Search results for: surface properties

Authors: Óscar Muñoz Garrigós, José Manuel Bernabeu Aubán

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Time-sensitive services are the base of the cloud services industry. Keeping low service saturation is essential for controlling response time. All auto-scalable services make use of reactive auto-scaling. However, reactive auto-scaling has few in-depth studies. This presentation shows a model for reactive auto-scaling methodologies with a MAPE-k architecture. Queuing theory can compute different properties of static services but lacks some parameters related to the transition between models. Our model uses queuing theory parameters to relate the transition between models. It associates MAPE-k related times, the sampling frequency, the cooldown period, the number of requests that an instance can handle per unit of time, the number of incoming requests at a time instant, and a function that describes the acceleration in the service's ability to handle more requests. This model is later used as a solution to horizontally auto-scale time-sensitive services composed of microservices, reevaluating the model’s parameters periodically to allocate resources. The solution requires limiting the acceleration of the growth in the number of incoming requests to keep a constrained response time. Business benefits determine such limits. The solution can add a dynamic number of instances and remains valid under different system sizes. The study includes performance recommendations to improve results according to the incoming load shape and business benefits. The exposed methodology is tested in a simulation. The simulator contains a load generator and a service composed of two microservices, where the frontend microservice depends on a backend microservice with a 1:1 request relation ratio. A common request takes 2.3 seconds to be computed by the service and is discarded if it takes more than 7 seconds. Both microservices contain a load balancer that assigns requests to the less loaded instance and preemptively discards requests if they are not finished in time to prevent resource saturation. When load decreases, instances with lower load are kept in the backlog where no more requests are assigned. If the load grows and an instance in the backlog is required, it returns to the running state, but if it finishes the computation of all requests and is no longer required, it is permanently deallocated. A few load patterns are required to represent the worst-case scenario for reactive systems: the following scenarios test response times, resource consumption and business costs. The first scenario is a burst-load scenario. All methodologies will discard requests if the rapidness of the burst is high enough. This scenario focuses on the number of discarded requests and the variance of the response time. The second scenario contains sudden load drops followed by bursts to observe how the methodology behaves when releasing resources that are lately required. The third scenario contains diverse growth accelerations in the number of incoming requests to observe how approaches that add a different number of instances can handle the load with less business cost. The exposed methodology is compared against a multiple threshold CPU methodology allocating/deallocating 10 or 20 instances, outperforming the competitor in all studied metrics.

Keywords: reactive auto-scaling, auto-scaling, microservices, cloud computing

Procedia PDF Downloads 93

Authors: Natalie Hoyer

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Bridges in both roadway and railway systems depend on bearings to ensure extended service life and functionality. These bearings enable proper load distribution from the superstructure to the substructure while permitting controlled movement of the superstructure. The design of bridge bearings, according to Eurocode DIN EN 1337 and the relevant sections of DIN EN 1993, increasingly requires the use of thick plates, especially for long-span bridges. However, these plate thicknesses exceed the limits specified in the national appendix of DIN EN 1993-2. Furthermore, compliance with DIN EN 1993-1-10 regulations regarding material toughness and through-thickness properties necessitates further modifications. Consequently, these standards cannot be directly applied to the selection of bearing materials without supplementary guidance and design rules. In this context, a recommendation was developed in 2011 to regulate the selection of appropriate steel grades for bearing components. Prior to the initiation of the research project underlying this contribution, this recommendation had only been available as a technical bulletin. Since July 2023, it has been integrated into guideline 804 of the German railway. However, recent findings indicate that certain bridge-bearing components are exposed to high fatigue loads, which necessitate consideration in structural design, material selection, and calculations. Therefore, the German Centre for Rail Traffic Research called a research project with the objective of defining a proposal to expand the current standards in order to implement a sufficient choice of steel material for bridge bearings to avoid brittle fracture, even for thick plates and components subjected to specific fatigue loads. The results obtained from theoretical considerations, such as finite element simulations and analytical calculations, are validated through large-scale component tests. Additionally, experimental observations are used to calibrate the calculation models and modify the input parameters of the design concept. Within the large-scale component tests, a brittle failure is artificially induced in a bearing component. For this purpose, an artificially generated initial defect is introduced at the previously defined hotspot into the specimen using spark erosion. Then, a dynamic load is applied until the crack initiation process occurs to achieve realistic conditions in the form of a sharp notch similar to a fatigue crack. This initiation process continues until the crack length reaches a predetermined size. Afterward, the actual test begins, which requires cooling the specimen with liquid nitrogen until a temperature is reached where brittle fracture failure is expected. In the next step, the component is subjected to a quasi-static tensile test until failure occurs in the form of a brittle failure. The proposed paper will present the latest research findings, including the results of the conducted component tests and the derived definition of the initial crack size in bridge bearings.

Keywords: bridge bearings, brittle fracture, fatigue, initial crack size, large-scale tests

Procedia PDF Downloads 44

Authors: Maria De Los Angeles Ortega, Denis Bruneau, Patrick Sebastian, Jean-Pierre Nadeau, Alain Sommier, Saed Raji

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Phase change materials (PCM) present attractive features that made them a passive solution for thermal comfort assessment in buildings during summer time. They show a large storage capacity per volume unit in comparison with other structural materials like bricks or concrete. If their use is matched with the peak load periods, they can contribute to the reduction of the primary energy consumption related to cooling applications. Despite these promising characteristics, they present some drawbacks. Commercial PCMs, as paraffines, offer a low thermal conductivity affecting the overall performance of the system. In some cases, the material can be enhanced, adding other elements that improve the conductivity, but in general, a design of the unit that optimizes the thermal performance is sought. The material selection is the departing point during the designing stage, and it does not leave plenty of room for optimization. The PCM melting point depends highly on the atmospheric characteristics of the building location. The selection must relay within the maximum, and the minimum temperature reached during the day. The geometry of the PCM container and the geometrical distribution of these containers are designing parameters, as well. They significantly affect the heat transfer, and therefore its phenomena must be studied exhaustively. During its lifetime, an air-PCM unit in a building must cool down the place during daytime, while the melting of the PCM occurs. At night, the PCM must be regenerated to be ready for next uses. When the system is not in service, a minimal amount of thermal exchanges is desired. The aforementioned functions result in the presence of sensible and latent heat storage and release. Hence different types of mechanisms drive the heat transfer phenomena. An experimental test was designed to study the heat transfer phenomena occurring in a circular tube bundle air-PCM exchanger. An in-line arrangement was selected as the geometrical distribution of the containers. With the aim of visual identification, the containers material and a section of the test bench were transparent. Some instruments were placed on the bench for measuring temperature and velocity. The PCM properties were also available through differential scanning calorimeter (DSC) tests. An evolution of the temperature during both cycles, melting and solidification were obtained. The results showed some phenomena at a local level (tubes) and on an overall level (exchanger). Conduction and convection appeared as the main heat transfer mechanisms. From these results, two approaches to analyze the heat transfer were followed. The first approach described the phenomena in a single tube as a series of thermal resistances, where a pure conduction controlled heat transfer was assumed in the PCM. For the second approach, the temperature measurements were used to find some significant dimensionless numbers and parameters as Stefan, Fourier and Rayleigh numbers, and the melting fraction. These approaches allowed us to identify the heat transfer phenomena during both cycles. The presence of natural convection during melting might have been stated from the influence of the Rayleigh number on the correlations obtained.

Keywords: phase change materials, air-PCM exchangers, convection, conduction

Procedia PDF Downloads 178

Authors: Razia Hossaini, Maryam Hosseini

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Background and Objective: The impact of smoking on the shift in oral microbial composition has been questioned. This study aims to compare the oral microbiome between Turkish patients with dental caries and healthy individuals. Materials and Methods: An observational case-control study was conducted from January to June 2024, involving 270 young adults (180 with dental caries and 90 healthy controls). Participants were matched by age, gender, education, sugar consumption, and tooth brushing habits. Oral samples were collected using sterilized swabs and preserved in a PBS-glycerol solution. The cultured bacterial samples were characterized based on their morphological characteristics, Gram staining properties, hemolysis patterns, and biochemical tests including methyl red, sugar fermentation, Simmons citrate utilization, coagulase production, and catalase activity. These tests were conducted to accurately identify the bacterial species present. Subsequently, the relationship between smoking and oral health was evaluated, with a particular focus on assessing the smoking-induced changes in the composition of the oral microbiota using statistical analyses. Results: The study’s results demonstrate a clear association between smoking and an increased risk of dental caries, as well as significant shifts in the oral microbiota of smokers (p=0.04). These findings emphasize the critical need for public health initiatives that target smoking cessation as a means of improving oral health outcomes. Since smokers are 1.28 times more likely to develop dental caries than non-smokers, public health campaigns should incorporate messages that highlight the direct impact of smoking on oral health, alongside the well-established risks such as lung disease and cardiovascular conditions.The observed alterations in the oral microbiota—specifically the higher prevalence of pathogens like Escherichia coli, Pseudomonas aeruginosa, Streptococcus mutans, and Lactobacillus acidophilus in patients with dental caries—suggest that smoking not only predisposes individuals to dental decay but also creates an environment conducive to the growth of harmful bacteria. Public health interventions could therefore focus on the dual benefit of smoking cessation: reducing the incidence of dental caries and restoring a healthier oral microbiome. Additionally, the reduced presence of beneficial or less pathogenic species such as Neisseria and Micrococcus luteus in smokers implies that smoking alters the protective balance of the oral microbiome. This further underscores the importance of preventive oral health strategies tailored to smokers. Conclusion: Smoking significantly impacts oral health by promoting dysbiosis, increasing cariogenic bacteria, and reducing beneficial bacteria, which contributes to the development of dental caries. These findings highlight the need for integrated public health efforts that address both smoking cessation and oral health promotion. By raising awareness of the specific oral health risks associated with smoking, public health initiatives could help reduce the burden of dental caries and other smoking-related oral diseases, ultimately improving quality of life for individuals and reducing healthcare costs.

Keywords: smoking, dysbiosis, bacteria, oral health, dental decay

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Authors: Miroslav Premrov, Andrej Štrukelj, Erika Kozem Šilih

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The utilization of prefabricated timber-wall elements with double glazing, called as double-skin façade element (DSF), represents an innovative structural approach in the context of new high-rise timber construction, simultaneously combining sustainable solutions with improved energy efficiency and living quality. In addition to the minimum energy needs of buildings, the design of modern buildings is also increasingly focused on the optimal indoor comfort, in particular on sufficient natural light indoors. An optimally energy-designed building with an optimal layout of glazed areas around the building envelope represents a great potential in modern timber construction. Usually, all these transparent façade elements, because of energy benefits, are primary asymmetrical oriented and if they are considered as non-resisting against a horizontal load impact, a strong torsion effects in the building can appear. The problem of structural stability against a strong horizontal load impact of such modern timber buildings especially increase in a case of high-rise structures where additional bracing elements have to be used. In such a case, special diagonal bracing systems or other bracing solutions with common timber wall elements have to be incorporated into the structure of the building to satisfy all prescribed resisting requirements given by the standards. However, all such structural solutions are usually not environmentally friendly and also not contribute to an improved living comfort, or they are not accepted by the architects at all. Consequently, it is a special need to develop innovative load-bearing timber-glass wall elements which are in the same time environmentally friendly, can increase internal comfort in the building, but are also load-bearing. The new developed load-bearing DSF elements can be a good answer on all these requirements. Timber-glass façade elements DSF wall elements consist of two transparent layers, thermal-insulated three-layered glass pane on the internal side and an additional single-layered glass pane on the external side of the wall. The both panes are separated by an air channel which can be of any dimensions and can have a significant influence on the thermal insulation or acoustic response of such a wall element. Most already published studies on DSF elements primarily deal only with energy and LCA solutions and do not address any structural problems. In previous studies according to experimental analysis and mathematical modeling it was already presented a possible benefit of such load-bearing DSF elements, especially comparing with previously developed load-bearing single-skin timber wall elements, but they were not applicate yet in any high-rise timber structure. Therefore, in the presented study specially selected 10-storey prefabricated timber building constructed in a cross-laminated timber (CLT) structural wall system is analyzed using the developed DSF elements in a sense to increase a structural lateral stability of the whole building. The results evidently highlight the importance the load-bearing DSF elements, as their incorporation can have a significant impact on the overall behavior of the structure through their influence on the stiffness properties. Taking these considerations into account is crucial to ensure compliance with seismic design codes and to improve the structural resilience of high-rise timber buildings.

Keywords: glass, high-rise buildings, numerical analysis, timber

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Authors: Amine Ganibardi, Cherif Arab Ali

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This paper addresses the data cleaning issue as a part of web usage data preprocessing within the scope of Web Usage Mining. Weblog data recorded by web servers within log files reflect usage activity, i.e., End-users’ clicks and underlying user-agents’ hits. As Web Usage Mining is interested in End-users’ behavior, user-agents’ hits are referred to as noise to be cleaned-off before mining. Filtering hits from clicks is not trivial for two reasons, i.e., a server records requests interlaced in sequential order regardless of their source or type, website resources may be set up as requestable interchangeably by end-users and user-agents. The current methods are content-centric based on filtering heuristics of relevant/irrelevant items in terms of some cleaning attributes, i.e., website’s resources filetype extensions, website’s resources pointed by hyperlinks/URIs, http methods, user-agents, etc. These methods need exhaustive extra-weblog data and prior knowledge on the relevant and/or irrelevant items to be assumed as clicks or hits within the filtering heuristics. Such methods are not appropriate for dynamic/responsive Web for three reasons, i.e., resources may be set up to as clickable by end-users regardless of their type, website’s resources are indexed by frame names without filetype extensions, web contents are generated and cancelled differently from an end-user to another. In order to overcome these constraints, a clustering-based cleaning method centered on the logging structure is proposed. This method focuses on the statistical properties of the logging structure at the requested and referring resources attributes levels. It is insensitive to logging content and does not need extra-weblog data. The used statistical property takes on the structure of the generated logging feature by webpage requests in terms of clicks and hits. Since a webpage consists of its single URI and several components, these feature results in a single click to multiple hits ratio in terms of the requested and referring resources. Thus, the clustering-based method is meant to identify two clusters based on the application of the appropriate distance to the frequency matrix of the requested and referring resources levels. As the ratio clicks to hits is single to multiple, the clicks’ cluster is the smallest one in requests number. Hierarchical Agglomerative Clustering based on a pairwise distance (Gower) and average linkage has been applied to four logfiles of dynamic/responsive websites whose click to hits ratio range from 1/2 to 1/15. The optimal clustering set on the basis of average linkage and maximum inter-cluster inertia results always in two clusters. The evaluation of the smallest cluster referred to as clicks cluster under the terms of confusion matrix indicators results in 97% of true positive rate. The content-centric cleaning methods, i.e., conventional and advanced cleaning, resulted in a lower rate 91%. Thus, the proposed clustering-based cleaning outperforms the content-centric methods within dynamic and responsive web design without the need of any extra-weblog. Such an improvement in cleaning quality is likely to refine dependent analysis.

Keywords: clustering approach, data cleaning, data preprocessing, weblog data, web usage data

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Authors: Аndrey Marchenko, Oleg Linkov, Alexander Osetrov, Sergiy Kravchenko

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The low-calorie of gases include biogas, coal gas, coke oven gas, associated petroleum gas, gases sewage, etc. These gases are usually released into the atmosphere or burned on flares, causing substantial damage to the environment. However, with the right approach, low-calorie gas fuel can become a valuable source of energy. Specified determines the relevance of areas related to the development of low-calorific gas utilization technologies. As an example, in the work considered one of way of utilization of coalmine gas, because Ukraine ranks fourth in the world in terms of coal mine gas emission (4.7% of total global emissions, or 1.2 billion m³ per year). Experts estimate that coal mine gas is actively released in the 70-80 percent of existing mines in Ukraine. The main component of coal mine gas is methane (25-60%) Methane in 21 times has a greater impact on the greenhouse effect than carbon dioxide disposal problem has become increasingly important in the context of the increasing need to address the problems of climate, ecology and environmental protection. So marked causes negative effect of both local and global nature. The efforts of the United Nations and the World Bank led to the adoption of the program 'Zero Routine Flaring by 2030' dedicated to the cessation of these gases burn in flares and disposing them with the ability to generate heat and electricity. This study proposes to use coal gas as a fuel for gas engines to generate heat and electricity. Analyzed the physical-chemical properties of low-calorie gas fuels were allowed to choose a suitable engine, as well as estimate the influence of the composition of the fuel at its techno-economic indicators. Most suitable for low-calorie gas is engine with pre-combustion chamber jet ignition. In Ukraine is accumulated extensive experience in exploitation and production of gas engines with capacity of 1100 kW type GD100 (10GDN 207/2 * 254) fueled by natural gas. By using system pre- combustion chamber jet ignition and quality control in the engines type GD100 introduces the concept of burning depleted burn fuel mixtures, which in turn leads to decrease in the concentration of harmful substances of exhaust gases. The main problems of coal mine gas as a fuel for ICE is low calorific value, the presence of components that adversely affect combustion processes and terms of operation of the ICE, the instability of the composition, weak ignition. In some cases, these problems can be solved by adaptation engine design using coal mine gas as fuel (changing compression ratio, fuel injection quantity increases, change ignition time, increase energy plugs, etc.). It is shown that the use of coal mine gas engines with prechamber has not led to significant changes in the indicator parameters (ηi = 0.43 - 0.45). However, this significantly increases the volumetric fuel consumption, which requires increased fuel injection quantity to ensure constant nominal engine power. Thus, the utilization of low-calorie gas fuels in stationary gas engine type-based GD100 will significantly reduce emissions of harmful substances into the atmosphere when the generate cheap electricity and heat.

Keywords: gas engine, low-calorie gas, methane, pre-combustion chamber, utilization

Procedia PDF Downloads 264

Authors: Ruolan Zhang, Ryo Imai, Naoko Senda, Tomoyuki Sakai

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Enzymes have attracted increasing attentions in industrial manufacturing for their applicability in catalyzing complex chemical reactions under mild conditions. Directed evolution has become a powerful approach to optimize enzymes and exploit their full potentials under the circumstance of insufficient structure-function knowledge. With the incorporation of cell-free synthetic biotechnology, rapid enzyme synthesis can be realized because no cloning procedure such as transfection is needed. Its open environment also enables direct enzyme measurement. These properties of cell-free biotechnology lead to excellent throughput of enzymes generation. However, the capabilities of current screening methods have limitations. Fluorescence-based assay needs applicable fluorescent label, and the reliability of acquired enzymatic activity is influenced by fluorescent label’s binding affinity and photostability. To acquire the natural activity of an enzyme, another method is to combine pre-screening step and high-performance liquid chromatography (HPLC) measurement. But its throughput is limited by necessary time investment. Hundreds of variants are selected from libraries, and their enzymatic activities are then identified one by one by HPLC. The turn-around-time is 30 minutes for one sample by HPLC, which limits the acquirable enzyme improvement within reasonable time. To achieve the real high-throughput enzyme screening, i.e., obtain reliable enzyme improvement within reasonable time, a widely applicable high-throughput measurement of enzymatic reactions is highly demanded. Here, a high-throughput screening method using broadband coherent anti-Stokes Raman spectroscopy (CARS) was proposed. CARS is one of coherent Raman spectroscopy, which can identify label-free chemical components specifically from their inherent molecular vibration. These characteristic vibrational signals are generated from different vibrational modes of chemical bonds. With the broadband CARS, chemicals in one sample can be identified from their signals in one broadband CARS spectrum. Moreover, it can magnify the signal levels to several orders of magnitude greater than spontaneous Raman systems, and therefore has the potential to evaluate chemical's concentration rapidly. As a demonstration of screening with CARS, alcohol dehydrogenase, which converts ethanol and nicotinamide adenine dinucleotide oxidized form (NAD+) to acetaldehyde and nicotinamide adenine dinucleotide reduced form (NADH), was used. The signal of NADH at 1660 cm⁻¹, which is generated from nicotinamide in NADH, was utilized to measure the concentration of it. The evaluation time for CARS signal of NADH was determined to be as short as 0.33 seconds while having a system sensitivity of 2.5 mM. The time course of alcohol dehydrogenase reaction was successfully measured from increasing signal intensity of NADH. This measurement result of CARS was consistent with the result of a conventional method, UV-Vis. CARS is expected to have application in high-throughput enzyme screening and realize more reliable enzyme improvement within reasonable time.

Keywords: Coherent Anti-Stokes Raman Spectroscopy, CARS, directed evolution, enzyme screening, Raman spectroscopy

Procedia PDF Downloads 141

Authors: Kamolvara Sirisuksakulchai, Soamwadee Chaianansutcharit, Kazunori Sato

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Solid Oxide Fuel Cells (SOFCs) have been considered as one of the most efficient large unit power generators for household and industrial applications. The efficiency of an electronic cell depends mainly on the electrochemical reactions in the anode. The development of anode materials has been intensely studied to achieve higher kinetic rates of redox reactions and lower internal resistance. Recent studies have introduced an efficient cermet (ceramic-metallic) material for its ability in fuel oxidation and oxide conduction. This could expand the reactive site, also known as the triple-phase boundary (TPB), thus increasing the overall performance. In this study, a bimetallic catalyst Ni₀.₇₅Co₀.₂₅Oₓ was combined with Gd₀.₁Ce₀.₉O₁.₉₅ (GDC) to be used as a cermet anode (NiCo-GDC) for an anode-supported type SOFC. The synthesis of Ni₀.₇₅Co₀.₂₅Oₓ was carried out by ball milling NiO and Co3O4 powders in ethanol and calcined at 1000 °C. The Gd₀.₁Ce₀.₉O₁.₉₅ was prepared by a urea co-precipitation method. Precursors of Gd(NO₃)₃·6H₂O and Ce(NO₃)₃·6H₂O were dissolved in distilled water with the addition of urea and were heated subsequently. The heated mixture product was filtered and rinsed thoroughly, then dried and calcined at 800 °C and 1500 °C, respectively. The two powders were combined followed by pelletization and sintering at 1100 °C to form an anode support layer. The fabrications of an electrolyte layer and cathode layer were conducted. The electrochemical performance in H₂ was measured from 800 °C to 600 °C while for CH₄ was from 750 °C to 600 °C. The maximum power density at 750 °C in H₂ was 13% higher than in CH₄. The difference in performance was due to higher polarization resistances confirmed by the impedance spectra. According to the standard enthalpy, the dissociation energy of C-H bonds in CH₄ is slightly higher than the H-H bond H₂. The dissociation of CH₄ could be the cause of resistance within the anode material. The results from lower temperatures showed a descending trend of power density in relevance to the increased polarization resistance. This was due to lowering conductivity when the temperature decreases. The long-term stability was measured at 750 °C in CH₄ monitoring at 12-hour intervals. The maximum power density tends to increase gradually with time while the resistances were maintained. This suggests the enhanced stability from charge transfer activities in doped ceria due to the transition of Ce⁴⁺ ↔ Ce³⁺ at low oxygen partial pressure and high-temperature atmosphere. However, the power density started to drop after 60 h, and the cell potential also dropped from 0.3249 V to 0.2850 V. These phenomena was confirmed by a shifted impedance spectra indicating a higher ohmic resistance. The observation by FESEM and EDX-mapping suggests the degradation due to mass transport of ions in the electrolyte while the anode microstructure was still maintained. In summary, the electrochemical test and stability test for 60 h was achieved by NiCo-GDC cermet anode. Coke deposition was not detected after operation in CH₄, hence this confirms the superior properties of the bimetallic cermet anode over typical Ni-GDC.

Keywords: bimetallic catalyst, ceria-based SOFCs, methane oxidation, solid oxide fuel cell

Procedia PDF Downloads 154

Authors: Panagiota Katsikouli, William Hamilton Byrne, Thomas Gammeltoft-Hansen, Tijs Slaats

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An individual who demonstrates a well-founded fear of persecution or faces real risk of being subjected to torture is eligible for asylum. In Danish law, the exact legal thresholds reflect those established by international conventions, notably the 1951 Refugee Convention and the 1950 European Convention for Human Rights. These international treaties, however, remain largely silent when it comes to how states should assess asylum claims. As a result, national authorities are typically left to determine an individual’s legal eligibility on a narrow basis consisting of an oral testimony, which may itself be hampered by several factors, including imprecise language interpretation, insecurity or lacking trust towards the authorities among applicants. The leaky ground, on which authorities must assess their subjective perceptions of asylum applicants' credibility, questions whether, in all cases, adjudicators make the correct decision. Moreover, the subjective element in these assessments raises questions on whether individual asylum cases could be afflicted by implicit biases or stereotyping amongst adjudicators. In fact, recent studies have uncovered significant correlations between decision outcomes and the experience and gender of the assigned judge, as well as correlations between asylum outcomes and entirely external events such as weather and political elections. In this study, we analyze a publicly available dataset containing approximately 8,000 summaries of asylum cases, initially rejected, and re-tried by the Refugee Appeals Board (RAB) in Denmark. First, we look for variations in the recognition rates, with regards to a number of applicants’ features: their country of origin/nationality, their identified gender, their identified religion, their ethnicity, whether torture was mentioned in their case and if so, whether it was supported or not, and the year the applicant entered Denmark. In order to extract those features from the text summaries, as well as the final decision of the RAB, we applied natural language processing and regular expressions, adjusting for the Danish language. We observed interesting variations in recognition rates related to the applicants’ country of origin, ethnicity, year of entry and the support or not of torture claims, whenever those were made in the case. The appearance (or not) of significant variations in the recognition rates, does not necessarily imply (or not) bias in the decision-making progress. None of the considered features, with the exception maybe of the torture claims, should be decisive factors for an asylum seeker’s fate. We therefore investigate whether the decision can be predicted on the basis of these features, and consequently, whether biases are likely to exist in the decisionmaking progress. We employed a number of machine learning classifiers, and found that when using the applicant’s country of origin, religion, ethnicity and year of entry with a random forest classifier, or a decision tree, the prediction accuracy is as high as 82% and 85% respectively. tentially predictive properties with regards to the outcome of an asylum case. Our analysis and findings call for further investigation on the predictability of the outcome, on a larger dataset of 17,000 cases, which is undergoing.

Keywords: asylum adjudications, automated decision-making, machine learning, text mining

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Authors: Päärn Paiste, Margit Kõiv, Riho Mõtlep, Kalle Kirsimäe

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For small-scale wastewater management, the treatment wetlands (TWs) as a low cost alternative to conventional treatment facilities, can be used. However, P removal capacity of TW systems is usually problematic. P removal in TWs is mainly dependent on the physico–chemical and hydrological properties of the filter material. Highest P removal efficiency has been shown trough Ca-phosphate precipitation (i.e. active filtration) in Ca-rich alkaline filter materials, e.g. industrial by-products like hydrated oil shale ash (HOSA), metallurgical slags. In this contribution we report preliminary results of a full-scale TW system using HOSA material for P removal for a municipal wastewater at Nõo site, Estonia. The main goals of this ongoing project are to evaluate: a) the long-term P removal efficiency of HOSA using real waste water; b) the effect of high organic loading rate; c) variable P-loading effects on the P removal mechanism (adsorption/direct precipitation); and d) the form and composition of phosphate precipitates. Onsite full-scale experiment with two concurrent filter systems for treatment of municipal wastewater was established in September 2013. System’s pretreatment steps include septic tank (2 m2) and vertical down-flow LECA filters (3 m2 each), followed by horizontal subsurface HOSA filters (effective volume 8 m3 each). Overall organic and hydraulic loading rates of both systems are the same. However, the first system is operated in a stable hydraulic loading regime and the second in variable loading regime that imitates the wastewater production in an average household. Piezometers for water and perforated sample containers for filter material sampling were incorporated inside the filter beds to allow for continuous in-situ monitoring. During the 18 months of operation the median removal efficiency (inflow to outflow) of both systems were over 99% for TP, 93% for COD and 57% for TN. However, we observed significant differences in the samples collected in different points inside the filter systems. In both systems, we observed development of preferred flow paths and zones with high and low loadings. The filters show formation and a gradual advance of a “dead” zone along the flow path (zone with saturated filter material characterized by ineffective removal rates), which develops more rapidly in the system working under variable loading regime. The formation of the “dead” zone is accompanied by the growth of organic substances on the filter material particles that evidently inhibit the P removal. Phase analysis of used filter materials using X-ray diffraction method reveals formation of minor amounts of amorphous Ca-phosphate precipitates. This finding is supported by ATR-FTIR and SEM-EDS measurements, which also reveal Ca-phosphate and authigenic carbonate precipitation. Our first experimental results demonstrate that organic pollution and loading regime significantly affect the performance of hydrated ash filters. The material analyses also show that P is incorporated into a carbonate substituted hydroxyapatite phase.

Keywords: active filtration, apatite, hydrated oil shale ash, organic pollution, phosphorus

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Authors: Dimitra C. Banti, Gesthimani Liona, Petros Samaras, Manasis Mitrakas

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Municipal and industrial wastewaters are often treated biologically, by the activated sludge process (ASP). The ASP not only requires large aeration and sedimentation tanks, but also generates large quantities of excess sludge. An alternative technology is the membrane bioreactor (MBR), which replaces two stages of the conventional ASP—clarification and settlement—with a single, integrated biotreatment and clarification step. The advantages offered by the MBR over conventional treatment include reduced footprint and sludge production through maintaining a high biomass concentration in the bioreactor. Notwithstanding these advantages, the widespread application of the MBR process is constrained by membrane fouling. Fouling leads to permeate flux decline, making more frequent membrane cleaning and replacement necessary and resulting to increased operating costs. In general, membrane fouling results from the interaction between the membrane material and the components in the activated sludge liquor. The latter includes substrate components, cells, cell debris and microbial metabolites, such as Extracellular Polymeric Substances (EPS) and Sludge Microbial Products (SMPs). The challenge for effective MBR operation is to minimize the rate of Transmembrane Pressure (TMP) increase. This can be achieved by several ways, one of which is the addition of specific additives, that enhance the coagulation and flocculation of compounds, which are responsible for fouling, hence reducing biofilm formation on the membrane surface and limiting the fouling rate. In this project the effectiveness of a non-commercial composite coagulant was studied as an agent for fouling control in a lab scale MBR system consisting in two aerated tanks. A flat sheet membrane module with 0.40 um pore size was submerged into the second tank. The system was fed by50 L/d of municipal wastewater collected from the effluent of the primary sedimentation basin. The TMP increase rate, which is directly related to fouling growth, was monitored by a PLC system. EPS, MLSS and MLVSS measurements were performed in samples of mixed liquor; in addition, influent and effluent samples were collected for the determination of physicochemical characteristics (COD, BOD5, NO3-N, NH4-N, Total N and PO4-P). The coagulant was added in concentrations 2, 5 and 10mg/L during a period of 2 weeks and the results were compared with the control system (without coagulant addition). EPS fractions were extracted by a three stages physical-thermal treatment allowing the identification of Soluble EPS (SEPS) or SMP, Loosely Bound EPS (LBEPS) and Tightly Bound EPS (TBEPS). Proteins and carbohydrates concentrations were measured in EPS fractions by the modified Lowry method and Dubois method, respectively. Addition of 2 mg/L coagulant concentration did not affect SEPS proteins in comparison with control process and their values varied between 32 to 38mg/g VSS. However a coagulant dosage of 5mg/L resulted in a slight increase of SEPS proteins at 35-40 mg/g VSS while 10mg/L coagulant further increased SEPS to 44-48mg/g VSS. Similar results were obtained for SEPS carbohydrates. Carbohydrates values without coagulant addition were similar to the corresponding values measured for 2mg/L coagulant; the addition of mg/L coagulant resulted to a slight increase of carbohydrates SEPS to 6-7mg/g VSS while a dose of 10 mg/L further increased carbohydrates content to 9-10mg/g VSS. Total LBEPS and TBEPS, consisted of proteins and carbohydrates of LBEPS and TBEPS respectively, presented similar variations by the addition of the coagulant. Total LBEPS at 2mg/L dose were almost equal to 17mg/g VSS, and their values increased to 22 and 29 mg/g VSS during the addition of 5 mg/L and 10 mg/L of coagulant respectively. Total TBEPS were almost 37 mg/g VSS at a coagulant dose of 2 mg/L and increased to 42 and 51 mg/g VSS at 5 mg/L and 10 mg/L doses, respectively. Therefore, it can be concluded that coagulant addition could potentially affect microorganisms activities, excreting EPS in greater amounts. Nevertheless, EPS increase, mainly SEPS increase, resulted to a higher membrane fouling rate, as justified by the corresponding TMP increase rate. However, the addition of the coagulant, although affected the EPS content in the reactor mixed liquor, did not change the filtration process: an effluent of high quality was produced, with COD values as low as 20-30 mg/L.

Keywords: extracellular polymeric substances, MBR, membrane fouling, EPS

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Authors: Manuel Alejandro Taborda Ceballos, Martin Sommerfeld

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Transport phenomena and dispersion of non-spherical particle in turbulent flows are found everywhere in industrial application and processes. Powder handling, pollution control, pneumatic transport, particle separation are just some examples where the particle encountered are not only spherical. These types of multiphase flows are wall bounded and mostly highly turbulent. The particles found in these processes are rarely spherical but may have various shapes (e.g., fibers, and rods). Although research related to the behavior of regular non-spherical particles in turbulent flows has been carried out for many years, it is still necessary to refine models, especially near walls where the interaction fiber-wall changes completely its behavior. Imaging-based experimental studies on dispersed particle-laden flows have been applied for many decades for a detailed experimental analysis. These techniques have the advantages that they provide field information in two or three dimensions, but have a lower temporal resolution compared to point-wise techniques such as PDA (phase-Doppler anemometry) and derivations therefrom. The applied imaging techniques in dispersed two-phase flows are extensions from classical PIV (particle image velocimetry) and PTV (particle tracking velocimetry) and the main emphasis was simultaneous measurement of the velocity fields of both phases. In a similar way, such data should also provide adequate information for validating the proposed models. Available experimental studies on the behavior of non-spherical particles are uncommon and mostly based on planar light-sheet measurements. Especially for elongated non-spherical particles, however, three-dimensional measurements are needed to fully describe their motion and to provide sufficient information for validation of numerical computations. For further providing detailed experimental results allowing a validation of numerical calculations of non-spherical particle dispersion in turbulent flows, a water channel test facility was built around a horizontal closed water channel. Into this horizontal main flow, a small cross-jet laden with fiber-like particles was injected, which was also solely driven by gravity. The dispersion of the fibers was measured by applying imaging techniques based on a LED array for backlighting and high-speed cameras. For obtaining the fluid velocity fields, almost neutrally buoyant tracer was used. The discrimination between tracer and fibers was done based on image size which was also the basis to determine fiber orientation with respect to the inertial coordinate system. The synchronous measurement of fluid velocity and fiber properties also allow the collection of statistics of fiber orientation, velocity fields of tracer and fibers, the angular velocity of the fibers and the orientation between fiber and instantaneous relative velocity. Consequently, an experimental study the behavior of elongated non-spherical particles in wall bounded turbulent flows was achieved. The development of a comprehensive analysis was succeeded, especially near the wall region, where exists hydrodynamic wall interaction effects (e.g., collision or lubrication) and abrupt changes of particle rotational velocity. This allowed us to predict numerically afterwards the behavior of non-spherical particles within the frame of the Euler/Lagrange approach, where the particles are therein treated as “point-particles”.

Keywords: crossflow, non-spherical particles, particle tracking velocimetry, PIV

Procedia PDF Downloads 86

Authors: Inna Kornienko, Svetlana Guryeva, Anatoly Shekhter, Elena Petersen

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Transplantation is an effective treatment option for patients suffering from different end-stage diseases. However, it is plagued by a constant shortage of donor organs and the subsequent need of a lifelong immunosuppressive therapy for the patient. Currently some researchers look towards using of pig organs to replace human organs for transplantation since the matrix derived from porcine organs is a convenient substitute for the human matrix. As an initial step to create a new ex vivo tissue engineered model, optimized protocols have been created to obtain organ-specific acellular matrices and evaluated their potential as tissue engineered scaffolds for culture of normal cells and tumor cell lines. These protocols include decellularization by perfusion in a bioreactor system and immersion-agitation on an orbital shaker with use of various detergents (SDS, Triton X-100) and freezing. Complete decellularization – in terms of residual DNA amount – is an important predictor of probability of immune rejection of materials of natural origin. However, the signs of cellular material may still remain within the matrix even after harsh decellularization protocols. In this regard, the matrices obtained from tissues of low-immunogenic pigs with α3Galactosyl-tranferase gene knock out (GalT-KO) may be a promising alternative to native animal sources. The research included a study of induced effect of frozen and fresh fragments of GalT-KO skin on healing of full-thickness plane wounds in 80 rats. Commercially available wound dressings (Ksenoderm, Hyamatrix and Alloderm) as well as allogenic skin were used as a positive control and untreated wounds were analyzed as a negative control. The results were evaluated on the 4th day after grafting, which corresponds to the time of start of normal wound epithelization. It has been shown that a non-specific immune response in models treated with GalT-Ko pig skin was milder than in all the control groups. Research has been performed to measure technical skin characteristics: stiffness and elasticity properties, corneometry, tevametry, and cutometry. These metrics enabled the evaluation of hydratation level, corneous layer husking level, as well as skin elasticity and micro- and macro-landscape. These preliminary data may contribute to development of personalized transplantable organs from GalT-Ko pigs with significantly limited potential of immune rejection. By applying growth factors to a decellularized skin sample it is possible to achieve various regenerative effects based on the particular situation. In this particular research BMP2 and Heparin-binding EGF-like growth factor have been used. Ideally, a bioengineered organ must be biocompatible, non-immunogenic and support cell growth. Porcine organs are attractive for xenotransplantation if severe immunologic concerns can be bypassed. The results indicate that genetically modified pig tissues with knock-outed α3Galactosyl-tranferase gene may be used for production of low-immunogenic matrix suitable for transplantation.

Keywords: decellularization, low-immunogenic, matrix, scaffolds, transplants

Procedia PDF Downloads 275

Authors: S. N. T. I. Sampath, J. M. S. Jayasinghe, A. P. Attanayake, V. Karunaratne

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Diabetes mellitus is one of the major public health posers throughout the world today that incidence and associated with increasing mortality. Insufficient regulation of the blood glucose level might be serious effects for health and its necessity to identify new therapeutics that have ability to reduce hyperglycaemic condition in the human body. Even though synthetic antidiabetic drugs are more effective to control diabetes mellitus, there are considerable side effects have been reported. Thus, there is an increasing demand for searching new natural products having high antidiabetic activity with lesser side effects. The purposes of the present study were to evaluate different physical parameters and in-vitro and in-vivo antidiabetic potential of the selected combined medicinal plant extracts mixture composed of leaves of Murraya koenigii, cloves of Allium sativum, fruits of Garcinia queasita and seeds of Piper nigrum. The selected plants parts were mixed and ground together and extracted sequentially into the hexane, ethyl acetate and methanol. Solvents were evaporated and they were further dried by freeze-drying to obtain a fine powder of each extract. Various physical parameters such as moisture, total ash, acid insoluble ash and water soluble ash were evaluated using standard test procedures. In-vitro antidiabetic activity of combined plant extracts mixture was screened using enzyme assays such as α-amylase inhibition assay and α-glucosidase inhibition assay. The acute anti-hyperglycaemic activity was performed using oral glucose tolerance test for the streptozotocin induced diabetic Wistar rats to find out in-vivo antidiabetic activity of combined plant extracts mixture and it was assessed through total oral glucose tolerance curve (TAUC) values. The percentage of moisture content, total ash content, acid insoluble ash content and water soluble ash content were ranged of 7.6-17.8, 8.1-11.78, 0.019-0.134 and 6.2-9.2 respectively for the plant extracts and those values were less than standard values except the methanol extract. The hexane and ethyl acetate extracts exhibited highest α-amylase (IC50 = 25.7 ±0.6; 27.1 ±1.2 ppm) and α-glucosidase (IC50 = 22.4 ±0.1; 33.7 ±0.2 ppm) inhibitory activities than methanol extract (IC50 = 360.2 ±0.6; 179.6 ±0.9 ppm) when compared with the acarbose positive control (IC50 = 5.7 ±0.4; 17.1 ±0.6 ppm). The TAUC values for hexane, ethyl acetate, and methanol extracts and glibenclamide (positive control) treated rats were 8.01 ±0.66; 8.05 ±1.07; 8.40±0.50; 5.87 ±0.93 mmol/L.h respectively, whereas in diabetic control rats the TAUC value was 13.22 ±1.07 mmol/L.h. Administration of plant extracts treated rats significantly suppressed (p<0.05) the rise in plasma blood glucose levels compared to control rats but less significant than glibenclamide. The obtained results from in-vivo and in-vitro antidiabetic study showed that the hexane and ethyl acetate extracts of selected combined plant mixture might be considered as a potential source to isolate natural antidiabetic agents and physical parameters of hexane and ethyl acetate extracts will helpful to develop antidiabetic drug with further standardize properties.

Keywords: diabetes mellitus, in-vitro antidiabetic assays, medicinal plants, standardization

Procedia PDF Downloads 131

Authors: Chen Jiang, Eric Jordan, Maurice Gell, Balakrishnan Nair

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Nuclear fusion, one of the most promising options for reliably generating large amounts of carbon-free energy in the future, has seen a plethora of ground-breaking technological advances in recent years. An efficient and durable “breeding blanket”, needed to ensure a reactor’s self-sufficiency by maintaining the optimal coolant temperature as well as by minimizing radiation dosage behind the blanket, still remains a technological challenge for the various reactor designs for commercial fusion power plants. A relatively new dual-coolant lead-lithium (DCLL) breeder design has exhibited great potential for high-temperature (>700oC), high-thermal-efficiency (>40%) fusion reactor operation. However, the structural material, namely reduced activation ferritic-martensitic (RAFM) steel, is not chemically stable in contact with molten Pb-17%Li coolant. Thus, to utilize this new promising reactor design, the demand for effective corrosion-resistant coatings on RAFM steels represents a pressing need. Solution Spray Technologies LLC (SST) is developing a double-layer ceramic coating design to address the corrosion protection of RAFM steels, using a novel solution and solution/suspension plasma spray technology through a US Department of Energy-funded project. Plasma spray is a coating deposition method widely used in many energy applications. Novel derivatives of the conventional powder plasma spray process, known as the solution-precursor and solution/suspension-hybrid plasma spray process, are powerful methods to fabricate thin, dense ceramic coatings with complex compositions necessary for the corrosion protection in DCLL breeders. These processes can be used to produce ultra-fine molten splats and to allow fine adjustment of coating chemistry. Thin, dense ceramic coatings with chosen chemistry for superior chemical stability in molten Pb-Li, low activation properties, and good radiation tolerance, is ideal for corrosion-protection of RAFM steels. A key challenge is to accommodate its CTE mismatch with the RAFM substrate through the selection and incorporation of appropriate bond layers, thus allowing for enhanced coating durability and robustness. Systematic process optimization is being used to define the optimal plasma spray conditions for both the topcoat and bond-layer, and X-ray diffraction and SEM-EDS are applied to successfully validate the chemistry and phase composition of the coatings. The plasma-sprayed double-layer corrosion resistant coatings were also deposited onto simulated RAFM steel substrates, which are being tested separately under thermal cycling, high-temperature moist air oxidation as well as molten Pb-Li capsule corrosion conditions. Results from this testing on coated samples, and comparisons with bare RAFM reference samples will be presented and conclusions will be presented assessing the viability of the new ceramic coatings to be viable corrosion prevention systems for DCLL breeders in commercial nuclear fusion reactors.

Keywords: breeding blanket, corrosion protection, coating, plasma spray

Procedia PDF Downloads 308

Authors: Pedro A. Marques, Francisco Monteiro, Alessandra Zumbo, Alessia Simonini, Miguel A. Mendez

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Cryogenic fuels such as Liquid Hydrogen (LH₂) must be transported and stored at extremely low temperatures. Without expensive active cooling solutions, preventing fuel boil-off over time is impossible. Hence, one must resort to venting systems at the cost of significant energy and fuel mass loss. These losses increase significantly in propellant tanks installed on vehicles, as the presence of external accelerations induces sloshing. Sloshing increases heat and mass transfer rates and leads to significant pressure oscillations, which might further trigger propellant venting. To make LH₂ economically viable, it is essential to minimize these factors by using advanced control techniques. However, these require accurate modelling and a full understanding of the tank's thermodynamics. The present research aims to implement a simple thermodynamic model capable of predicting the state of a cryogenic fuel tank under different operating conditions (i.e., filling, pressurization, fuel extraction, long-term storage, and sloshing). Since this model relies on a set of closure parameters to drive the system's transient response, it must be calibrated using experimental or numerical data. This work focuses on the former approach, wherein the model is calibrated through an experimental campaign carried out on a reduced-scale model of a cryogenic tank. The thermodynamic model of the system is composed of three control volumes: the ullage, the liquid, and the insulating walls. Under this lumped formulation, the governing equations are derived from energy and mass balances in each region, with mass-averaged properties assigned to each of them. The gas-liquid interface is treated as an infinitesimally thin region across which both phases can exchange mass and heat. This results in a coupled system of ordinary differential equations, which must be closed with heat and mass transfer coefficients between each control volume. These parameters are linked to the system evolution via empirical relations derived from different operating regimes of the tank. The derivation of these relations is carried out using an inverse method to find the optimal relations that allow the model to reproduce the available data. This approach extends classic system identification methods beyond linear dynamical systems via a nonlinear optimization step. Thanks to the data-driven assimilation of the closure problem, the resulting model accurately predicts the evolution of the tank's thermodynamics at a negligible computational cost. The lumped model can thus be easily integrated with other submodels to perform complete system simulations in real time. Moreover, by setting the model in a dimensionless form, a scaling analysis allowed us to relate the tested configurations to a representative full-size tank for naval applications. It was thus possible to compare the relative importance of different transport phenomena between the laboratory model and the full-size prototype among the different operating regimes.

Keywords: destratification, hydrogen, modeling, pressure-drop, pressurization, sloshing, thermodynamics

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Authors: Priyanka Sharma, Ranjita Das, Mohan C. Kalita, Debajit Thakur

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Background: Actinomycetes are the richest source of novel bioactive secondary metabolites such as antibiotics, enzymes and other therapeutically useful metabolites with diverse biological activities. The present study aims at the antimicrobial potential and genetic diversity of culturable Actinomycetes isolated from protected forest ecosystems of Assam which includes Kaziranga National Park (26°30˝-26°45˝N and 93°08˝-93°36˝E), Pobitora Wildlife Sanctuary (26º12˝-26º16˝N and 91º58˝-92º05˝E) and Gibbon Wildlife Sanctuary (26˚40˝-26˚45˝N and 94˚20˝-94˚25˝E) which are located in the North-eastern part of India. Northeast India is a part of the Indo-Burma mega biodiversity hotspot and most of the protected forests of this region are still unexplored for the isolation of effective antibiotic-producing Actinomycetes. Thus, there is tremendous possibility that these virgin forests could be a potential storehouse of novel microorganisms, particularly Actinomycetes, exhibiting diverse biological properties. Methodology: Soil samples were collected from different ecological niches of the protected forest ecosystems of Assam and Actinomycetes were isolated by serial dilution spread plate technique using five selective isolation media. Preliminary screening of Actinomycetes for an antimicrobial activity was done by spot inoculation method and the secondary screening by disc diffusion method against several test pathogens, including multidrug resistant Staphylococcus aureus (MRSA). The strains were further screened for the presence of antibiotic synthetic genes such as type I polyketide synthases (PKS-I), type II polyketide synthases (PKS-II) and non-ribosomal peptide synthetases (NRPS) genes. Genetic diversity of the Actinomycetes producing antimicrobial metabolites was analyzed through 16S rDNA-RFLP using Hinf1 restriction endonuclease. Results: Based on the phenotypic characterization, a total of 172 morphologically distinct Actinomycetes were isolated and screened for antimicrobial activity by spot inoculation method on agar medium. Among the strains tested, 102 (59.3%) strains showed activity against Gram-positive bacteria, 98 (56.97%) against Gram-negative bacteria, 92 (53.48%) against Candida albicans MTCC 227 and 130 (75.58%) strains showed activity against at least one of the test pathogens. Twelve Actinomycetes exhibited broad spectrum antimicrobial activity in the secondary screening. The taxonomic identification of these twelve strains by 16S rDNA sequencing revealed that Streptomyces was found to be the predominant genus. The PKS-I, PKS-II and NRPS genes detection indicated diverse bioactive products of these twelve Actinomycetes. Genetic diversity by 16S rDNA-RFLP indicated that Streptomyces was the dominant genus amongst the antimicrobial metabolite producing Actinomycetes. Conclusion: These findings imply that Actinomycetes from the protected forest ecosystems of Assam, India, are a potential source of bioactive secondary metabolites. These areas are as yet poorly studied and represent diverse and largely unscreened ecosystem for the isolation of potent Actinomycetes producing antimicrobial secondary metabolites. Detailed characterization of the bioactive Actinomycetes as well as purification and structure elucidation of the bioactive compounds from the potent Actinomycetes is the subject of ongoing investigation. Thus, to exploit Actinomycetes from such unexplored forest ecosystems is a way to develop bioactive products.

Keywords: Actinomycetes, antimicrobial activity, forest ecosystems, RFLP

Procedia PDF Downloads 391

Authors: Ting Wu, Feiting Hu, Xinyue Zhang, Shuxin Tang, Xiaoyun Xu

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As a by-product of yuba, processing wastewater of Yuba (PWY) contains many bioactive components such as soybean isoflavones, soybean polysaccharides and soybean oligosaccharides, which is a good source of prebiotics and has a potential of high value utilization. The use of Lactobacillus plantarum to ferment PWY can be considered as a potential biogenic element, which can regulate the balance of intestinal microbiota. In this study, firstly, Lactobacillus plantarum was used to ferment PWY to improve its content of active components and antioxidant activity. Then, the health effect of fermented processing wastewater of yuba (FPWY) was measured in vitro. Finally, microencapsulation technology was used applied to improve the sustained release of FPWY and reduce the loss of active components in the digestion process, as well as to improving the activity of FPWY. The main results are as follows: (1) FPWY presented a good antioxidant capacity with DPPH free radical scavenging ability (0.83 ± 0.01 mmol Trolox/L), ABTS free radical scavenging ability (7.47 ± 0.35 mmol Trolox/L) and iron ion reducing ability (1.11 ± 0.07 mmol Trolox/L). Compared with non-fermented processing wastewater of yuba (NFPWY), there was no significant difference in the content of total soybean isoflavones, but the content of glucoside soybean isoflavones decreased, and aglyconic soybean isoflavones increased significantly. After fermentation, PWY can effectively reduce the soluble monosaccharides, disaccharides and oligosaccharides, such as glucose, fructose, galactose, trehalose, stachyose, maltose, raffinose and sucrose. (2) FPWY can significantly enhance the growth of beneficial bacteria such as Bifidobacterium, Ruminococcus and Akkermansia, significantly inhibit the growth of harmful bacteria E.coli, regulate the structure of intestinal microbiota, and significantly increase the content of short-chain fatty acids such as acetic acid, propionic acid, butyric acid, isovaleric acid. Higher amount of lactic acid in the gut can be further broken down into short chain fatty acids. (3) In order to improve the stability of soybean isoflavones in FPWY during digestion, sodium alginate and chitosan were used as wall materials for embedding. The FPWY freeze-dried powder was embedded by the method of acute-coagulation bath. The results show that when the core wall ratio is 3:1, the concentration of chitosan is 1.5%, the concentration of sodium alginate is 2.0%, and the concentration of calcium is 3%, the embossing rate is 53.20%. In the simulated in vitro digestion stage, the release rate of microcapsules reached 59.36% at the end of gastric digestion and 82.90% at the end of intestinal digestion. Therefore, the core materials with good sustained-release performance of microcapsules were almost all released. The structural analysis results of FPWY microcapsules show that the microcapsules have good mechanical properties. Its hardness, springness, cohesiveness, gumminess, chewiness and resilience were 117.75± 0.21 g, 0.76±0.02, 0.54±0.01, 63.28±0.71 g·sec, 48.03±1.37 g·sec, 0.31±0.01, respectively. Compared with the unembedded FPWY, the infrared spectrum results showed that the microcapsules had embedded effect on the FPWY freeze-dried powder.

Keywords: processing wastewater of yuba, lactobacillus plantarum, intestinal microbiota, microcapsule

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Authors: Soma Ghosh, Balaram Mohapatra, Pinaki Sar, Abhijeet Mukherjee

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Microbial role in arsenic (As) mobilization in the groundwater aquifers of Brahmaputra river basin (BRB) in India, severely threatened by high concentrations of As, remains largely unknown. The present study, therefore, is a molecular and ecophysiological characterization of an indigenous bacterium strain IIIJ3-1 isolated from As contaminated groundwater of BRB and application of this strain in several microcosm set ups differing in their organic carbon (OC) source and terminal electron acceptors (TEA), to understand its role in As dissolution under aerobic and anaerobic conditions. Strain IIIJ3-1 was found to be a new facultative anaerobic, gram-positive, endospore-forming strain capable of arsenite (As3+) oxidation and dissimilatory arsenate (As5+) reduction. The bacterium exhibited low genomic (G+C)% content (45 mol%). Although, its 16S rRNA gene sequence revealed a maximum similarity of 99% with Bacillus cereus ATCC 14579(T) but the DNA-DNA relatedness of their genomic DNAs was only 49.9%, which remains well below the value recommended to delimit different species. Abundance of fatty acids iC17:0, iC15:0 and menaquinone (MK) 7 though corroborates its taxonomic affiliation with B. cereus sensu-lato group, presence of hydroxy fatty acids (HFAs), C18:2, MK5 and MK6 marked its uniqueness. Besides being highly As resistant (MTC=10mM As3+, 350mM As5+), metabolically diverse, efficient aerobic As3+ oxidizer; it exhibited near complete dissimilatory reduction of As5+ (1 mM). Utilization of various carbon sources with As5+ as TEA revealed lactate to serve as the best electron donor. Aerobic biotransformation assay yielded a lower Km for As3+ oxidation than As5+ reduction. Arsenic homeostasis was found to be conferred by the presence of arr, arsB, aioB, and acr3(1) genes. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) analysis of this bacterium revealed reduction in cell size upon exposure to As and formation of As-rich electron opaque dots following growth with As3+. Incubation of this strain with sediment (sterilised) collected from BRB aquifers under varying OC, TEA and redox conditions revealed that the strain caused highest As mobilization from solid to aqueous phase under anaerobic condition with lactate and nitrate as electron donor and acceptor, respectively. Co-release of highest concentrations of oxalic acid, a well known bioweathering agent, considerable fold increase in viable cell counts and SEM-EDX and X-ray diffraction analysis of the sediment after incubation under this condition indicated that As release is consequent to microbial bioweathering of the minerals. Co-release of other elements statistically proves decoupled release of As with Fe and Zn. Principle component analysis also revealed prominent role of nitrate under aerobic and/or anaerobic condition in As release by strain IIIJ3-1. This study, therefore, is the first to isolate, characterize and reveal As mobilization property of a strain belonging to the Bacillus cereus sensu lato group isolated from highly As contaminated aquifers of Brahmaputra River Basin.

Keywords: anaerobic microcosm, arsenic rich electron opaque dots, Arsenic release, Bacillus strain IIIJ3-1

Procedia PDF Downloads 127

Authors: B. Philip, J. Littlewood, R. Radford, N. Evans, T. Whyman, D. P. Jones

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UK buildings and energy infrastructures are heavily dependent on natural gas, a large proportion of which is used for domestic space heating. However, approximately half of the gas consumed in the UK is imported. Improving energy security and reducing carbon emissions are major government drivers for reducing gas dependency. In order to do so there needs to be a wholesale shift in the energy provision to householders without impacting on thermal comfort levels, convenience or cost of supply to the end user. Heat pumps are seen as a potential alternative in modern well insulated homes, however, can the same be said of older homes? A large proportion of housing stock in Britain was built prior to 1919. The age of the buildings bears testimony to the quality of construction; however, their thermal performance falls far below the minimum currently set by UK building standards. In recent years significant sums of money have been invested to improve energy efficiency and combat fuel poverty in some of the most deprived areas of Wales. Increasing energy efficiency of older properties remains a significant challenge, which cannot be achieved through insulation and air-tightness interventions alone, particularly when alterations to historically important architectural features of the building are not permitted. This paper investigates the energy demand of pre-1919 dwellings in a former Welsh mining village, the feasibility of meeting that demand using water from the disused mine workings to supply a district heat network and potential barriers to success of the scheme. The use of renewable solar energy generation and storage technologies, both thermal and electrical, to reduce the load and offset increased electricity demand, are considered. A wholistic surveying approach to provide a more accurate assessment of total household heat demand is proposed. Several surveying techniques, including condition surveys, air permeability, heat loss calculations, and thermography were employed to provide a clear picture of energy demand. Additional insulation can bring unforeseen consequences which are detrimental to the fabric of the building, potentially leading to accelerated dilapidation of the asset being ‘protected’. Increasing ventilation should be considered in parallel, to compensate for the associated reduction in uncontrolled infiltration. The effectiveness of thermal performance improvements are demonstrated and the detrimental effects of incorrect material choice and poor installation are highlighted. The findings show estimated heat demand to be in close correlation to household energy bills. Major areas of heat loss were identified such that improvements to building thermal performance could be targeted. The findings demonstrate that the use of heat pumps in older buildings is viable, provided sufficient improvement to thermal performance is possible. Addition of passive solar thermal and photovoltaic generation can help reduce the load and running cost for the householder. The results were used to predict future heat demand following energy efficiency improvements, thereby informing the size of heat pumps required.

Keywords: heat demand, heat pump, renewable energy, retrofit

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Authors: Jae Won Lee, Kyung Hyun Min, Hong Jae Lee, Sang Cheon Lee

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To date, imaging techniques have attracted much attention in medicine because the detection of diseases at an early stage provides greater opportunities for successful treatment. Consequently, over the past few decades, diverse imaging modalities including magnetic resonance (MR), positron emission tomography, computed tomography, and ultrasound (US) have been developed and applied widely in the field of clinical diagnosis. However, each of the above-mentioned imaging modalities possesses unique strengths and intrinsic weaknesses, which limit their abilities to provide accurate information. Therefore, multimodal imaging systems may be a solution that can provide improved diagnostic performance. Among the current medical imaging modalities, US is a widely available real-time imaging modality. It has many advantages including safety, low cost and easy access for patients. However, its low spatial resolution precludes accurate discrimination of diseased region such as cancer sites. In contrast, MR has no tissue-penetrating limit and can provide images possessing exquisite soft tissue contrast and high spatial resolution. However, it cannot offer real-time images and needs a comparatively long imaging time. The characteristics of these imaging modalities may be considered complementary, and the modalities have been frequently combined for the clinical diagnostic process. Biominerals such as calcium carbonate (CaCO3) and calcium phosphate (CaP) exhibit pH-dependent dissolution behavior. They demonstrate pH-controlled drug release due to the dissolution of minerals in acidic pH conditions. In particular, the application of this mineralization technique to a US contrast agent has been reported recently. The CaCO3 mineral reacts with acids and decomposes to generate calcium dioxide (CO2) gas in an acidic environment. These gas-generating mineralized nanoparticles generated CO2 bubbles in the acidic environment of the tumor, thereby allowing for strong echogenic US imaging of tumor tissues. On the basis of this previous work, it was hypothesized that the loading of MR contrast agents into the CaCO3 mineralized nanoparticles may be a novel strategy in designing a contrast agent for dual imaging. Herein, CaCO3 mineralized nanoparticles that were capable of generating CO2 bubbles to trigger the release of entrapped MR contrast agents in response to tumoral acidic pH were developed for the purposes of US and MR dual-modality imaging of tumors. Gd2O3 nanoparticles were selected as an MR contrast agent. A key strategy employed in this study was to prepare Gd2O3 nanoparticle-loaded mineralized nanoparticles (Gd2O3-MNPs) using block copolymer-templated CaCO3 mineralization in the presence of calcium cations (Ca2+), carbonate anions (CO32-) and positively charged Gd2O3 nanoparticles. The CaCO3 core was considered suitable because it may effectively shield Gd2O3 nanoparticles from water molecules in the blood (pH 7.4) before decomposing to generate CO2 gas, triggering the release of Gd2O3 nanoparticles in tumor tissues (pH 6.4~7.4). The kinetics of CaCO3 dissolution and CO2 generation from the Gd2O3-MNPs were examined as a function of pH and pH-dependent in vitro magnetic relaxation; additionally, the echogenic properties were estimated to demonstrate the potential of the particles for the tumor-specific US and MR imaging.

Keywords: calcium carbonate, mineralization, ultrasound imaging, magnetic resonance imaging

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Authors: Tibor Ajtai, Noémi Utry, Máté Pintér, Gábor Szabó, Zoltán Bozóki

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Beyond its climate and health related issues ambient light absorbing carbonaceous particulate matter (LAC) has also become a great scientific interest in terms of its regulations recently. It has been experimentally demonstrated in recent studies, that LAC is dominantly composed of traffic and wood burning aerosol particularly under wintertime urban conditions, when the photochemical and biological activities are negligible. Several methods have been introduced to quantitatively apportion aerosol fractions emitted by wood burning and traffic but most of them require costly and time consuming off-line chemical analysis. As opposed to chemical features, the microphysical properties of airborne particles such as optical absorption and size distribution can be easily measured on-line, with high accuracy and sensitivity, especially under highly polluted urban conditions. Recently a new method has been proposed for the apportionment of wood burning and traffic aerosols based on the spectral dependence of their absorption quantified by the Aerosol Angström Exponent (AAE). In this approach the absorption coefficient is deduced from transmission measurement on a filter accumulated aerosol sample and the conversion factor between the measured optical absorption and the corresponding mass concentration (the specific absorption cross section) are determined by on-site chemical analysis. The recently developed multi-wavelength photoacoustic instruments provide novel, in-situ approach towards the reliable and quantitative characterization of carbonaceous particulate matter. Therefore, it also opens up novel possibilities on the source apportionment through the measurement of light absorption. In this study, we demonstrate an in-situ spectral characterization method of the ambient carbon fraction based on light absorption and size distribution measurements using our state-of-the-art multi-wavelength photoacoustic instrument (4λ-PAS) and Single Mobility Particle Sizer (SMPS) The carbonaceous particulate selective source apportionment study was performed for ambient particulate matter in the city center of Szeged, Hungary where the dominance of traffic and wood burning aerosol has been experimentally demonstrated earlier. The proposed model is based on the parallel, in-situ measurement of optical absorption and size distribution. AAEff and AAEwb were deduced from the measured data using the defined correlation between the AOC(1064nm)/AOC(266nm) and N100/N20 ratios. σff(λ) and σwb(λ) were determined with the help of the independently measured temporal mass concentrations in the PM1 mode. Furthermore, the proposed optical source apportionment is based on the assumption that the light absorbing fraction of PM is exclusively related to traffic and wood burning. This assumption is indirectly confirmed here by the fact that the measured size distribution is composed of two unimodal size distributions identified to correspond to traffic and wood burning aerosols. The method offers the possibility of replacing laborious chemical analysis with simple in-situ measurement of aerosol size distribution data. The results by the proposed novel optical absorption based source apportionment method prove its applicability whenever measurements are performed at an urban site where traffic and wood burning are the dominant carbonaceous sources of emission.

Keywords: absorption, size distribution, source apportionment, wood burning, traffic aerosol

Procedia PDF Downloads 227

Authors: Lewis J. Woollin, Robert I. Davidson, Paul Watson, Philip J. Hyde

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Introduction: In-vitro testing of arthroplasty materials is of paramount importance when ensuring that they can withstand the performance requirements encountered in-vivo. One common machine used for in-vitro testing is a pin-on-plate tribometer, an early stage screening device that generates data on the wear characteristics of arthroplasty bearing materials. These devices test vertically loaded rotating cylindrical pins acting against reciprocating plates, representing the bearing surfaces. In this study, a pin-on-plate machine has been developed that provides several improvements over current technology, thereby progressing arthroplasty bearing research. Historically, pin-on-plate tribometers have been used to investigate the performance of arthroplasty bearing materials under conditions commonly encountered during a standard gait cycle; nominal operating pressures of 2-6 MPa and an operating frequency of 1 Hz are typical. There has been increased interest in using pin-on-plate machines to test more representative in-vivo conditions, due to the drive to test 'beyond compliance', as well as their testing speed and economic advantages over hip simulators. Current pin-on-plate machines do not accommodate the increased performance requirements associated with more extreme kinematic conditions, therefore a next-generation pin-on-plate tribometer has been developed to bridge the gap between current technology and future research requirements. Methodology: The design was driven by several physiologically relevant requirements. Firstly, an increased loading capacity was essential to replicate the peak pressures that occur in the natural hip joint during running and chair-rising, as well as increasing the understanding of wear rates in obese patients. Secondly, the introduction of mid-cycle load variation was of paramount importance, as this allows for an approximation of the loads present in a gait cycle to be applied and to test the fatigue properties of materials. Finally, the rig must be validated against previous-generation pin-on-plate and arthroplasty wear data. Results: The resulting machine is a twelve station device that is split into three sets of four stations, providing an increased testing capacity compared to most current pin-on-plate tribometers. The loading of the pins is generated using a pneumatic system, which can produce contact pressures of up to 201 MPa on a 3.2 mm² round pin face. This greatly exceeds currently achievable contact pressures in literature and opens new research avenues such as testing rim wear of mal-positioned hip implants. Additionally, the contact pressure of each set can be changed independently of the others, allowing multiple loading conditions to be tested simultaneously. Using pneumatics also allows the applied pressure to be switched ON/OFF mid-cycle, another feature not currently reported elsewhere, which allows for investigation into intermittent loading and material fatigue. The device is currently undergoing a series of validation tests using Ultra-High-Molecular-Weight-Polyethylene pins and 316L Stainless Steel Plates (polished to a Ra < 0.05 µm). The operating pressures will be between 2-6 MPa, operating at 1 Hz, allowing for validation of the machine against results reported previously in the literature. The successful production of this next-generation pin-on-plate tribometer will, following its validation, unlock multiple previously unavailable research avenues.

Keywords: arthroplasty, mechanical design, pin-on-plate, total joint replacement, wear testing

Procedia PDF Downloads 94

Authors: L. Malic, X. Zhang, D. Brassard, L. Clime, J. Daoud, C. Luebbert, V. Barrere, A. Boutin, S. Bidawid, N. Corneau, J. Farber, T. Veres

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The incidence of infections caused by foodborne pathogens such as Listeria monocytogenes (L. monocytogenes) poses a great potential threat to public health and safety. These issues are further exacerbated by legal repercussions due to “zero tolerance” food safety standards adopted in developed countries. Unfortunately, a large number of related disease outbreaks are caused by pathogens present in extremely low counts currently undetectable by available techniques. The development of highly sensitive and rapid detection of foodborne pathogens is therefore crucial, and requires robust and efficient pre-analytical sample preparation. Immunomagnetic separation is a popular approach to sample preparation. Microfluidic chips combined with external magnets have emerged as viable high throughput methods. However, external magnets alone are not suitable for the capture of nanoparticles, as very strong magnetic fields are required. Devices that incorporate externally applied magnetic field and microstructures of a soft magnetic material have thus been used for local field amplification. Unfortunately, very complex and costly fabrication processes used for integration of soft magnetic materials in the reported proof-of-concept devices would prohibit their use as disposable tools for food and water safety or diagnostic applications. We present a sample preparation magnetic microfluidic device implemented in low-cost thermoplastic polymers using fabrication techniques suitable for mass-production. The developed magnetic capture chip (M-chip) was employed for rapid capture and release of L. monocytogenes conjugated to immunomagnetic nanoparticles (IMNs) in buffer and beef filtrate. The M-chip relies on a dense array of Nickel-coated high-aspect ratio pillars for capture with controlled magnetic field distribution and a microfluidic channel network for sample delivery, waste, wash and recovery. The developed Nickel-coating process and passivation allows generation of switchable local perturbations within the uniform magnetic field generated with a pair of permanent magnets placed at the opposite edges of the chip. This leads to strong and reversible trapping force, wherein high local magnetic field gradients allow efficient capture of IMNs conjugated to L. monocytogenes flowing through the microfluidic chamber. The experimental optimization of the M-chip was performed using commercially available magnetic microparticles and fabricated silica-coated iron-oxide nanoparticles. The fabricated nanoparticles were optimized to achieve the desired magnetic moment and surface functionalization was tailored to allow efficient capture antibody immobilization. The integration, validation and further optimization of the capture and release protocol is demonstrated using both, dead and live L. monocytogenes through fluorescence microscopy and plate- culture method. The capture efficiency of the chip was found to vary as function of listeria to nanoparticle concentration ratio. The maximum capture efficiency of 30% was obtained and the 24-hour plate-culture method allowed the detection of initial sample concentration of only 16 cfu/ml. The device was also very efficient in concentrating the sample from a 10 ml initial volume. Specifically, 280% concentration efficiency was achieved in 17 minutes only, demonstrating the suitability of the system for food safety applications. In addition, flexible design and low-cost fabrication process will allow rapid sample preparation for applications beyond food and water safety, including point-of-care diagnosis.

Keywords: array of pillars, bacteria isolation, immunomagnetic sample preparation, polymer microfluidic device

Procedia PDF Downloads 280

Authors: Guillaume Bélanger, Jean-Philippe Fontaine, Clémence Hauduc

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There is an undeniable thirst from organic chemists and from the pharmaceutical industry to access complex alkaloids with short syntheses. While medicinal chemists are interested in the fascinating wide range of biological properties of alkaloids, synthetic chemists are rather interested in finding new routes to access these challenging natural products of often low availability from nature. To synthesize complex polycyclic cores of natural products, reaction cascades or sequences performed one-pot offer a neat advantage over classical methods for their rapid increase in molecular complexity in a single operation. In counterpart, reaction cascades need to be run on substrates bearing all the required functional groups necessary for the key cyclizations. Chemoselectivity is thus a major issue associated with such a strategy, in addition to diastereocontrol and regiocontrol for the overall transformation. In the pursuit of synthetic efficiency, our research group developed an innovative one-pot transformation of linear substrates into bi- and tricyclic adducts applied to the construction of Aspidospermatan-type alkaloids. The latter is a rich class of indole alkaloids bearing a unique bridged azatricyclic core. Despite many efforts toward the synthesis of members of this family, efficient and versatile synthetic routes are still coveted. Indeed, very short, non-racemic approaches are rather scarce: for example, in the cases of aspidospermidine and aspidospermine, syntheses are all fifteen steps and over. We envisaged a unified approach to access several members of the Aspidospermatan alkaloids family. The key sequence features a highly chemoselective formamide activation that triggers a Vilsmeier-Haack cyclization, followed by an azomethine ylide generation and intramolecular cycloaddition. Despite the high density and variety of functional groups on the substrates (electron-rich and electron-poor alkenes, nitrile, amide, ester, enol ether), the sequence generated three new carbon-carbon bonds and three rings in a single operation with good yield and high chemoselectivity. A detailed study of amide, nucleophile, and dipolarophile variations to finally get to the successful combination required for the key transformation will be presented. To complete the indoline fragment of the natural products, we developed an original approach. Indeed, all reported routes to Aspidospermatan alkaloids introduce the indoline or indole early in the synthesis. In our work, the indoline needs to be installed on the azatricyclic core after the key cyclization sequence. As a result, typical Fischer indolization is not suited since this reaction is known to fail on such substrates. We thus envisaged a unique photocatalyzed decarboxylative radical cyclization. The development of this reaction as well as the scope and limitations of the methodology, will also be presented. The original Vilsmeier-Haack and azomethine ylide cyclization sequence as well as the new photocatalyzed decarboxylative radical cyclization will undoubtedly open access to new routes toward polycyclic indole alkaloids and derivatives of pharmaceutical interest in general.

Keywords: Aspidospermatan alkaloids, azomethine ylide cycloaddition, decarboxylative radical cyclization, indole and indoline synthesis, one-pot sequential cyclizations, photocatalysis, Vilsmeier-Haack Cyclization

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Authors: Mirijam Vrabec, Marian Janak, Bojan Ambrozic, Angelja K. Surca, Nastja Rogan Smuc, Nina Zupancic, Saso Sturm

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Natural microdiamonds and moissanite (SiC) can form during the orogenic events under ultrahigh-pressure metamorphic conditions (UHP), when parts of Earth’s crust are subducted to extreme depths. So far, such processes were identified only in few places on the Earth, and therefore, represent unique opportunity to study the evolution of the Earth’s deep interior. An important discovery of microdiamonds and moissanite was reported from Pohorje, (Slovenia), where they occurred as single or polyphase inclusions in garnets. Metasedimentary rocks from Pohorje are predominantly gneisses representing parts of the Austroalpine metamorphic units of the Eastern Alps. During Cretaceous orogeny, (ca. 95–92 Ma) continental crustal rocks were deeply subducted to the mantle depths (below 100 km) and metamorphosed at pressures exceeding 3.5 GPa and temperatures between 800–850 °C. Microstructural and phase analysis of the inclusions as well as detailed elemental analysis of host garnets were carried out combining several analytical techniques: optical microscope in plane polarized transmitted light, electron probe microanalysis (EPMA) with wavelength-dispersive x-ray spectrometry (WDS) and field-emission scanning microscope (FEG-SEM) with energy-dispersive x-ray spectroscopy (EDS). Micro-Raman analysis revealed sharp, first order diamond bands sometimes accompanied by graphite bands implying that transformation of diamond back to graphite occurred. To study the chemical and crystallographic relationship between microdiamonds and co-inclusions, advanced techniques of transmission electron microscopy (TEM) were applied, which included high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), combined with EDS and electron energy-loss spectroscopy (EELS). To prepare electron transparent TEM lamellae selectively a dual-beam Focused Ion Beam/SEM (FIB/SEM) was employed. Detailed study of TEM lamellae, which was cross-sectioned from the highly faceted inclusion body located within the host garnet crystal matrix, revealed rich and rather complex internal structure. Namely, the negative crystal facets of the main inclusion body were typically decorated with up to 1 μm thick amorphous layer, reflecting the general garnet composition with slight variations in Fe/Ca content. Within these layers, ELNES analysis revealed the presence of a 28–30 nm thick layer of amorphous carbon. The very last section of this layer corresponds to composition of SiO2. Within the inclusion, besides diamond and moissanite alumosilicate mineral with pronounced layered structure, iron sulfides and chlorine were identified under TEM and CO2 and CH4 using Raman. Moissanite is found as single crystal or composed from numerous highly textured nano-crystals with the average size of 10 nm. Moissanite inclusions were found embedded inside the amorphous crust implying that moissanite crystalized well before the deposition of the amorphous layer. From the microstructural, crystallographic and chemical observations so far we can deduce, that polyphase inclusions in diamond bearing garnets from Pohorje most probably crystallized from reduced supercritical fluids. Based on layered interface structure of the host mineral multiphase process of crystallization is possible. The presence of microdiamonds and moissanite in rocks from Pohorje demonstrates that these parts of the Eastern Alps were subducted to extreme depths, and were subsequently exhumed back to the Earth's surface without complete breakdown of UHP mineral phases, allowing a rear and exceptional opportunity to study them in-situ.

Keywords: diamond, fluid inclusions, moissanite, TEM, UHP metamorphism.

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Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo

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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.

Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality

Procedia PDF Downloads 199

Authors: Pablo Reche

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Since 1980’s aquaculture has become the biggest economic activity in southern Chile, being Salmo salar and Oncorhynchus mykiss the main finfish species. High fish density makes both species prone to contract diseases, what drives the industry to big losses, affecting greatly the local economy. Three are the most concerning infective agents, the infectious salmon anemia virus (ISAv), the bacteria Piscirickettsia salmonis and the copepod Caligus rogercresseyi. To regulate the industry the government arranged the salmon farms within management areas named as barrios, which coordinate the fallowing periods and antibiotics treatments of their salmon farms. In turn, barrios are gathered into larger management areas, named as macrozonas whose purpose is to minimize the risk of disease transmission between them and to enclose the outbreaks within their boundaries. However, disease outbreaks still happen and transmission to neighbor sites enlarges the initial event. Salmon disease agents are mostly transported passively by local currents. Thus, to understand how transmission occurs it must be firstly studied the physical environment. In Chile, salmon farming takes place in the inner seas of the southernmost regions of western Patagonia, between 41.5ºS-55ºS. This coastal marine system is characterised by western winds, latitudinally modulated by the position of the South-Eats Pacific high-pressure centre, high precipitation rates and freshwater inflows from the numerous glaciers (including the largest ice cap out of Antarctic and Greenland). All of these forcings meet in a complex bathymetry and coastline system - deep fjords, shallow sills, narrow straits, channels, archipelagos, inlets, and isolated inner seas- driving an estuarine circulation (fast outflows westwards on surface and slow deeper inflows eastwards). Such a complex system is modelled on the numerical model MIKE3, upon whose 3D current fields particle-track-biological models (one for each infective agent) are decoupled. Each agent biology is parameterized by functions for maturation and mortality (reproduction not included). Such parameterizations are depending upon environmental factors, like temperature and salinity, so their lifespan will depend upon the environmental conditions those virtual agents encounter on their way while passively transported. CLIC (Connectivity-Langrangian–IFOP-Chile) is a service platform that supports the graphical visualization of the connectivity matrices calculated from the particle trajectories files resultant of the particle-track-biological models. On CLIC users can select, from a high-resolution grid (~1km), the areas the connectivity will be calculated between them. These areas can be barrios and macrozonas. Users also can select what nodes of these areas are allowed to release and scatter particles from, depth and frequency of the initial particle release, climatic scenario (winter/summer) and type of particle (ISAv, Piscirickettsia salmonis, Caligus rogercresseyi plus an option for lifeless particles). Results include probabilities downstream (where the particles go) and upstream (where the particles come from), particle age and vertical distribution, all of them aiming to understand how currently connectivity works to eventually propose a minimum risk zonation for aquaculture purpose. Preliminary results in Chiloe inner sea shows that the risk depends not only upon dynamic conditions but upon barrios location with respect to their neighbors.

Keywords: aquaculture zonation, Caligus rogercresseyi, Chilean Patagonia, coastal oceanography, connectivity, infectious salmon anemia virus, Piscirickettsia salmonis

Procedia PDF Downloads 155

Authors: Fadi Al Khatib, Raouf Mbarki, Malek Adouni

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In various sport and recreational activities, the patellofemoral joint undergoes large forces and moments while accommodating the significant knee joint movement. In doing so, this joint is commonly the source of anterior knee pain related to instability in normal patellar tracking and excessive pressure syndrome. One well-observed explanation of the instability of the normal patellar tracking is the patellofemoral ligaments and patellar tendon damage. Improved knowledge of the damage mechanism mediating ligaments and tendon injuries can be a great help not only in rehabilitation and prevention procedures but also in the design of better reconstruction systems in the management of knee joint disorders. This damage mechanism, specifically due to excessive mechanical loading, has been linked to the micro level of the fibred structure precisely to the tropocollagen molecules and their connection density. We argue defining a clear frame starting from the bottom (micro level) to up (macro level) in the hierarchies of the soft tissue may elucidate the essential underpinning on the state of the ligaments damage. To do so, in this study a multiscale fibril reinforced hyper elastoplastic Finite Element model that accounts for the synergy between molecular and continuum syntheses was developed to determine the short-term stresses/strains patellofemoral ligaments and tendon response. The plasticity of the proposed model is associated only with the uniaxial deformation of the collagen fibril. The yield strength of the fibril is a function of the cross-link density between tropocollagen molecules, defined here by a density function. This function obtained through a Coarse-graining procedure linking nanoscale collagen features and the tissue level materials properties using molecular dynamics simulations. The hierarchies of the soft tissues were implemented using the rule of mixtures. Thereafter, the model was calibrated using a statistical calibration procedure. The model then implemented into a real structure of patellofemoral ligaments and patellar tendon (OpenKnee) and simulated under realistic loading conditions. With the calibrated material parameters the calculated axial stress lies well with the experimental measurement with a coefficient of determination (R2) equal to 0.91 and 0.92 for the patellofemoral ligaments and the patellar tendon respectively. The ‘best’ prediction of the yielding strength and strain as compared with the reported experimental data yielded when the cross-link density between the tropocollagen molecule of the fibril equal to 5.5 ± 0.5 (patellofemoral ligaments) and 12 (patellar tendon). Damage initiation of the patellofemoral ligaments was located at the femoral insertions while the damage of the patellar tendon happened in the middle of the structure. These predicted finding showed a meaningful correlation between the cross-link density of the tropocollagen molecules and the stiffness of the connective tissues of the extensor mechanism. Also, damage initiation and propagation were documented with this model, which were in satisfactory agreement with earlier observation. To the best of our knowledge, this is the first attempt to model ligaments from the bottom up, predicted depending to the tropocollagen cross-link density. This approach appears more meaningful towards a realistic simulation of a damaging process or repair attempt compared with certain published studies.

Keywords: tropocollagen, multiscale model, fibrils, knee ligaments

Procedia PDF Downloads 128