis of composites was carried out. The mentioned composites consisted of the polymer matrix and gold nanoparticles that were introduced into the polymer network. The synthesis was conducted with the use of a crosslinking agent, and photoinitiator and the materials were obtained by means of the photopolymerization process. Next, incubation studies were conducted using selected liquids that simulated fluids are occurring in the human body. The study allows determining the biocompatibility of the tested composites in relation to selected environments. Next, the chemical structure of the composites was characterized as well as their sorption properties. Conclusions: Conducted research allowed for the preliminary characterization of prepared polymer composites containing gold nanoparticles in the viewpoint of their application for biomedical use. Tested materials were characterized by biocompatibility in tested environments. What is more, synthesized composites exhibited relatively high swelling capacity that is essential in the viewpoint of their potential application as drug carriers. During such an application, composite swells and at the same time releases from its interior introduced active substance; therefore, it is important to check the swelling ability of such material. Acknowledgements: The authors would like to thank The National Science Centre (Grant no: UMO - 2016/21/D/ST8/01697) for providing financial support to this project. This paper is based upon work from COST Action (CA18113), supported by COST (European Cooperation in Science and Technology).

Keywords: nanocomposites, gold nanoparticles, drug carriers, swelling properties

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154 An Economic Way to Toughen Poly Acrylic Acid Superabsorbent Polymer Using Hyper Branched Polymer

Authors: Nazila Dehbari, Javad Tavakoli, Yakani Kambu, Youhong Tang

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Superabsorbent hydrogels (SAP), as an enviro-sensitive material have been widely used for industrial and biomedical applications due to their unique structure and capabilities. Poor mechanical properties of SAPs - which is extremely related to their large volume change – count as a great weakness in adopting for high-tech applications. Therefore, improving SAPs’ mechanical properties via toughening methods by mixing different types of cross-linked polymer or introducing energy-dissipating mechanisms is highly focused. In this work, in order to change the intrinsic brittle character of commercialized Poly Acrylic Acid (here as SAP) to be semi-ductile, a commercial available highly branched tree-like dendritic polymers with numerous –OH end groups known as hyper-branched polymer (HB) has been added to PAA-SAP system in a single step, cost effective and environment friendly solvent casting method. Samples were characterized by FTIR, SEM and TEM and their physico-chemical characterization including swelling capabilities, hydraulic permeability, surface tension and thermal properties had been performed. Toughness energy, stiffness, elongation at breaking point, viscoelastic properties and samples extensibility were mechanical properties that had been performed and characterized as a function of samples lateral cracks’ length in different HB concentration. Addition of HB to PAA-SAP significantly improved mechanical and surface properties. Increasing equilibrium swelling ratio by about 25% had been experienced by the SAP-HB samples in comparison with SAPs; however, samples swelling kinetics remained without changes as initial rate of water uptake and equilibrium time haven’t been subjected to any changes. Thermal stability analysis showed that HB is participating in hybrid network formation while improving mechanical properties. Samples characterization by TEM showed that, the aggregated HB polymer binders into nano-spheres with diameter in range of 10–200 nm. So well dispersion in the SAP matrix occurred as it was predictable due to the hydrophilic character of the numerous hydroxyl groups at the end of HB which enhance the compatibility of HB with PAA-SAP. As the profused -OH groups in HB could react with -COOH groups in the PAA-SAP during the curing process, the formation of a 2D structure in the SAP-HB could be attributed to the strong interfacial adhesion between HB and the PAA-SAP matrix which hinders the activity of PAA chains (SEM analysis). FTIR spectra introduced new peaks at 1041 and 1121 cm-1 that attributed to the C–O(–OH) stretching hydroxyl and O–C stretching ester groups of HB polymer binder indicating the incorporation of HB polymer into the SAP structure. SAP-HB polymer has significant effects on the final mechanical properties. The brittleness of PAA hydrogels are decreased by introducing HB as the fracture energies of hydrogels increased from 8.67 to 26.67. PAA-HBs’ stretch ability enhanced about 10 folds while reduced as a function of different notches depth.

Keywords: superabsorbent polymer, toughening, viscoelastic properties, hydrogel network

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153 Numerical Analysis of NOₓ Emission in Staged Combustion for the Optimization of Once-Through-Steam-Generators

Authors: Adrien Chatel, Ehsan Askari Mahvelati, Laurent Fitschy

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Once-Through-Steam-Generators are commonly used in the oil-sand industry in the heavy fuel oil extraction process. They are composed of three main parts: the burner, the radiant and convective sections. Natural gas is burned through staged diffusive flames stabilized by the burner. The heat generated by the combustion is transferred to the water flowing through the piping system in the radiant and convective sections. The steam produced within the pipes is then directed to the ground to reduce the oil viscosity and allow its pumping. With the rapid development of the oil-sand industry, the number of OTSG in operation has increased as well as the associated emissions of environmental pollutants, especially the Nitrous Oxides (NOₓ). To limit the environmental degradation, various international environmental agencies have established regulations on the pollutant discharge and pushed to reduce the NOₓ release. To meet these constraints, OTSG constructors have to rely on more and more advanced tools to study and predict the NOₓ emission. With the increase of the computational resources, Computational Fluid Dynamics (CFD) has emerged as a flexible tool to analyze the combustion and pollutant formation process. Moreover, to optimize the burner operating condition regarding the NOx emission, field characterization and measurements are usually accomplished. However, these kinds of experimental campaigns are particularly time-consuming and sometimes even impossible for industrial plants with strict operation schedule constraints. Therefore, the application of CFD seems to be more adequate in order to provide guidelines on the NOₓ emission and reduction problem. In the present work, two different software are employed to simulate the combustion process in an OTSG, namely the commercial software ANSYS Fluent and the open source software OpenFOAM. RANS (Reynolds-Averaged Navier–Stokes) equations combined with the Eddy Dissipation Concept to model the combustion and closed by the k-epsilon model are solved. A mesh sensitivity analysis is performed to assess the independence of the solution on the mesh. In the first part, the results given by the two software are compared and confronted with experimental data as a mean to assess the numerical modelling. Flame temperatures and chemical composition are used as reference fields to perform this validation. Results show a fair agreement between experimental and numerical data. In the last part, OpenFOAM is employed to simulate several operating conditions, and an Emission Characteristic Map of the combustion system is generated. The sources of high NOₓ production inside the OTSG are pointed and correlated to the physics of the flow. CFD is, therefore, a useful tool for providing an insight into the NOₓ emission phenomena in OTSG. Sources of high NOₓ production can be identified, and operating conditions can be adjusted accordingly. With the help of RANS simulations, an Emission Characteristics Map can be produced and then be used as a guide for a field tune-up.

Keywords: combustion, computational fluid dynamics, nitrous oxides emission, once-through-steam-generators

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152 MANIFEST-2, a Global, Phase 3, Randomized, Double-Blind, Active-Control Study of Pelabresib (CPI-0610) and Ruxolitinib vs. Placebo and Ruxolitinib in JAK Inhibitor-Naïve Myelofibrosis Patients

Authors: Claire Harrison, Raajit K. Rampal, Vikas Gupta, Srdan Verstovsek, Moshe Talpaz, Jean-Jacques Kiladjian, Ruben Mesa, Andrew Kuykendall, Alessandro Vannucchi, Francesca Palandri, Sebastian Grosicki, Timothy Devos, Eric Jourdan, Marielle J. Wondergem, Haifa Kathrin Al-Ali, Veronika Buxhofer-Ausch, Alberto Alvarez-Larrán, Sanjay Akhani, Rafael Muñoz-Carerras, Yury Sheykin, Gozde Colak, Morgan Harris, John Mascarenhas

Abstract:

Myelofibrosis (MF) is characterized by bone marrow fibrosis, anemia, splenomegaly and constitutional symptoms. Progressive bone marrow fibrosis results from aberrant megakaryopoeisis and expression of proinflammatory cytokines, both of which are heavily influenced by bromodomain and extraterminal domain (BET)-mediated gene regulation and lead to myeloproliferation and cytopenias. Pelabresib (CPI-0610) is an oral small-molecule investigational inhibitor of BET protein bromodomains currently being developed for the treatment of patients with MF. It is designed to downregulate BET target genes and modify nuclear factor kappa B (NF-κB) signaling. MANIFEST-2 was initiated based on data from Arm 3 of the ongoing Phase 2 MANIFEST study (NCT02158858), which is evaluating the combination of pelabresib and ruxolitinib in Janus kinase inhibitor (JAKi) treatment-naïve patients with MF. Primary endpoint analyses showed splenic and symptom responses in 68% and 56% of 84 enrolled patients, respectively. MANIFEST-2 (NCT04603495) is a global, Phase 3, randomized, double-blind, active-control study of pelabresib and ruxolitinib versus placebo and ruxolitinib in JAKi treatment-naïve patients with primary MF, post-polycythemia vera MF or post-essential thrombocythemia MF. The aim of this study is to evaluate the efficacy and safety of pelabresib in combination with ruxolitinib. Here we report updates from a recent protocol amendment. The MANIFEST-2 study schema is shown in Figure 1. Key eligibility criteria include a Dynamic International Prognostic Scoring System (DIPSS) score of Intermediate-1 or higher, platelet count ≥100 × 10^9/L, spleen volume ≥450 cc by computerized tomography or magnetic resonance imaging, ≥2 symptoms with an average score ≥3 or a Total Symptom Score (TSS) of ≥10 using the Myelofibrosis Symptom Assessment Form v4.0, peripheral blast count <5% and Eastern Cooperative Oncology Group performance status ≤2. Patient randomization will be stratified by DIPSS risk category (Intermediate-1 vs Intermediate-2 vs High), platelet count (>200 × 10^9/L vs 100–200 × 10^9/L) and spleen volume (≥1800 cm^3 vs <1800 cm^3). Double-blind treatment (pelabresib or matching placebo) will be administered once daily for 14 consecutive days, followed by a 7 day break, which is considered one cycle of treatment. Ruxolitinib will be administered twice daily for all 21 days of the cycle. The primary endpoint is SVR35 response (≥35% reduction in spleen volume from baseline) at Week 24, and the key secondary endpoint is TSS50 response (≥50% reduction in TSS from baseline) at Week 24. Other secondary endpoints include safety, pharmacokinetics, changes in bone marrow fibrosis, duration of SVR35 response, duration of TSS50 response, progression-free survival, overall survival, conversion from transfusion dependence to independence and rate of red blood cell transfusion for the first 24 weeks. Study recruitment is ongoing; 400 patients (200 per arm) from North America, Europe, Asia and Australia will be enrolled. The study opened for enrollment in November 2020. MANIFEST-2 was initiated based on data from the ongoing Phase 2 MANIFEST study with the aim of assessing the efficacy and safety of pelabresib and ruxolitinib in JAKi treatment-naïve patients with MF. MANIFEST-2 is currently open for enrollment.

Keywords: CPI-0610, JAKi treatment-naïve, MANIFEST-2, myelofibrosis, pelabresib

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151 Globalization of Pesticide Technology and Sustainable Agriculture

Authors: Gagandeep Kaur

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The pesticide industry is a big supplier of agricultural inputs. The uses of pesticides control weeds, fungal diseases, etc., which causes of yield losses in agricultural production. In agribusiness and agrichemical industry, Globalization of markets, competition and innovation are the dominant trends. By the tradition of increasing the productivity of agro-systems through generic, universally applicable technologies, innovation in the agrichemical industry is limited. The marketing of technology of agriculture needs to deal with some various trends such as locally-organized forces that envision regionalized sustainable agriculture in the future. Agricultural production has changed dramatically over the past century. Before World War second agricultural production was featured as a low input of money, high labor, mixed farming and low yields. Although mineral fertilizers were applied already in the second half of the 19th century, most f the crops were restricted by local climatic, geological and ecological conditions. After World War second, in the period of reconstruction, political and socioeconomic pressure changed the nature of agricultural production. For a growing population, food security at low prices and securing farmer income at acceptable levels became political priorities. Current agricultural policy the new European common agricultural policy is aimed to reduce overproduction, liberalization of world trade and the protection of landscape and natural habitats. Farmers have to increase the quality of their productivity and they have to control costs because of increased competition from the world market. Pesticides should be more effective at lower application doses, less toxic and not pose a threat to groundwater. There is a big debate taking place about how and whether to mitigate the intensive use of pesticides. This debate is about the future of agriculture which is sustainable agriculture. This is possible by moving away from conventional agriculture. Conventional agriculture is featured as high inputs and high yields. The use of pesticides in conventional agriculture implies crop production in a wide range. To move away from conventional agriculture is possible through the gradual adoption of less disturbing and polluting agricultural practices at the level of the cropping system. For a healthy environment for crop production in the future there is a need for the maintenance of chemical, physical or biological properties. There is also required to minimize the emission of volatile compounds in the atmosphere. Companies are limiting themselves to a particular interpretation of sustainable development, characterized by technological optimism and production-maximizing. So the main objective of the paper will present the trends in the pesticide industry and in agricultural production in the era of Globalization. The second objective is to analyze sustainable agriculture. Companies of pesticides seem to have identified biotechnology as a promising alternative and supplement to the conventional business of selling pesticides. The agricultural sector is in the process of transforming its conventional mode of operation. Some experts give suggestions to farmers to move towards precision farming and some suggest engaging in organic farming. The methodology of the paper will be historical and analytical. Both primary and secondary sources will be used.

Keywords: globalization, pesticides, sustainable development, organic farming

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150 Effect of Organics on Radionuclide Partitioning in Nuclear Fuel Storage Ponds

Authors: Hollie Ashworth, Sarah Heath, Nick Bryan, Liam Abrahamsen, Simon Kellet

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Sellafield has a number of fuel storage ponds, some of which have been open to the air for a number of decades. This has caused corrosion of the fuel resulting in a release of some activity into solution, reduced water clarity, and accumulation of sludge at the bottom of the pond consisting of brucite (Mg(OH)2) and other uranium corrosion products. Both of these phases are also present as colloidal material. 90Sr and 137Cs are known to constitute a small volume of the radionuclides present in the pond, but a large fraction of the activity, thus they are most at risk of challenging effluent discharge limits. Organic molecules are known to be present also, due to the ponds being open to the air, with occasional algal blooms restricting visibility further. The contents of the pond need to be retrieved and safely stored, but dealing with such a complex, undefined inventory poses a unique challenge. This work aims to determine and understand the sorption-desorption interactions of 90Sr and 137Cs to brucite and uranium phases, with and without the presence of organic molecules from chemical degradation and bio-organisms. The influence of organics on these interactions has not been widely studied. Partitioning of these radionuclides and organic molecules has been determined through LSC, ICP-AES/MS, and UV-vis spectrophotometry coupled with ultrafiltration in both binary and ternary systems. Further detailed analysis into the surface and bonding environment of these components is being investigated through XAS techniques and PHREEQC modelling. Experiments were conducted in CO2-free or N2 atmosphere across a high pH range in order to best simulate conditions in the pond. Humic acid used in brucite systems demonstrated strong competition against 90Sr for the brucite surface regardless of the order of addition of components. Variance of pH did have a small effect, however this range (10.5-11.5) is close to the pHpzc of brucite, causing the surface to buffer the solution pH towards that value over the course of the experiment. Sorption of 90Sr to UO2 obeyed Ho’s rate equation and demonstrated a slow second-order reaction with respect to the sharing of valence electrons from the strontium atom, with the initial rate clearly dependent on pH, with the equilibrium concentration calculated at close to 100% sorption. There was no influence of humic acid seen when introduced to these systems. Sorption of 137Cs to UO3 was significant, with more than 95% sorbed in just over 24 hours. Again, humic acid showed no influence when introduced into this system. Both brucite and uranium based systems will be studied with the incorporation of cyanobacterial cultures harvested at different stages of growth. Investigation of these systems provides insight into, and understanding of, the effect of organics on radionuclide partitioning to brucite and uranium phases at high pH. The majority of sorption-desorption work for radionuclides has been conducted at neutral to acidic pH values, and mostly without organics. These studies are particularly important for the characterisation of legacy wastes at Sellafield, with a view to their safe retrieval and storage.

Keywords: caesium, legacy wastes, organics, sorption-desorption, strontium, uranium

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149 Assessment of Tidal Influence in Spatial and Temporal Variations of Water Quality in Masan Bay, Korea

Authors: S. J. Kim, Y. J. Yoo

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Slack-tide sampling was carried out at seven stations at high and low tides for a tidal cycle, in summer (7, 8, 9) and fall (10), 2016 to determine the differences of water quality according to tides in Masan Bay. The data were analyzed by Pearson correlation and factor analysis. The mixing state of all the water quality components investigated is well explained by the correlation with salinity (SAL). Turbidity (TURB), dissolved silica (DSi), nitrite and nitrate nitrogen (NNN) and total nitrogen (TN), which find their way into the bay from the streams and have no internal source and sink reaction, showed a strong negative correlation with SAL at low tide, indicating the property of conservative mixing. On the contrary, in summer and fall, dissolved oxygen (DO), hydrogen sulfide (H2S) and chemical oxygen demand with KMnO4 (CODMn) of the surface and bottom water, which were sensitive to an internal source and sink reaction, showed no significant correlation with SAL at high and low tides. The remaining water quality parameters showed a conservative or a non-conservative mixing pattern depending on the mixing characteristics at high and low tides, determined by the functional relationship between the changes of the flushing time and the changes of the characteristics of water quality components of the end-members in the bay. Factor analysis performed on the concentration difference data sets between high and low tides helped in identifying the principal latent variables for them. The concentration differences varied spatially and temporally. Principal factors (PFs) scores plots for each monitoring situation showed high associations of the variations to the monitoring sites. At sampling station 1 (ST1), temperature (TEMP), SAL, DSi, TURB, NNN and TN of the surface water in summer, TEMP, SAL, DSi, DO, TURB, NNN, TN, reactive soluble phosphorus (RSP) and total phosphorus (TP) of the bottom water in summer, TEMP, pH, SAL, DSi, DO, TURB, CODMn, particulate organic carbon (POC), ammonia nitrogen (AMN), NNN, TN and fecal coliform (FC) of the surface water in fall, TEMP, pH, SAL, DSi, H2S, TURB, CODMn, AMN, NNN and TN of the bottom water in fall commonly showed up as the most significant parameters and the large concentration differences between high and low tides. At other stations, the significant parameters showed differently according to the spatial and temporal variations of mixing pattern in the bay. In fact, there is no estuary that always maintains steady-state flow conditions. The mixing regime of an estuary might be changed at any time from linear to non-linear, due to the change of flushing time according to the combination of hydrogeometric properties, inflow of freshwater and tidal action, And furthermore the change of end-member conditions due to the internal sinks and sources makes the occurrence of concentration difference inevitable. Therefore, when investigating the water quality of the estuary, it is necessary to take a sampling method considering the tide to obtain average water quality data.

Keywords: conservative mixing, end-member, factor analysis, flushing time, high and low tide, latent variables, non-conservative mixing, slack-tide sampling, spatial and temporal variations, surface and bottom water

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148 Chemical Composition and Insecticidal Activity of Three Essential Oil and Beauvericin Nanogel on Plodia Interpunctella (Lepidoptera: Pyralidae)

Authors: Magda Mahmoud Amin Sabbour, El-Sayed H. Shaurub

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The Indian meal moth Plodia interpunctella (Hübner) (Lepidoptera: Pyralidae), of stored grain pests which destroy the seed completely. Their larval stages feed on the nutrient germinating kernels part found in the seeds grain. This leads to a reduction causing a badness to seed germination and seed viability. It controlled by many insecticides which pollute and cusses a harmful diseases to human being. Three tested oils were evaluated on this target pests. Plant extracts, essential oils and medical oils are materials which used to control many stored pests. Plant oils extracts have a lower effects on parasites and predators and not pollute the medium. By using the apparatus gas chromatography flame ionization detector gas chromatography–analysis of three essential oil tested. This research was point to explore and appreciation the activity of three oils and nano gel Beauvericin against P. interpunctella in the laboratory conditions and in the store conditions. The three essential oil tested proved that, percentage of α-Pinene recoded 7.76, 7.72 and 6.66 for C. cyminum, A. squamosal and G. officinale respectively. The composition of the β-Pinene recoded 4.61, 8.92 and 30.63 for the corresponding oils tested. Results showed that after analytically the oils tested, the effective compound of C. cyminum oil are p-cyinene and Terpinene. Results obtained show that the LC50 recorded 125, 112, 55 and 20 ppm after P. interpunctella treated with medical oils of Guaiacum officinale, Annona squamosa, Cuminum cyminum and Beauvericin 3% respectively. The accumulative mortality of P. interpunctella after treated with A.squamosa oil-loaded nanogels which showed that it is the highest oils from infestations recoded when the seed treated with 3% after 48 days, the accumulations obtained 44% at followed by 24 after24 days of storage. Results, cleared that the seed protection by G. officinale recorded 40% at concentrations of 3% after 48 days of storage seeds. C. cyminum was the highest mortality by 98, at concentrations 3%. The highest seed protection proved after C. cyminum oil-loaded nanogels 14% followed by G. officinale 29% and A.squamosa 44%.when the seeds treated with Beauvericin 3%. Results of this work cleared that the essential medical oils have a useful action effect on target insects. Plant essential and medical oils, their active ingredient have potentially high bioactivity against on P. interpunctella. The medical and essential oils incorporation and usage the nano-formulation release stopped the highly degradation vaporization and the increasing in the constancy, and save the lower effectiveness of the dosage/application. The research results proved that the highest seed protection obtained after C. cyminum oil-loaded nanogels followed by G. officinale and A.squamosa. It could be complemented that P. interpunctella were more susceptible to medical oils loaded nanogel (MOLNs ) than medical oils only (MO). MOLNs had best lower amount of the residual activity than MO only. MOLNs might mend the insecticidal action of the medical oil tested by the slow effective release of the medical oils to control P. interpunctella mostly at the lower doses.

Keywords: Cuminum cyminum, annona squamosa, guaiacum officinale, beauvericin 3 %, plodia interpunctella

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147 Characterization of Potato Starch/Guar Gum Composite Film Modified by Ecofriendly Cross-Linkers

Authors: Sujosh Nandi, Proshanta Guha

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Synthetic plastics are preferred for food packaging due to high strength, stretch-ability, good water vapor and gas barrier properties, transparency and low cost. However, environmental pollution generated by these synthetic plastics is a major concern of modern human civilization. Therefore, use of biodegradable polymers as a substitute for synthetic non-biodegradable polymers are encouraged to be used even after considering drawbacks related to mechanical and barrier properties of the films. Starch is considered one of the potential raw material for the biodegradable polymer, encounters poor water barrier property and mechanical properties due to its hydrophilic nature. That apart, recrystallization of starch molecules occurs during aging which decreases flexibility and increases elastic modulus of the film. The recrystallization process can be minimized by blending of other hydrocolloids having similar structural compatibility, into the starch matrix. Therefore, incorporation of guar gum having a similar structural backbone, into the starch matrix can introduce a potential film into the realm of biodegradable polymer. However, hydrophilic nature of both starch and guar gum, water barrier property of the film is low. One of the prospective solution to enhance this could be modification of the potato starch/guar gum (PSGG) composite film using cross-linker. Over the years, several cross-linking agents such as phosphorus oxychloride, sodium trimetaphosphate, etc. have been used to improve water vapor permeability (WVP) of the films. However, these chemical cross-linking agents are toxic, expensive and take longer time to degrade. Therefore, naturally available carboxylic acid (tartaric acid, malonic acid, succinic acid, etc.) had been used as a cross-linker and found that water barrier property enhanced substantially. As per our knowledge, no works have been reported with tartaric acid and succinic acid as a cross-linking agent blended with the PSGG films. Therefore, the objective of the present study was to examine the changes in water vapor barrier property and mechanical properties of the PSGG films after cross-linked with tartaric acid (TA) and succinic acid (SA). The cross-linkers were blended with PSGG film-forming solution at four different concentrations (4, 8, 12 & 16%) and cast on teflon plate at 37°C for 20 h. From the fourier-transform infrared spectroscopy (FTIR) study of the developed films, a band at 1720cm-1 was observed which is attributed to the formation of ester group in the developed films. On the other hand, it was observed that tensile strength (TS) of the cross-linked film decreased compared to non-cross linked films, whereas strain at break increased by several folds. Moreover, the results depicted that tensile strength diminished with increasing the concentration of TA or SA and lowest TS (1.62 MPa) was observed for 16% SA. That apart, maximum strain at break was also observed for TA at 16% and the reason behind this could be a lesser degree of crystallinity of the TA cross-linked films compared to SA. However, water vapor permeability of succinic acid cross-linked film was reduced significantly, but it was enhanced significantly by addition of tartaric acid.

Keywords: cross linking agent, guar gum, organic acids, potato starch

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146 Fly-Ash/Borosilicate Glass Based Geopolymers: A Mechanical and Microstructural Investigation

Authors: Gianmarco Taveri, Ivo Dlouhy

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Geopolymers are well-suited materials to abate CO2 emission coming from the Portland cement production, and then replace them, in the near future, in building and other applications. The cost of production of geopolymers may be seen the only weakness, but the use of wastes as raw materials could provide a valid solution to this problem, as demonstrated by the successful incorporation of fly-ash, a by-product of thermal power plants, and waste glasses. Recycled glass in waste-derived geopolymers was lately employed as a further silica source. In this work we present, for the first time, the introduction of recycled borosilicate glass (BSG). BSG is actually a waste glass, since it derives from dismantled pharmaceutical vials and cannot be reused in the manufacturing of the original articles. Owing to the specific chemical composition (BSG is an ‘alumino-boro-silicate’), it was conceived to provide the key components of zeolitic networks, such as amorphous silica and alumina, as well as boria (B2O3), which may replace Al2O3 and contribute to the polycondensation process. The solid–state MAS NMR spectroscopy was used to assess the extent of boron oxide incorporation in the structure of geopolymers, and to define the degree of networking. FTIR spectroscopy was utilized to define the degree of polymerization and to detect boron bond vibration into the structure. Mechanical performance was tested by means of 3 point bending (flexural strength), chevron notch test (fracture toughness), compression test (compressive strength), micro-indentation test (Vicker’s hardness). Spectroscopy (SEM and Confocal spectroscopy) was performed on the specimens conducted to failure. FTIR showed a characteristic absorption band attributed to the stretching modes of tetrahedral boron ions, whose tetrahedral configuration is compatible to the reaction product of geopolymerization. 27Al NMR and 29Si NMR spectra were instrumental in understanding the extent of the reaction. 11B NMR spectroscopies evidenced a change of the trigonal boron (BO3) inside the BSG in favor of a quasi-total tetrahedral boron configuration (BO4). Thanks to these results, it was inferred that boron is part of the geopolymeric structure, replacing the Si in the network, similarly to the aluminum, and therefore improving the quality of the microstructure, in favor of a more cross-linked network. As expected, the material gained as much as 25% in compressive strength (45 MPa) compared to the literature, whereas no improvements were detected in flexural strength (~ 5 MPa) and superficial hardness (~ 78 HV). The material also exhibited a low fracture toughness (0.35 MPa*m1/2), with a tangible brittleness. SEM micrographies corroborated this behavior, showing a ragged surface, along with several cracks, due to the high presence of porosity and impurities, acting as preferential points for crack initiation. The 3D pattern of the surface fracture, following the confocal spectroscopy, evidenced an irregular crack propagation, whose proclivity was mainly, but not always, to follow the porosity. Hence, the crack initiation and propagation are largely unpredictable.

Keywords: borosilicate glass, characterization, fly-ash, geopolymerization

Procedia PDF Downloads 179
145 Oxidative Dehydrogenation and Hydrogenation of Malic Acid over Transition Metal Oxides

Authors: Gheorghiţa Mitran, Adriana Urdă, Mihaela Florea, Octavian Dumitru Pavel, Florentina Neaţu

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Oxidative dehydrogenation and hydrogenation reactions of L-malic acid are interesting ways for its transformation into valuable products, including oxaloacetic, pyruvic and malonic acids but also 1,4-butanediol and 1,2,4-butanetriol. Keto acids have a range of applicationsin many chemical syntheses as pharmaceuticals, food additives and cosmetics. 3-Hydroxybutyrolactone and 1,2,4-butanetriol are used for the synthesis of chiral pharmaceuticals and other fine chemicals, while 1,4-butanediol can be used for organic syntheses, such as polybutylene succinate (PBS), polybutylene terephthalate (PBT), and for production of tetrahydrofuran (THF). L-malic acid is a non-toxic and natural organic acid present in fruits, and it is the main component of wine alongside tartaric acid representing about 90% of the wine total acidity. Iron oxides dopped with cobalt (CoxFe3-xO4; x= 0; 0.05; 0.1; 0.15) were studied as catalysts in these reactions. There is no mention in the literature of non-noble transition metal catalysts for these reactions. The method used for catalysts preparation was coprecipitation, whileBET XRD, XPS, FTIR and UV-VIS spectroscopy were used for the physicochemical properties evaluation.TheXRD patterns revealed the presence of α-Fe2O3 rhombohedral hematite structure, with cobalt atoms well dispersed and embedded in this structure. The studied samples are highly crystalline, with a crystallite size ranged from 58 to 65 nm. The optical absorption properties were investigated using UV-Vis spectroscopy, emphasizing the presence of bands that correspond with the reported hematite nanoparticle. Likewise, the presence of bands corresponding to lattice vibration of hexagonal hematite structurehas been evidenced in DRIFT spectra. Oxidative dehydrogenation of malic acid was studied using as solvents for malic acid ethanol or water(2, 5 and 10% malic acid in 5 mL solvent)at room temperature, while the hydrogenation reaction was evaluated in water as solvent (5%), in the presence of 1% catalyst. The oxidation of malic acid into oxaloacetic acid is the first step, after that, oxaloacetic acid is rapidly decarboxylated to malonic acid or pyruvic acid, depending on the active site. The concentration of malic acid in solution, it, in turn, has an influence on conversionthis decreases when the concentration of malic acid in the solution is high. The spent catalysts after the oxidative dehydrogenation of malic acid in ethanol were characterized by DRIFT spectroscopy and the presence of oxaloacetic, pyruvic and malonicacids, along with unreacted malic acidwere observed on the surface. The increase of the ratio of Co/Fe on the surface has an influence on the malic acid conversion and on the pyruvic acid yield, while the yield of malonic acid is influenced by the percentage of iron on the surface (determined from XPS). Oxaloacetic acid yield reaches a maximumat one hour of reaction, being higher when ethanol is used as a solvent, after which it suddenly decreases. The hydrogenation of malic acid occurs by consecutive reactions with the production of 3-hydroxy-butyrolactone, 1,2,4-butanetriol and 1,4-butanediol. Malic acid conversion increases with cobalt loading increasing up to Co/Fe ratio of 0.1, after which it has a slight decrease, while the yield in 1,4-butanediol is directly proportional to the cobalt content.

Keywords: malic acid, oxidative dehydrogenation, hydrogenation, oxaloacetic acid

Procedia PDF Downloads 152
144 Design, Implementation, and Evaluation of ALS-PBL Model in the EMI Classroom

Authors: Yen-Hui Lu

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In the past two decades, in order to increase university visibility and internationalization, English as a medium of instruction (EMI) has become one of the main language policies in higher education institutions where English is not a dominant language. However, given the complex, discipline-embedded nature of academic communication, academic literacy does not come with students’ everyday language experience, and it is a challenge for all students. Particularly, to engage students in the effective learning process of discipline concepts in the EMI classrooms, teachers need to provide explicit academic language instruction to assist students in deep understanding of discipline concepts. To bridge the gap between academic language development and discipline learning in the EMI classrooms, the researcher incorporates academic language strategies and key elements of project-based learning (PBL) into an Academic Language Strategy driven PBL (ALS-PBL) model. With clear steps and strategies, the model helps EMI teachers to scaffold students’ academic language development in the EMI classrooms. ALS-PBL model includes three major stages: preparation, implementation, and assessment. First, in the preparation stage, ALS-PBL teachers need to identify learning goals for both content and language learning and to design PBL topics for investigation. Second, during the implementation stage, ALS-PBL teachers use the model as a guideline to create a lesson structure and class routine. There are five important elements in the implementation stage: (1) academic language preparation, (2) connecting background knowledge, (3) comprehensible input, (4) academic language reinforcement, and (5) sustained inquiry and project presentation. Finally, ALS-PBL teachers use formative assessments such as student learning logs, teachers’ feedback, and peer evaluation to collect detailed information that demonstrates students’ academic language development in the learning process. In this study, ALS-PBL model was implemented in an interdisciplinary course entitled “Science is Everywhere”, which was co-taught by five professors from different discipline backgrounds, English education, civil engineering, business administration, international business, and chemical engineering. The purpose of the course was to cultivate students’ interdisciplinary knowledge as well as English competency in disciplinary areas. This study used a case-study design to systematically investigate students’ learning experiences in the class using ALS-PBL model. The participants of the study were 22 college students with different majors. This course was one of the elective EMI courses in this focal university. The students enrolled in this EMI course to fulfill the school language policy, which requires the students to complete two EMI courses before their graduation. For the credibility, this study used multiple methods to collect data, including classroom observation, teachers’ feedback, peer assessment, student learning log, and student focus-group interviews. Research findings show four major successful aspects of implementing ALS-PBL model in the EMI classroom: (1) clear focus on both content and language learning, (2) meaningful practice in authentic communication, (3) reflective learning in academic language strategies, and (4) collaborative support in content knowledge.This study will be of value to teachers involved in delivering English as well as content lessons to language learners by providing a theoretically-sound practical model for application in the classroom.

Keywords: academic language development, content and language integrated learning, english as a medium of instruction, project-based learning

Procedia PDF Downloads 59
143 Biomaterials Solutions to Medical Problems: A Technical Review

Authors: Ashish Thakur

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This technical paper was written in view of focusing the biomaterials and its various applications in modern industries. Author tires to elaborate not only the medical, infect plenty of application in other industries. The scope of the research area covers the wide range of physical, biological and chemical sciences that underpin the design of biomaterials and the clinical disciplines in which they are used. A biomaterial is now defined as a substance that has been engineered to take a form which, alone or as part of a complex system, is used to direct, by control of interactions with components of living systems, the course of any therapeutic or diagnostic procedure. Biomaterials are invariably in contact with living tissues. Thus, interactions between the surface of a synthetic material and biological environment must be well understood. This paper reviews the benefits and challenges associated with surface modification of the metals in biomedical applications. The paper also elaborates how the surface characteristics of metallic biomaterials, such as surface chemistry, topography, surface charge, and wettability, influence the protein adsorption and subsequent cell behavior in terms of adhesion, proliferation, and differentiation at the biomaterial–tissue interface. The chapter also highlights various techniques required for surface modification and coating of metallic biomaterials, including physicochemical and biochemical surface treatments and calcium phosphate and oxide coatings. In this review, the attention is focused on the biomaterial-associated infections, from which the need for anti-infective biomaterials originates. Biomaterial-associated infections differ markedly for epidemiology, aetiology and severity, depending mainly on the anatomic site, on the time of biomaterial application, and on the depth of the tissues harbouring the prosthesis. Here, the diversity and complexity of the different scenarios where medical devices are currently utilised are explored, providing an overview of the emblematic applicative fields and of the requirements for anti-infective biomaterials. In addition to this, chapter introduces nanomedicine and the use of both natural and synthetic polymeric biomaterials, focuses on specific current polymeric nanomedicine applications and research, and concludes with the challenges of nanomedicine research. Infection is currently regarded as the most severe and devastating complication associated to the use of biomaterials. Osteoporosis is a worldwide disease with a very high prevalence in humans older than 50. The main clinical consequences are bone fractures, which often lead to patient disability or even death. A number of commercial biomaterials are currently used to treat osteoporotic bone fractures, but most of these have not been specifically designed for that purpose. Many drug- or cell-loaded biomaterials have been proposed in research laboratories, but very few have received approval for commercial use. Polymeric nanomaterial-based therapeutics plays a key role in the field of medicine in treatment areas such as drug delivery, tissue engineering, cancer, diabetes, and neurodegenerative diseases. Advantages in the use of polymers over other materials for nanomedicine include increased functionality, design flexibility, improved processability, and, in some cases, biocompatibility.

Keywords: nanomedicine, tissue, infections, biomaterials

Procedia PDF Downloads 239
142 Hydro-Mechanical Characterization of PolyChlorinated Biphenyls Polluted Sediments in Interaction with Geomaterials for Landfilling

Authors: Hadi Chahal, Irini Djeran-Maigre

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This paper focuses on the hydro-mechanical behavior of polychlorinated biphenyl (PCB) polluted sediments when stored in landfills and the interaction between PCBs and geosynthetic clay liners (GCL) with respect to hydraulic performance of the liner and the overall performance and stability of landfills. A European decree, adopted in the French regulation forbids the reintroducing of contaminated dredged sediments containing more than 0,64mg/kg Σ 7 PCBs to rivers. At these concentrations, sediments are considered hazardous and a remediation process must be adopted to prevent the release of PCBs into the environment. Dredging and landfilling polluted sediments is considered an eco-environmental remediation solution. French regulations authorize the storage of PCBs contaminated components with less than 50mg/kg in municipal solid waste facilities. Contaminant migration via leachate may be possible. The interactions between PCBs contaminated sediments and the GCL barrier present in the bottom of a landfill for security confinement are not known. Moreover, the hydro-mechanical behavior of stored sediments may affect the performance and the stability of the landfill. In this article, hydro-mechanical characterization of the polluted sediment is presented. This characterization led to predict the behavior of the sediment at the storage site. Chemical testing showed that the concentration of PCBs in sediment samples is between 1.7 and 2,0 mg/kg. Physical characterization showed that the sediment is organic silty sand soil (%Silt=65, %Sand=27, %OM=8) characterized by a high plasticity index (Ip=37%). Permeability tests using permeameter and filter press showed that sediment permeability is in the order of 10-9 m/s. Compressibility tests showed that the sediment is a very compressible soil with Cc=0,53 and Cα =0,0086. In addition, effects of PCB on the swelling behavior of bentonite were studied and the hydraulic performance of the GCL in interaction with PCBs was examined. Swelling tests showed that PCBs don’t affect the swelling behavior of bentonite. Permeability tests were conducted on a 1.0 m pilot scale experiment, simulating a storage facility. PCBs contaminated sediments were directly placed over a passive barrier containing GCL to study the influence of the direct contact of polluted sediment leachate with the GCL. An automatic water system has been designed to simulate precipitation. Effluent quantity and quality have been examined. The sediment settlements and the water level in the sediment have been monitored. The results showed that desiccation affected the behavior of the sediment in the pilot test and that laboratory tests alone are not sufficient to predict the behavior of the sediment in landfill facility. Furthermore, the concentration of PCB in the sediment leachate was very low ( < 0,013 µg/l) and that the permeability of the GCL was affected by other components present in the sediment leachate. Desiccation and cracks were the main parameters that affected the hydro-mechanical behavior of the sediment in the pilot test. In order to reduce these infects, the polluted sediment should be stored at a water content inferior to its shrinkage limit (w=39%). We also propose to conduct other pilot tests with the maximum concentration of PCBs allowed in municipal solid waste facility of 50 mg/kg.

Keywords: geosynthetic clay liners, landfill, polychlorinated biphenyl, polluted dredged materials

Procedia PDF Downloads 95
141 Functionalizing Gold Nanostars with Ninhydrin as Vehicle Molecule for Biomedical Applications

Authors: Swati Mishra

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In recent years, there has been an explosion in Gold NanoParticle (GNP) research, with a rapid increase in publications in diverse fields, including imaging, bioengineering, and molecular biology. GNPs exhibit unique physicochemical properties, including surface plasmon resonance (SPR) and bind amine and thiol groups, allowing surface modification and use in biomedical applications. Nanoparticle functionalization is the subject of intense research at present, with rapid progress being made towards developing biocompatible, multi-functional particles. In the present study, the photochemical method has been done to functionalize various-shaped GNPs like nanostars by the molecules like ninhydrin. Ninhydrin is bactericidal, virucidal, fungicidal, antigen-antibody reactive, and used in fingerprint technology in forensics. The GNPs functionalized with ninhydrin efficiently will bind to the amino acids on the target protein, which is of eminent importance during the pandemic, especially where long-term treatments of COVID- 19 bring many side effects of the drugs. The photochemical method is adopted as it provides low thermal load, selective reactivity, selective activation, and controlled radiation in time, space, and energy. The GNPs exhibit their characteristic spectrum, but a distinctly blue or redshift in the peak will be observed after UV irradiation, ensuring efficient ninhydrin binding. Now, the bound ninhydrin in the GNP carrier, upon chemically reacting with any amino acid, will lead to the formation of Rhumann purple. A common method of GNP production includes citrate reduction of Au [III] derivatives such as aurochloric acid (HAuCl4) in water to Au [0] through a one-step synthesis of size-tunable GNPs. The following reagents are prepared to validate the approach. Reagent A solution 1 is0.0175 grams ninhydrin in 5 ml Millipore water Reagent B 30 µl of HAuCl₄.3H₂O in 3 ml of solution 1 Reagent C 1 µl of gold nanostars in 3 ml of solution 1 Reagent D 6 µl of cetrimonium bromide (CTAB) in 3 ml of solution1 ReagentE 1 µl of gold nanostars in 3 ml of ethanol ReagentF 30 µl of HAuCl₄.₃H₂O in 3 ml of ethanol ReagentG 30 µl of HAuCl₄.₃H₂O in 3 ml of solution 2 ReagentH solution 2 is0.0087 grams ninhydrin in 5 ml Millipore water ReagentI 30 µl of HAuCl₄.₃H₂O in 3 ml of water The reagents were irradiated at 254 nm for 15 minutes, followed by their UV Visible spectroscopy. The wavelength was selected based on the one reported for excitation of a similar molecule Pthalimide. It was observed that the solution B and G deviate around 600 nm, while C peaks distinctively at 567.25 nm and 983.9 nm. Though it is tough to say about the chemical reaction happening, butATR-FTIR of reagents will ensure that ninhydrin is not forming Rhumann purple in the absence of amino acids. Therefore, these experiments, we achieved the functionalization of gold nanostars with ninhydrin corroborated by the deviation in the spectrum obtained in a mixture of GNPs and ninhydrin irradiated with UV light. It prepares them as a carrier molecule totake up amino acids for targeted delivery or germicidal action.

Keywords: gold nanostars, ninhydrin, photochemical method, UV visible specgtroscopy

Procedia PDF Downloads 118
140 Rapid Atmospheric Pressure Photoionization-Mass Spectrometry (APPI-MS) Method for the Detection of Polychlorinated Dibenzo-P-Dioxins and Dibenzofurans in Real Environmental Samples Collected within the Vicinity of Industrial Incinerators

Authors: M. Amo, A. Alvaro, A. Astudillo, R. Mc Culloch, J. C. del Castillo, M. Gómez, J. M. Martín

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Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of course comprise a range of highly toxic compounds that may exist as particulates within the air or accumulate within water supplies, soil, or vegetation. They may be created either ubiquitously or naturally within the environment as a product of forest fires or volcanic eruptions. It is only since the industrial revolution, however, that it has become necessary to closely monitor their generation as a byproduct of manufacturing/combustion processes, in an effort to mitigate widespread contamination events. Of course, the environmental concentrations of these toxins are expected to be extremely low, therefore highly sensitive and accurate methods are required for their determination. Since ionization of non-polar compounds through electrospray and APCI is difficult and inefficient, we evaluate the performance of a novel low-flow Atmospheric Pressure Photoionization (APPI) source for the trace detection of various dioxins and furans using rapid Mass Spectrometry workflows. Air, soil and biota (vegetable matter) samples were collected monthly during one year from various locations within the vicinity of an industrial incinerator in Spain. Analytes were extracted and concentrated using soxhlet extraction in toluene and concentrated by rotavapor and nitrogen flow. Various ionization methods as electrospray (ES) and atmospheric pressure chemical ionization (APCI) were evaluated, however, only the low-flow APPI source was capable of providing the necessary performance, in terms of sensitivity, required for detecting all targeted analytes. In total, 10 analytes including 2,3,7,8-tetrachlorodibenzodioxin (TCDD) were detected and characterized using the APPI-MS method. Both PCDDs and PCFDs were detected most efficiently in negative ionization mode. The most abundant ion always corresponded to the loss of a chlorine and addition of an oxygen, yielding [M-Cl+O]- ions. MRM methods were created in order to provide selectivity for each analyte. No chromatographic separation was employed; however, matrix effects were determined to have a negligible impact on analyte signals. Triple Quadrupole Mass Spectrometry was chosen because of its unique potential for high sensitivity and selectivity. The mass spectrometer used was a Sciex´s Qtrap3200 working in negative Multi Reacting Monitoring Mode (MRM). Typically mass detection limits were determined to be near the 1-pg level. The APPI-MS2 technology applied to the detection of PCDD/Fs allows fast and reliable atmospheric analysis, minimizing considerably operational times and costs, with respect other technologies available. In addition, the limit of detection can be easily improved using a more sensitive mass spectrometer since the background in the analysis channel is very low. The APPI developed by SEADM allows polar and non-polar compounds ionization with high efficiency and repeatability.

Keywords: atmospheric pressure photoionization-mass spectrometry (APPI-MS), dioxin, furan, incinerator

Procedia PDF Downloads 183
139 Optimizing Stormwater Sampling Design for Estimation of Pollutant Loads

Authors: Raja Umer Sajjad, Chang Hee Lee

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Stormwater runoff is the leading contributor to pollution of receiving waters. In response, an efficient stormwater monitoring program is required to quantify and eventually reduce stormwater pollution. The overall goals of stormwater monitoring programs primarily include the identification of high-risk dischargers and the development of total maximum daily loads (TMDLs). The challenge in developing better monitoring program is to reduce the variability in flux estimates due to sampling errors; however, the success of monitoring program mainly depends on the accuracy of the estimates. Apart from sampling errors, manpower and budgetary constraints also influence the quality of the estimates. This study attempted to develop optimum stormwater monitoring design considering both cost and the quality of the estimated pollutants flux. Three years stormwater monitoring data (2012 – 2014) from a mix land use located within Geumhak watershed South Korea was evaluated. The regional climate is humid and precipitation is usually well distributed through the year. The investigation of a large number of water quality parameters is time-consuming and resource intensive. In order to identify a suite of easy-to-measure parameters to act as a surrogate, Principal Component Analysis (PCA) was applied. Means, standard deviations, coefficient of variation (CV) and other simple statistics were performed using multivariate statistical analysis software SPSS 22.0. The implication of sampling time on monitoring results, number of samples required during the storm event and impact of seasonal first flush were also identified. Based on the observations derived from the PCA biplot and the correlation matrix, total suspended solids (TSS) was identified as a potential surrogate for turbidity, total phosphorus and for heavy metals like lead, chromium, and copper whereas, Chemical Oxygen Demand (COD) was identified as surrogate for organic matter. The CV among different monitored water quality parameters were found higher (ranged from 3.8 to 15.5). It suggests that use of grab sampling design to estimate the mass emission rates in the study area can lead to errors due to large variability. TSS discharge load calculation error was found only 2 % with two different sample size approaches; i.e. 17 samples per storm event and equally distributed 6 samples per storm event. Both seasonal first flush and event first flush phenomena for most water quality parameters were observed in the study area. Samples taken at the initial stage of storm event generally overestimate the mass emissions; however, it was found that collecting a grab sample after initial hour of storm event more closely approximates the mean concentration of the event. It was concluded that site and regional climate specific interventions can be made to optimize the stormwater monitoring program in order to make it more effective and economical.

Keywords: first flush, pollutant load, stormwater monitoring, surrogate parameters

Procedia PDF Downloads 213
138 Hexahydropyrimidine-2,4-Diones: Synthesis and Cytotoxic Activity

Authors: M. Koksal, T. Ozyazici, E. Gurdal, M. Yarım, E. Demirpolat, M. B. Y. Aycan

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The discovery of new drugs in cancer chemotherapy is still a major topic because of severe side effects, selectivity problems and resistance development potential of existing drugs. In recent years, combined anticancer therapies or multi-acting drugs are clinically preferred over traditional cytotoxic treatment, with the aim of avoiding resistance and toxic side effects. Arrangement of multi-acting targets can be carried out either by combination of several drugs with different mechanisms or by usage of a single chemical compound capable of regulating several targets of a disease with multiple factors. In literature, several pyrimidine and piperazine derivatives have been involved in the structure of many compounds which have been used as chemotherapeutic agents along with wide clinical applications. The aim of this study is to combine pyrimidine and piperazine core structures to research and develop novel piperazinylpyrimidine derivatives with selective cytotoxicity over cancer cells. In this study, a group of novel 6-fluorophenyl-3-[2-(substitutedpiperazinyl)ethyl] hexahydropyrimidine-2,4-dione derivatives designed to observe the desired anticancer activity due to pyrimidine and piperazine based scaffolds. Target compounds were obtained by the reaction of appropriate piperazine derivatives and 6-(2/4-fluorophenyl)-3-(2-chloroethyl)hexahydropyrimidine-2,4-dione. The synthetic pathway of 6-(2/4-fluorophenyl)-3-(2-chloroethyl)hexahydropyrimidine-2,4-dione was started with Rodionov reaction using aldehyde, malonic acid and ammonium acetate in ethanol. Isolated β-fluorophenyl-β-amino acids were treated with 2-chloroethylisocyanate in the presence of an aqueous sodium hydroxide solution at room temperature to yield the sodium salts of the corresponding ureido acids. By addition of a mineral acid, ureido acids were precipitated. Later, these ureido acids were refluxed in thionyl chloride to give the 6-(2/4-fluorophenyl)-3-(2-chloroethyl)hexahydropyrimidine-2,4-di-one which were furthermore treated with secondary amines. Structures of purified compounds were characterized with IR, 1H-NMR, 13C-NMR, mass spectroscopies and elemental analysis. All of the compounds gave satisfactory analytical and spectroscopic data, which were in full accordance with their depicted structures. In IR spectra of the compounds, N-H group was seen at 3230-3213 cm⁻¹. C-H was seen at 3100-2820 cm⁻¹ and C=O vibrational peaks were observed approximately at 1725 and 1665 cm⁻¹ in accordance with literature. In the NMR spectra of target compounds, the methylene protons of piperazine give two separate multiplet peaks around 3.5 and 4.5 ppm representing the successful N-alkylation of the structure. The cytotoxic activity of the synthesized compounds was investigated on human bronchial epithelial (BEAS 2B), lung (A549), colon adenocarcinoma (COLO205) and breast (MCF7) cell lines, by means of sulphorhodamine B (SRB) assays in triplicate. IC₅₀ values of the screened derivatives were found in range of 11.8-78 µM. This project was supported by The Scientific and Technological Research Council of Turkey (TUBITAK, Project no: 215S157).

Keywords: cytotoxicity, hexahydropyrimidine, piperazine, sulphorhodamine B assay

Procedia PDF Downloads 130
137 Supercritical Water Gasification of Organic Wastes for Hydrogen Production and Waste Valorization

Authors: Laura Alvarez-Alonso, Francisco Garcia-Carro, Jorge Loredo

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Population growth and industrial development imply an increase in the energy demands and the problems caused by emissions of greenhouse effect gases, which has inspired the search for clean sources of energy. Hydrogen (H₂) is expected to play a key role in the world’s energy future by replacing fossil fuels. The properties of H₂ make it a green fuel that does not generate pollutants and supplies sufficient energy for power generation, transportation, and other applications. Supercritical Water Gasification (SCWG) represents an attractive alternative for the recovery of energy from wastes. SCWG allows conversion of a wide range of raw materials into a fuel gas with a high content of hydrogen and light hydrocarbons through their treatment at conditions higher than those that define the critical point of water (temperature of 374°C and pressure of 221 bar). Methane used as a transport fuel is another important gasification product. The number of different uses of gas and energy forms that can be produced depending on the kind of material gasified and type of technology used to process it, shows the flexibility of SCWG. This feature allows it to be integrated with several industrial processes, as well as power generation systems or waste-to-energy production systems. The final aim of this work is to study which conditions and equipment are the most efficient and advantageous to explore the possibilities to obtain streams rich in H₂ from oily wastes, which represent a major problem both for the environment and human health throughout the world. In this paper, the relative complexity of technology needed for feasible gasification process cycles is discussed with particular reference to the different feedstocks that can be used as raw material, different reactors, and energy recovery systems. For this purpose, a review of the current status of SCWG technologies has been carried out, by means of different classifications based on key features as the feed treated or the type of reactor and other apparatus. This analysis allows to improve the technology efficiency through the study of model calculations and its comparison with experimental data, the establishment of kinetics for chemical reactions, the analysis of how the main reaction parameters affect the yield and composition of products, or the determination of the most common problems and risks that can occur. The results of this work show that SCWG is a promising method for the production of both hydrogen and methane. The most significant choices of design are the reactor type and process cycle, which can be conveniently adopted according to waste characteristics. Regarding the future of the technology, the design of SCWG plants is still to be optimized to include energy recovery systems in order to reduce costs of equipment and operation derived from the high temperature and pressure conditions that are necessary to convert water to the SC state, as well as to find solutions to remove corrosion and clogging of components of the reactor.

Keywords: hydrogen production, organic wastes, supercritical water gasification, system integration, waste-to-energy

Procedia PDF Downloads 121
136 Effect of Methoxy and Polyene Additional Functionalized Group on the Photocatalytic Properties of Polyene-Diphenylaniline Organic Chromophores for Solar Energy Applications

Authors: Ife Elegbeleye, Nnditshedzeni Eric, Regina Maphanga, Femi Elegbeleye, Femi Agunbiade

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The global potential of other renewable energy sources such as wind, hydroelectric, bio-mass, and geothermal is estimated to be approximately 13 %, with hydroelectricity constituting a larger percentage. Sunlight provides by far the largest of all carbon-neutral energy sources. More energy from the sunlight strikes the Earth in one hour (4.3 × 1020 J) than all the energy consumed on the planet in a year (4.1 × 1020 J), hence, solar energy remains the most abundant clean, renewable energy resources for mankind. Photovoltaic (PV) devices such as silicon solar cells, dye sensitized solar cells are utilized for harnessing solar energy. Polyene-diphenylaniline organic molecules are important sets of molecules that has stirred many research interest as photosensitizers in TiO₂ semiconductor-based dye sensitized solar cells (DSSCs). The advantages of organic dye molecule over metal-based complexes are higher extinction coefficient, moderate cost, good environmental compatibility, and electrochemical properties. The polyene-diphenylaniline organic dyes with basic configuration of donor-π-acceptor are affordable, easy to synthesize and possess chemical structures that can easily be modified to optimize their photocatalytic and spectral properties. The enormous interest in polyene-diphenylaniline dyes as photosensitizers is due to their fascinating spectral properties which include visible light to near infra-red-light absorption. In this work, density functional theory approach via GPAW software, Avogadro and ASE were employed to study the effect of methoxy functionalized group on the spectral properties of polyene-diphenylaniline dyes and their photons absorbing characteristics in the visible region to near infrared region of the solar spectrum. Our results showed that the two-phenyl based complexes D5 and D7 exhibits maximum absorption peaks at 750 nm and 850 nm, while D9 and D11 with methoxy group shows maximum absorption peak at 800 nm and 900 nm respectively. The highest absorption wavelength is notable for D9 and D11 containing additional polyene and methoxy groups. Also, D9 and D11 chromophores with the methoxy group shows lower energy gap of 0.98 and 0.85 respectively than the corresponding D5 and D7 dyes complexes with energy gap of 1.32 and 1.08. The analysis of their electron injection kinetics ∆Ginject into the band gap of TiO₂ shows that D9 and D11 with the methoxy group has higher electron injection kinetics of -2.070 and -2.030 than the corresponding polyene-diphenylaniline complexes without the addition of polyene group with ∆Ginject values of -2.820 and -2.130 respectively. Our findings suggest that the addition of functionalized group as an extension of the organic complexes results in higher light harvesting efficiencies and bathochromic shift of the absorption spectra to higher wavelength which suggest higher current densities and open circuit voltage in DSSCs. The study suggests that the photocatalytic properties of organic chromophores/complexes with donor-π-acceptor configuration can be enhanced by the addition of functionalized groups.

Keywords: renewable energy resource, solar energy, dye sensitized solar cells, polyene-diphenylaniline organic chromophores

Procedia PDF Downloads 77
135 Mechanical and Durability Characteristics of Roller Compacted Geopolymer Concrete Using Recycled Concrete Aggregate

Authors: Syfur Rahman, Mohammad J. Khattak

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Every year a huge quantity of recycling concrete aggregate (RCA) is generated in the United States of America. Utilization of RCA can solve the storage problem, prevent environmental pollution, and reduce the construction cost. However, due to the overall low strength and durability characteristics of RCA, its usages are limited to a certain area like a landfill, low strength base material, replacement of a few percentages of virgin aggregates in Portland cement concrete, etc. This study focuses on the improvement of the strength and durability characteristics of RCA by introducing the concept of roller-compacted geopolymer concrete. In this research, developed roller-compacted geopolymer concrete (RCGPC) and roller-compacted cement concrete (RCC) mixtures containing 100% recycled concrete aggregate were evaluated and compared. Several selected RCGPC mixtures were investigated to find out the effect of mixture variables, including sodium hydroxide (NaOH) molar concentration, sodium silicate (Na₂SiO₃), to sodium hydroxide (NaOH) ratio on the strength, stiffness and durability characteristics of the developed RCGPC. Sodium hydroxide (NaOH) and sodium silicate (Na₂SiO₃) were mixed in different ratios to synthesize the alkali activator. American Concrete Pavement Association (ACPA) recommended RCC gradation was used with a maximum nominal aggregate size of 19 mm with a 4% fine particle passing 0.075 mm sieve. The mixtures were made using NaOH molar concentration of 8M and 10M along with, Na₂SiO₃ to NaOH ratio of 0 and 1 by mass and 15% class F fly ash. Optimum alkali content and moisture content were determined for each RCGPC and RCC mixtures, respectively, using modified proctor test. Compressive strength, semi-circular bending beam strength, and dynamic modulus test were conducted to evaluate the mechanistic characteristics of both mixtures. To determine the optimum curing conditions for RCGPC, effects of different curing temperature and curing duration on compressive strength were also studied. Sulphate attack and freeze-thaw tests were also carried out to assess the durability properties of the developed mixtures. X-ray diffraction (XRD) was used for morphology and microstructure analysis. From the optimum moisture content results, it was found that RCGPC has high alkali content, which was mainly due to the high absorption capacity of RCA. It was found that the mixtures with Na₂SiO₃ to NaOH ratio of 1 yielded about 60% higher compressive strength than the ratio of 0. Further, the mixtures using 10M NaOH concentrations and alkali ratio of 1 produced about 28 MPa of compressive strength, which was around 33% higher than 8M NaOH mixtures. Similar results were obtained for elastic and dynamic modulus of the mixtures. On the other hand, the semi-circular bending beam strength remained the same for both 8 and 10 molar NaOH geopolymer mixtures. Formation of new geopolymeric compounds and chemical bonds in the newly formed novel RCGPC mixtures were also discovered using XRD analysis. The results of mechanical and durability testing further revealed that RCGPC performed similarly to that of RCC mixtures. Based on the results of mechanical and durability testing, the developed RCGPC mixtures using 100% recycled concrete could be used as a cost-effective solution for the construction of pavement structures.

Keywords: roller compacted concrete, geopolymer concrete, recycled concrete aggregate, concrete pavement, fly ash

Procedia PDF Downloads 113
134 Intraspecific Biochemical Diversity of Dalmatian Pyrethrum Across the Different Bioclimatic Regions of Its Natural Distribution Area

Authors: Martina Grdiša, Filip Varga, Nina Jeran, Ante Turudić, Zlatko Šatović

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Dalmatian pyrethrum (Tanacetum cinerariifolium (Trevir.) Sch. Bip.) is a plant species that occurs naturally in the eastern Mediterranean. It is of immense economic importance as it synthesizes and accumulates the phytochemical compound pyrethrin. Pyrethrin consists of several monoterpene esters (pyrethrin I and II, cinerin I and II and jasmolin I and II), which have insecticidal and repellent activity through their synergistic action. In this study, 15 natural Dalmatian pyrethrum populations were sampled along their natural range in Croatia, Bosnia and Herzegovina and Montenegro to characterize and compare their pyrethrin profiles and to define the bioclimatic factors associated with the accumulation of each pyrethrin compound. Pyrethrins were extracted from the dried flower heads of Dalmatian pyrethrum using ultrasound-assisted extraction and the amount of each compound was quantified using high-performance liquid chromatography coupled to DAD-UV /VIS. The biochemical data were subjected to analysis of variance, correlation analysis and multivariate analysis. Quantitative variability within and among populations was found, with population P15 Vranjske Njive, Podgorica having the significantly highest pyrethrin I content (66.47% of total pyrethrin content), while the highest levels of total pyrethrin were found in P14 Budva (1.27% of dry flower weight; DW), followed by P08 Korčula (1.15% DW). Based on the environmental conditions at the sampling sites of the populations, five bioclimatic groups were distinguished, referred to as A, B, C, D, and E, each with rare chemical profile. The first group (A) consisted of the northern Adriatic population P01 Vrbnik, Krk and the population P06 Sevid - the coastal population of the central Adriatic, and generally differed significantly from the other bioclimatic groups by higher average jasmolin II values (2.13% of total pyrethrin). The second group (B) consisted of two central Adriatic island populations (P02 Telašćica, Dugi otok and P03 Žman, Dugi otok), while the remaining central Adriatic island populations were grouped in bioclimatic group C, which was characterized by the significantly highest average pyrethrin II (48.52% of total pyrethrin) and cinerin II (5.31% DW) content. The South Adriatic inland populations P10 Srđ and P11 Trebinje (Bosnia and Herzegovina), and the populations from Montenegro (P12 Grahovo, P13 Lovćen, P14 Budva and P15 Vranjske Njive, Podgorica) formed bioclimatic group E. This bioclimatic group was characterized by the highest average values for pyrethrin I (53.07 % of total pyrethrin), total pyrethrin content (1.06 % DW) and the ratio of pyrethrin I and II (1.85). Slightly lower values (although not significant) for the latter traits were detected in bioclimatic group D (southern Adriatic island populations P07 Vis, P08 Korčula and P09 Mljet). A weak but significant correlation was found between the levels of some pyrethrin compounds and bioclimatic variables (e.g., BIO03 Isothermality and BIO04 Temperature Seasonality), which explains part of the variability observed in the populations studied. This suggests the interconnection between bioclimatic variables and biochemical profiles either through the selection of adapted genotypes or through the ability of species to alter the expression of biochemical traits in response to environmental changes.

Keywords: biopesticides, biochemical variability, pyrethrin, Tanacetum cinerariifolium

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133 Silver-Doped Magnetite Titanium Oxide Nanoparticles for Photocatalytic Degradation of Organic Pollutants

Authors: Hanna Abbo, Siyasanga Noganta, Salam Titinchi

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The global lack of clean water for human sanitation and other purposes has become an emerging dilemma for human beings. The presence of organic pollutants in wastewater produced by textile industries, leather manufacturing and chemical industries is an alarming matter for a safe environment and human health. For the last decades, conventional methods have been applied for the purification of water but due to industrialization these methods fall short. Advanced oxidation processes and their reliable application in degradation of many contaminants have been reported as a potential method to reduce and/or alleviate this problem. Lately it has been assumed that incorporation of some metal nanoparticles such as magnetite nanoparticles as photocatalyst for Fenton reaction which could improve the degradation efficiency of contaminants. Core/shell nanoparticles, are extensively studied because of their wide applications in the biomedical, drug delivery, electronics fields and water treatment. The current study is centred on the synthesis of silver-doped Fe3O4/SiO2/TiO2 photocatalyst. Magnetically separable Fe3O4@SiO2@TiO2 composite with core–shell structure were synthesized by the deposition of uniform anatase TiO2 NPs on Fe3O4@SiO2 by using titanium butoxide (TBOT) as titanium source. Then, the silver is doped on SiO2 layer by hydrothermal method. Integration of magnetic nanoparticles was suggested to avoid the post separation difficulties associated with the powder form of the TiO2 catalyst, increase of the surface area and adsorption properties. The morphology, structure, composition, and magnetism of the resulting composites were characterized and their photocatalytic activities were also evaluated. The results demonstrate that TiO2 NPs were uniformly deposited on the Fe3O4@SiO2 surface. The silver nanoparticles were also uniformly distributed on the surface of TiO2 nanoparticles. The aim of this work is to study the suitability of photocatalysis for the treatment of aqueous streams containing organic pollutants such as methylene blue which is selected as a model compound to represent one of the pollutants existing in wastewaters. Various factors such as initial pollutant concentration, photocatalyst dose and wastewater matrix were studied for their effect on the photocatalytic degradation of the organic model pollutants using the as synthesized catalysts and compared with the commercial titanium dioxide (Aeroxide P25). Photocatalysis was found to be a potential purification method for the studied pollutant also in an industrial wastewater matrix with the removal percentages of over 81 % within 15 minutes. Methylene blue was removed most efficiently and its removal consumed the least of energy in terms of the specific applied energy. The magnetic Ag/SiO2/TiO2 composites show high photocatalytic performance and can be recycled three times by magnetic separation without major loss of activity, which meant that they can be used as efficient and conveniently renewable photocatalyst.

Keywords: Magnetite nanoparticles, Titanium, Photocatalyst, Organic pollutant, Water treatment

Procedia PDF Downloads 238
132 Biosurfactants Produced by Antarctic Bacteria with Hydrocarbon Cleaning Activity

Authors: Claudio Lamilla, Misael Riquelme, Victoria Saez, Fernanda Sepulveda, Monica Pavez, Leticia Barrientos

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Biosurfactants are compounds synthesized by microorganisms that show various chemical structures, including glycolipids, lipopeptides, polysaccharide-protein complex, phospholipids, and fatty acids. These molecules have attracted attention in recent years due to the amphipathic nature of these compounds, which allows their application in various activities related to emulsification, foaming, detergency, wetting, dispersion and solubilization of hydrophobic compounds. Microorganisms that produce biosurfactants are ubiquitous, not only present in water, soil, and sediments but in extreme conditions of pH, salinity or temperature such as those present in Antarctic ecosystems. Due to this, it is of interest to study biosurfactants producing bacterial strains isolated from Antarctic environments, with the potential to be used in various biotechnological processes. The objective of this research was to characterize biosurfactants produced by bacterial strains isolated from Antarctic environments, with potential use in biotechnological processes for the cleaning of sites contaminated with hydrocarbons. The samples were collected from soils and sediments in the South Shetland Islands and the Antarctic Peninsula, during the Antarctic Research Expedition INACH 2016, from both pristine and human occupied areas (influenced). The bacteria isolation was performed from solid R2A, M1 and LB media. The selection of strains producing biosurfactants was done by hemolysis test on blood agar plates (5%) and blue agar (CTAB). From 280 isolates, it was determined that 10 bacterial strains produced biosurfactants after stimulation with different carbon sources. 16S rDNA taxonomic markers, using the universal primers 27F-1492R, were used to identify these bacterias. Biosurfactants production was carried out in 250 ml flasks using Bushnell Hass liquid culture medium enriched with different carbon sources (olive oil, glucose, glycerol, and hexadecane) during seven days under constant stirring at 20°C. Each cell-free supernatant was characterized by physicochemical parameters including drop collapse, emulsification and oil displacement, as well as stability at different temperatures, salinity, and pH. In addition, the surface tension of each supernatant was quantified using a tensiometer. The strains with the highest activity were selected, and the production of biosurfactants was stimulated in six liters of culture medium. Biosurfactants were extracted from the supernatants with chloroform methanol (2:1). These biosurfactants were tested against crude oil and motor oil, to evaluate their displacement activity (detergency). The characterization by physicochemical properties of 10 supernatants showed that 80% of them produced the drop collapse, 60% had stability at different temperatures, and 90% had detergency activity in motor and olive oil. The biosurfactants obtained from two bacterial strains showed a high activity of dispersion of crude oil and motor oil with halos superior to 10 cm. We can conclude that bacteria isolated from Antarctic soils and sediments provide biological material of high quality for the production of biosurfactants, with potential applications in the biotechnological industry, especially in hydrocarbons -contaminated areas such as petroleum.

Keywords: antarctic, bacteria, biosurfactants, hydrocarbons

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131 Crystallization Based Resolution of Enantiomeric and Diastereomeric Derivatives of myo-Inositol

Authors: Nivedita T. Patil, M. T. Patil, M. S. Shashidhar, R. G. Gonnade

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Cyclitols are cycloalkane polyols which have raise attention since they have numerous biological and pharmaceutical properties. Among these, inositols are important cyclitols, which constitute a group of naturally occurring polyhydric alcohols. Myo, scyllo, allo, neo, D-chiro- are naturally occurring structural isomer of inositol while other four isomers (L-chiro, allo, epi-, and cis-inositol) are derived from myo-inositol by chemical synthesis. Myo-inositol, most abundant isomer, plays an important role in signal transduction process and for the treatment of type 2 diabetes, bacterial infections, stimulation of menstruation, ovulation in polycystic ovary syndrome, improvement of osteogenesis, and in treatment of neurological disorders. Considering the vast application of the derivatives, it becomes important to supply these compounds for further studies in quantitative amounts, but the synthesis of suitably protected chiral inositol derivatives is the key intermediates in most of the synthesis which is difficult. Chiral inositol derivatives could also be of interest to synthetic organic chemists as they could serve as potential starting materials for the synthesis of several natural products and their analogs. Thus, obtaining chiral myo-inositol derivatives in a more eco-friendly way is need for current inositol chemistry. Thus, the resolution of nonracemates by preferential crystallization of enantiomers has not been reported as a method for inositol derivatives. We are optimistic that this work might lead to the development of the two tosylate enantiomers as synthetic chiral pool molecules for organic synthesis. Resolution of racemic 4-O-benzyl 6-O-tosyl myo-inositol 1, 3, 5 orthoformate was successfully achieved on multigram scale by preferential crystallization, which is more scalable, eco-friendly method of separation than other reported methods. The separation of the conglomeric mixture of tosylate was achieved by suspending the mixture in ethyl acetate till the level of saturation is obtained. To this saturated clear solution was added seed crystal of the desired enantiomers. The filtration of the precipitated seed was carried out at its filtration window to get enantiomerically enriched tosylate, and the process was repeated alternatively. These enantiomerically enriched samples were recrystallized to get tosylate as pure enantiomers. The configuration of the resolved enantiomers was determined by converting it to previously reported dibenzyl ether myo-inositol, which is an important precursor for mono- and tetraphosphates. We have also developed a convenient and practical method for the preparation of enantiomeric 4-O and 6-O-allyl myo-inositol orthoesters by resolution of diastereomeric allyl dicamphante orthoesters on multigram scale. These allyl ethers can be converted to other chiral protected myo-inositol derivatives using routine synthetic transformations. The chiral allyl ethers can be obtained in gram quantities, and the methods are amenable to further scale-up due to the simple procedures involved. We believe that the work described enhances the pace of research to understand the intricacies of the myo-inositol cycle as the methods described provide efficient access to enantiomeric phosphoinositols, cyclitols, and their derivatives from the abundantly available myo-inositol as a starting material.

Keywords: cyclitols, diastereomers, enantiomers, myo-inositol, preferential crystallization, signal transduction

Procedia PDF Downloads 118
130 Carbon-Foam Supported Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Authors: Albert Mufundirwa, Satoru Yoshioka, K. Ogi, Takeharu Sugiyama, George F. Harrington, Bretislav Smid, Benjamin Cunning, Kazunari Sasaki, Akari Hayashi, Stephen M. Lyth

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Polymer electrolyte membrane fuel cells (PEMFCs) are electrochemical energy conversion devices used for portable, residential and vehicular applications due to their low emissions, high efficiency, and quick start-up characteristics. However, PEMFCs generally use expensive, Pt-based electrocatalysts as electrode catalysts. Due to the high cost and limited availability of platinum, research and development to either drastically reduce platinum loading, or replace platinum with alternative catalysts is of paramount importance. A combination of high surface area supports and nano-structured active sites is essential for effective operation of catalysts. We synthesize carbon foam supports by thermal decomposition of sodium ethoxide, using a template-free, gram scale, cheap, and scalable pyrolysis method. This carbon foam has a high surface area, highly porous, three-dimensional framework which is ideal for electrochemical applications. These carbon foams can have surface area larger than 2500 m²/g, and electron microscopy reveals that they have micron-scale cells, separated by few-layer graphene-like carbon walls. We applied this carbon foam as a platinum catalyst support, resulting in the improved electrochemical surface area and mass activity for the oxygen reduction reaction (ORR), compared to carbon black. Similarly, silver-decorated carbon foams showed higher activity and efficiency for electrochemical carbon dioxide conversion than silver-decorated carbon black. A promising alternative to Pt-catalysts for the ORR is iron-impregnated nitrogen-doped carbon catalysts (Fe-N-C). Doping carbon with nitrogen alters the chemical structure and modulates the electronic properties, allowing a degree of control over the catalytic properties. We have adapted our synthesis method to produce nitrogen-doped carbon foams with large surface area, using triethanolamine as a nitrogen feedstock, in a novel bottom-up protocol. These foams are then infiltrated with iron acetate (FeAc) and pyrolysed to form Fe-N-C foams. The resulting Fe-N-C foam catalysts have high initial activity (half-wave potential of 0.68 VRHE), comparable to that of commercially available Pt-free catalysts (e.g., NPC-2000, Pajarito Powder) in acid solution. In alkaline solution, the Fe-N-C carbon foam catalysts have a half-wave potential of 0.89 VRHE, which is higher than that of NPC-2000 by almost 10 mVRHE, and far out-performing platinum. However, the durability is still a problem at present. The lessons learned from X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements will be used to carefully design Fe-N-C catalysts for higher performance PEMFCs.

Keywords: carbon-foam, polymer electrolyte membrane fuel cells, platinum, Pt-free, Fe-N-C, ORR

Procedia PDF Downloads 148
129 Changes in Physicochemical Characteristics of a Serpentine Soil and in Root Architecture of a Hyperaccumulating Plant Cropped with a Legume

Authors: Ramez F. Saad, Ahmad Kobaissi, Bernard Amiaud, Julien Ruelle, Emile Benizri

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Agromining is a new technology that establishes agricultural systems on ultramafic soils in order to produce valuable metal compounds such as nickel (Ni), with the final aim of restoring a soil's agricultural functions. But ultramafic soils are characterized by low fertility levels and this can limit yields of hyperaccumulators and metal phytoextraction. The objectives of the present work were to test if the association of a hyperaccumulating plant (Alyssum murale) and a Fabaceae (Vicia sativa var. Prontivesa) could induce changes in physicochemical characteristics of a serpentine soil and in root architecture of a hyperaccumulating plant then lead to efficient agromining practices through soil quality improvement. Based on standard agricultural systems, consisting in the association of legumes and another crop such as wheat or rape, a three-month rhizobox experiment was carried out to study the effect of the co-cropping (Co) or rotation (Ro) of a hyperaccumulating plant (Alyssum murale) with a legume (Vicia sativa) and incorporating legume biomass to soil, in comparison with mineral fertilization (FMo), on the structure and physicochemical properties of an ultramafic soil and on root architecture. All parameters measured (biomass, C and N contents, and taken-up Ni) on Alyssum murale conducted in co-cropping system showed the highest values followed by the mineral fertilization and rotation (Co > FMo > Ro), except for root nickel yield for which rotation was better than the mineral fertilization (Ro > FMo). The rhizosphere soil of Alyssum murale in co-cropping had larger soil particles size and better aggregates stability than other treatments. Using geostatistics, co-cropped Alyssum murale showed a greater root surface area spatial distribution. Moreover, co-cropping and rotation-induced lower soil DTPA-extractable nickel concentrations than other treatments, but higher pH values. Alyssum murale co-cropped with a legume showed a higher biomass production, improved soil physical characteristics and enhanced nickel phytoextraction. This study showed that the introduction of a legume into Ni agromining systems could improve yields of dry biomass of the hyperaccumulating plant used and consequently, the yields of Ni. Our strategy can decrease the need to apply fertilizers and thus minimizes the risk of nitrogen leaching and underground water pollution. Co-cropping of Alyssum murale with the legume showed a clear tendency to increase nickel phytoextraction and plant biomass in comparison to rotation treatment and fertilized mono-culture. In addition, co-cropping improved soil physical characteristics and soil structure through larger and more stabilized aggregates. It is, therefore, reasonable to conclude that the use of legumes in Ni-agromining systems could be a good strategy to reduce chemical inputs and to restore soil agricultural functions. Improving the agromining system by the replacement of inorganic fertilizers could simultaneously be a safe way of rehabilitating degraded soils and a method to restore soil quality and functions leading to the recovery of ecosystem services.

Keywords: plant association, legumes, hyperaccumulating plants, ultramafic soil physicochemical properties

Procedia PDF Downloads 143
128 Effects of Temperature and Mechanical Abrasion on Microplastics

Authors: N. Singh, G. K. Darbha

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Since the last decade, a wave of research has begun to study the prevalence and impact of ever-increasing plastic pollution in the environment. The wide application and ubiquitous distribution of plastic have become a global concern due to its persistent nature. The disposal of plastics has emerged as one of the major challenges for waste management landfills. Microplastics (MPs) have found its existence in almost every environment, from the high altitude mountain lake to the deep sea sediments, polar icebergs, coral reefs, estuaries, beaches, and river, etc. Microplastics are fragments of plastics with size less than 5 mm. Microplastics can be classified as primary microplastics and secondary microplastics. Primary microplastics includes purposefully introduced microplastics into the end products for consumers (microbeads used in facial cleansers, personal care product, etc.), pellets (used in manufacturing industries) or fibres (from textile industries) which finally enters into the environment. Secondary microplastics are formed by disintegration of larger fragments under the exposure of sunlight, mechanical abrasive forces by rain, waves, wind and/or water. A number of factors affect the quantity of microplastic present in freshwater environments. In addition to physical forces, human population density proximal to the water body, proximity to urban centres, water residence time, and size of the water body also affects plastic properties. With time, other complex processes in nature such as physical, chemical and biological break down plastics by interfering with its structural integrity. Several studies demonstrate that microplastics found in wastewater sludge being used as manure for agricultural fields, thus having the tendency to alter the soil environment condition influencing the microbial population as well. Inadequate data are available on the fate and transport of microplastics under varying environmental conditions that are required to supplement important information for further research. In addition, microplastics have the tendency to absorb heavy metals and hydrophobic organic contaminants such as PAHs and PCBs from its surroundings and thus acting as carriers for these contaminants in the environment system. In this study, three kinds of microplastics (polyethylene, polypropylene and expanded polystyrene) of different densities were chosen. Plastic samples were placed in sand with different aqueous media (distilled water, surface water, groundwater and marine water). It was incubated at varying temperatures (25, 35 and 40 °C) and agitation levels (rpm). The results show that the number of plastic fragments enhanced with increase in temperature and agitation speed. Moreover, the rate of disintegration of expanded polystyrene is high compared to other plastics. These results demonstrate that temperature, salinity, and mechanical abrasion plays a major role in degradation of plastics. Since weathered microplastics are more harmful as compared to the virgin microplastics, long-term studies involving other environmental factors are needed to have a better understanding of degradation of plastics.

Keywords: environmental contamination, fragmentation, microplastics, temperature, weathering

Procedia PDF Downloads 135
127 Colocalization Analysis to Understand Yttrium Uptake in Saxifraga paniculata Using Complementary Imaging Technics

Authors: Till Fehlauer, Blanche Collin, Bernard Angeletti, Andrea Somogyi, Claire Lallemand, Perrine Chaurand, Cédric Dentant, Clement Levard, Jerome Rose

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Over the last decades, yttrium (Y) has gained importance in high-tech applications. It is an essential part of alloys and compounds used for lasers, displays, or cell phones, for example. Due to its chemical similarities with the lanthanides, Y is often considered a rare earth element (REE). Despite their increased usage, the environmental behavior of REEs remains poorly understood. Especially regarding their interactions with plants, many uncertainties exist. On the one hand, Y is known to have a negative effect on root development and germination, but on the other hand, it appears to promote plant growth at low concentrations. In order to understand these phenomena, a precise knowledge is necessary about how Y is absorbed by the plant and how it is handled once inside the organism. Contradictory studies exist, stating that due to a similar ionic radius, Y and the other REEs might be absorbed through Ca²⁺-channels, while others suspect that Y has a shared pathway with Al³⁺. In this study, laser ablation coupled ICP-MS, and synchrotron-based micro-X-ray fluorescence (µXRF, beamline Nanoscopium, SOLEIL, France) have been used in order to localize Y within the plant tissue and identify associated elements. The plant used in this study is Saxifraga paniculata, a rugged alpine plant that has shown an affinity for Y in previous studies (in prep.). Furthermore, Saxifraga paniculata performs guttation, which means that it possesses phloem sap secreting openings on the leaf surface that serve to regulate root pressure. These so-called hydathodes could provide special insights in elemental transport in plants. The plants have been grown on Y doped soil (500mg/kg DW) for four months. The results showed that Y was mainly concentrated in the roots of Saxifraga paniculata (260 ± 85mg/kg), and only a small amount was translocated to the leaves (10 ± 7.8mg/kg). µXRF analysis indicated that within the root transects, the majority of Y remained in the epidermis and hardly penetrated the stele. Laser ablation coupled ICP-MS confirmed this finding and showed a positive correlation in the roots between Y, Fe, Al, and to a lesser extent Ca. In the stem transect, Y was mainly detected in a hotspot of approximately 40µm in diameter situated in the endodermis area. Within the stem and especially in the hotspot, Y was highly colocalized with Al and Fe. Similar-sized Y hotspots have been detected in/on the leaves. All of them were strongly colocalized with Al and Fe, except for those situated within the hydathodes, which showed no colocalization with any of the measured elements. Accordingly, a relation between Y and Ca during root uptake remains possible, whereas a correlation to Fe and Al appears to be dominant in the aerial parts, suggesting common storage compartments, the formation of complexes, or a shared pathway during translocation.

Keywords: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Phytoaccumulation, Rare earth elements, Saxifraga paniculata, Synchrotron-based micro-X-ray fluorescence, Yttrium

Procedia PDF Downloads 127