Search results for: three-to-six phase matrix converter

Authors: Salha Mohamed Hussain

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As part of the review on the Malay Language curriculum and pedagogy in Singapore conducted in 2010, some recommendations were made to nurture active learners who are able to use the Malay Language efficiently in their daily lives. In response to the review, a new Malay Language teaching and learning package for primary school, called CEKAP (Cungkil – Elicit; Eksplorasi – Exploration; Komunikasi – Communication; Aplikasi – Application; Penilaian – Assessment), was developed from 2012 and implemented for Primary 1 in all primary schools from 2015. Resources developed in this package include the text book, activity book, teacher’s guide, big books, small readers, picture cards, flash cards, a game kit and Information and Communication Technology (ICT) resources. The development of the CEKAP package is continuous until 2020. This paper will look at a model incorporated in the development of the teaching materials in the new Malay Language Curriculum for Primary Schools and the rationale for each phase of development to ensure that the resources meet the needs of every pupil in the teaching and learning of Malay Language in the primary schools. This paper will also focus on the preliminary findings of the effectiveness of the model based on the feedback given by members of the working and steering committees. These members are academicians and educators who were appointed by the Ministry of Education to provide professional input on the soundness of pedagogical approach proposed in the revised syllabus and to make recommendations on the content of the new instructional materials. Quantitative data is derived from the interviews held with these members to gather their input on the model. Preliminary findings showed that the members provided positive feedback on the model and that the comprehensive process has helped to develop good and effective instructional materials for the schools. Some recommendations were also gathered from the interview sessions. This research hopes to provide useful information to those involved in the planning of materials development for teaching and learning.

Keywords: Malay language, materials development, model, primary school

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Authors: Sri Sai Ramya Bojedla, Falguni Pati

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Nature provides the best of solutions to humans. One such incredible gift to regenerative medicine is silk. The literature has publicized a long appreciation for silk owing to its incredible physical and biological assets. Its bioactive nature, unique mechanical strength, and processing flexibility make us curious to explore further to apply it in the clinics for the welfare of mankind. In this study, Antheraea mylitta and Bombyx mori silk fibroin microfibers are developed by two economical and straightforward steps via degumming and hydrolysis for the first time, and a bioactive composite is manufactured by mixing silk fibroin microfibers at various concentrations with polycaprolactone (PCL), a biocompatible, aliphatic semi-crystalline synthetic polymer. Reconstructive surgery in any part of the body except for the maxillofacial region deals with replacing its function. But answering both the aesthetics and function is of utmost importance when it comes to facial reconstruction as it plays a critical role in the psychological and social well-being of the patient. The main concern in developing adequate bone graft substitutes or a scaffold is the noteworthy variation in each patient's bone anatomy. Additionally, the anatomical shape and size will vary based on the type of defect. The advent of additive manufacturing (AM) or 3D printing techniques to bone tissue engineering has facilitated overcoming many of the restraints of conventional fabrication techniques. The acquired patient's CT data is converted into a stereolithographic (STL)-file which is further utilized by the 3D printer to create a 3D scaffold structure in an interconnected layer-by-layer fashion. This study aims to address the limitations of currently available materials and fabrication technologies and develop a customized biomaterial implant via 3D printing technology to reconstruct complex form, function, and aesthetics of the facial anatomy. These composite scaffolds underwent structural and mechanical characterization. Atomic force microscopic (AFM) and field emission scanning electron microscopic (FESEM) images showed the uniform dispersion of the silk fibroin microfibers in the PCL matrix. With the addition of silk, there is improvement in the compressive strength of the hybrid scaffolds. The scaffolds with Antheraea mylitta silk revealed higher compressive modulus than that of Bombyx mori silk. The above results of PCL-silk scaffolds strongly recommend their utilization in bone regenerative applications. Successful completion of this research will provide a great weapon in the maxillofacial reconstructive armamentarium.

Keywords: compressive modulus, 3d printing, maxillofacial reconstruction, natural fiber reinforced composites, silk fibroin microfibers

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Authors: Slah Eddine Ben Fadhel

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Despite the development of new pedagogic methods, current teaching practices put more emphasis on the learning products than on the processes learners deploy. In school syllabi, for instance, very little time is devoted to both the explanation and analysis of strategies aimed at resolving problems by means of targeting students’ metacognitive procedures. Within a cognitive framework, teaching/learning contexts are conceived of in terms of cognitive, metacognitive and affective activities intended for the treatment of information. During these activities, learners come to develop an array of knowledge and strategies which can be subsumed within an active and constructive process. Through the investigation of strategies and metacognition concepts, the purpose is to reflect upon the modalities at the heart of the learning process and to demonstrate, similarly, the inherent significance of a cognitive approach to learning. The scope of this paper is predicated on a study where the population is a group of 76 primary school pupils who experienced difficulty with learning French. The population was divided into two groups: the first group was submitted during three months to a strategy-based training to learn French. All through this phase, the teachers centred class activities round making learners aware of the strategies the latter deployed and geared them towards appraising the steps these learners had themselves taken by means of a variety of tools, most prominent among which is the logbook. The second group was submitted to the usual learning context with no recourse whatsoever to any strategy-oriented tasks. The results of both groups point out the improvement of linguistic competences in the French language in the case of those pupils who were trained by means of strategic procedures. Furthermore, this improvement was noted in relation with the native language (Arabic), a fact that tends to highlight the importance of the interdisciplinary investigation of (meta-)cognitive strategies. These results show that strategic learning promotes in pupils the development of a better awareness of their own processes, which contributes to improving their general linguistic competences.

Keywords: constructive approach, cognitive strategies, metacognition, learning

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Authors: Y. A. Prada, Fanny Guzman, Rafael Cabanzo, John J. Castillo, Enrique Mejia-Ospino

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In this work, we show the important results about of synthesis of photoluminiscents gold nanoclusters using a small peptide as template for biosensing applications. Interestingly, we design one peptide (NBC2854) homologue to conservative domain from 215 250 residue of a galactolectin protein which can recognize the proteophosphoglycans (PPG) from Leishmania. Peptide was synthetized by multiple solid phase synthesis using FMoc group methodology in acid medium. Finally, the peptide was purified by High-Performance Liquid Chromatography using a Vydac C-18 preparative column and the detection was at 215 nm using a Photo Diode Array detector. Molecular mass of this peptide was confirmed by MALDI-TOF and to verify the α-helix structure we use Circular Dichroism. By means of the methodology used we obtained a novel fluorescents gold nanoclusters (AuNC) using NBC2854 as a template. In this work, we described an easy and fast microsonic method for the synthesis of AuNC with ≈ 3.0 nm of hydrodynamic size and photoemission at 630 nm. The presence of cysteine residue in the C-terminal of the peptide allows the formation of Au-S bond which confers stability to Peptide-based gold nanoclusters. Interactions between the peptide and gold nanoclusters were confirmed by X-ray Photoemission and Raman Spectroscopy. Notably, from the ultrafine spectra shown in the MALDI-TOF analysis which containing only 3-7 KDa species was assigned to Au₈-₁₈[NBC2854]₂ clusters. Finally, we evaluated the Peptide-gold nanocluster as an optical biosensor based on fluorescence spectroscopy and the fluorescence signal of PPG (0.1 µg-mL⁻¹ to 1000 µg-mL⁻¹) was amplified at the same wavelength emission (≈ 630 nm). This can suggest that there is a strong interaction between PPG and Pep@AuNC, therefore, the increase of the fluorescence intensity can be related to the association mechanism that take place when the target molecule is sensing by the Pep@AuNC conjugate. Further spectroscopic studies are necessary to evaluate the fluorescence mechanism involve in the sensing of the PPG by the Pep@AuNC. To our best knowledge the fabrication of an optical biosensor based on Pep@AuNC for sensing biomolecules such as Proteophosphoglycans which are secreted in abundance by parasites Leishmania.

Keywords: biosensing, fluorescence, Leishmania, peptide-gold nanoclusters, proteophosphoglycans

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Authors: Katarzyna Bialik-Wąs, Klaudia Pluta, Dagmara Malina, Małgorzata Miastkowska

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In recent years, biocompatible hydrogels have been used more and more in medical applications, especially as modern dressings and drug delivery systems. The main goal of this research was the characteristics of bio-hybrid hydrogel materials incorporated with the nanocarrier-drug system, which enable the release in a gradual and prolonged manner, up to 7 days. Therefore, the use of such a combination will provide protection against mechanical damage and adequate hydration. The proposed bio-hybrid hydrogels are characterized by: transparency, biocompatibility, good mechanical strength, and the dual release system, which allows for gradual delivery of the active substance, even up to 7 days. Bio-hybrid hydrogels based on sodium alginate (SA), poly(vinyl alcohol) (PVA), glycerine, and Aloe vera solution (AV) were obtained through the chemical crosslinking method using poly(ethylene glycol) diacrylate as a crosslinking agent. Additionally, a nanocarrier-drug system was incorporated into SA/PVA/AV hydrogel matrix. Here, studies were focused on the release profiles of active substances from bio-hybrid hydrogels using the USP4 method (DZF II Flow-Through System, Erweka GmbH, Langen, Germany). The equipment incorporated seven in-line flow-through diffusion cells. The membrane was placed over support with an orifice of 1,5 cm in diameter (diffusional area, 1.766 cm²). All the cells were placed in a cell warmer connected with the Erweka heater DH 2000i and the Erweka piston pump HKP 720. The piston pump transports the receptor fluid via seven channels to the flow-through cells and automatically adapts the setting of the flow rate. All volumes were measured by gravimetric methods by filling the chambers with Milli-Q water and assuming a density of 1 g/ml. All the determinations were made in triplicate for each cell. The release study of the model active substance was carried out using a regenerated cellulose membrane Spectra/Por®Dialysis Membrane MWCO 6-8,000 Carl Roth® Company. These tests were conducted in buffer solutions – PBS at pH 7.4. A flow rate of receptor fluid of about 4 ml /1 min was selected. The experiments were carried out for 7 days at a temperature of 37°C. The released concentration of the model drug in the receptor solution was analyzed using UV-Vis spectroscopy (Perkin Elmer Company). Additionally, the following properties of the modified materials were studied: physicochemical, structural (FT-IR analysis), morphological (SEM analysis). Finally, the cytotoxicity tests using in vitro method were conducted. The obtained results exhibited that the dual release system allows for the gradual and prolonged delivery of the active substances, even up to 7 days.

Keywords: wound dressings, SA/PVA hydrogels, nanocarrier-drug system, USP4 method

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Authors: M.Younus, M. Athar Khan, Asif Adrees

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The present research endeavour was made to investigate the Public Health impact of Salmonellosis through consuming the meat and eggs of the carrier’s birds and to see the prevalence of Salmonella enteritidis and Salmonella typhimurium from poultry feed, poultry meat, and poultry eggs and their role in the chain of transmission of salmonellae to human beings and causing food poisoning. The ultimate objective was to generate data to improve the quality of poultry products and human health awareness. Salmonellosis is one of the most wide spread food borne zoonoses in all the continents of the world. The etiological agents Salmonella enteritidis and Salmonella typhimurium not only produce the disease but during the convalescent phase (after the recovery of disease) remain carriers for indefinite period of time. The carrier state was not only the source of spread of disease with in the poultry but also caused typhoid fever in humans. The chain of transmission started from poultry feed to poultry meat and ultimately to humans as dead end hosts. In this experiment a total number of 200 samples of human stool and blood were collected randomly (100 samples of human stool and 100 samples of human blood) of 100 patients suspected from food poisoning patients from different hospitals of Lahore area for the identification of Salmonella enteritidis and Salmonella typhimurium through PCR method in order to see the public health impact of Salmonellosis through consuming the meat and eggs of the carrier birds. On the average 14 and 10 stool samples were found positive against Salmonella enteritidis and Salmonella typhimurium from each of the 25 patients from each hospital respectively in case of suspected food poisoning patients. Similarly on an average 5% and 6% blood samples were found positive from 25 patients of each hospital respectively. There was a significant difference (P< 0.05) in the sero positivity of stool and blood samples of suspected food poisoning patients as far as Salmonella enteritidis and Salmonella typhimurium was concerned. However there was no significant difference (P<0.05) between the hospitals.

Keywords: salmonella, zoonosis, food, transmission, eggs

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Authors: Zarabizan Zakaria, Hayati Zainal

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The construction industry is one of the most important sectors that contribute to the nation’s economy and catalyze towards the growth of other industries. However, some construction projects have not been completed on its stipulated time and duration, scope and budget due to several factors. This problem arises due to the weaknesses of human factors, especially from ineffective leadership quality practiced by project managers and contractors in managing project teams. Therefore, a construction project should impose the element of Project Team. The project team is formed in the implementation of the project which includes the project brief, project scope, customer requirements and provided designs. Many organizations in the construction sector use teams to meet today's global competition and customer expectations, however, team effectiveness evaluation is required. In insuring the construction team is successful and effectiveness, the construction department must encourage, measure, set up, and evaluate or review the effectiveness of project team that was formed. In order to produce a better outcome for a high-end project, an effective and efficient project team is required which also help in increasing overall productivity. The purpose of this study is to determine the role of team effectiveness in the construction project team based on the overall construction project performance. It examines several different factors which related to team effectiveness. It also examines the relationship between team effectiveness factor and project performance aspect. Team Effect Review and Project Performance Review are developed to be used for data collection. Data collected were analyzed using several statistical tests. Results obtained from data analysis are validated using semi-structured interviews. Besides that, a comprehensive survey were developed to assess the way construction project teams in order to maintain its effectiveness throughout the project phase. In order to determine a project successful it has been found that Project Team Leadership is the most important factor. In addition, the definition of team effectiveness in the construction project team is developed based on the perspective of project clients and project team members. The results of this study are expected to provide an idea on the factors that are needed to be focused on improving the team's effectiveness towards project performance aspects. At the same time, the definition of team effectiveness from team members and owner views has been developed in order to provide a better understanding of the word team's effectiveness in construction projects.

Keywords: project team, leadership, construction project, project successful

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Authors: Peiming Li

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This paper presents an innovative blockchain-based approach to enhance the reliability and efficiency of federated learning systems. By integrating a decentralized oracle consensus mechanism into the federated learning framework, we address key challenges of data and model integrity. Our approach utilizes a network of redundant oracles, functioning as independent validators within an epoch-based training system in the federated learning model. In federated learning, data is decentralized, residing on various participants' devices. This scenario often leads to concerns about data integrity and model quality. Our solution employs blockchain technology to establish a transparent and tamper-proof environment, ensuring secure data sharing and aggregation. The decentralized oracles, a concept borrowed from blockchain systems, act as unbiased validators. They assess the contributions of each participant using a Hidden Markov Model (HMM), which is crucial for evaluating the consistency of participant inputs and safeguarding against model poisoning and malicious activities. Our methodology's distinct feature is its epoch-based training. An epoch here refers to a specific training phase where data is updated and assessed for quality and relevance. The redundant oracles work in concert to validate data updates during these epochs, enhancing the system's resilience to security threats and data corruption. The effectiveness of this system was tested using the Mnist dataset, a standard in machine learning for benchmarking. Results demonstrate that our blockchain-oriented federated learning approach significantly boosts system resilience, addressing the common challenges of federated environments. This paper aims to make these advanced concepts accessible, even to those with a limited background in blockchain or federated learning. We provide a foundational understanding of how blockchain technology can revolutionize data integrity in decentralized systems and explain the role of oracles in maintaining model accuracy and reliability.

Keywords: federated learning system, block chain, decentralized oracles, hidden markov model

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Authors: Boor Singh Lalia, Yarjan Abdul Samad, Raed Hashaikeh

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Three different kinds of solid polymer electrolytes were prepared using polyethylene oxide (PEO) as a base polymer, networked cellulose (NC) as a physical support and LiClO4 as a conductive salt for the electrolytes. Networked cellulose, a modified form of cellulose, is a biodegradable and environmentally friendly additive which provides a strong fibrous networked support for structural stability of the electrolytes. Although the PEO/NC/LiClO4 electrolyte retains its structural integrity and mechanical properties at 100oC as compared to pristine PEO-based polymer electrolytes, it suffers from poor ionic conductivity. To improve the room temperature conductivity of the electrolyte, PEO is replaced by the polyethylene glycol (PEG) which is a liquid phase that provides high mobility for Li+ ions transport in the electrolyte. PEG/NC/LiClO4 shows improvement in ionic conductivity compared to PEO/NC/LiClO4 at room temperature, but it is brittle and tends to form cracks during processing. An advanced solid polymer electrolyte with optimum ionic conductivity and mechanical properties is developed by using a ternary system: TEGDME/PEO/NC+LiClO4. At room temperature, this electrolyte exhibits an ionic conductivity to the order of 10-5 S/cm, which is very high compared to that of the PEO/LiClO4 electrolyte. Pristine PEO electrolytes start melting at 65 °C and completely lose its mechanical strength. Dynamic mechanical analysis of TEGDME: PEO: NC (70:20:10 wt%) showed an improvement of storage modulus as compared to the pristine PEO in the 60–120 °C temperature range. Also, with an addition of NC, the electrolyte retains its mechanical integrity at 100 oC which is beneficial for Li-ion battery operation at high temperatures. Differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA) studies revealed that the ternary polymer electrolyte is thermally stable in the lithium ion battery operational temperature range. As-prepared polymer electrolyte was used to assemble LiFePO4/ TEGDME/PEO/NC+LiClO4/Li half cells and their electrochemical performance was studied via cyclic voltammetry and charge-discharge cycling.

Keywords: solid polymer electrolyte, ionic conductivity, mechanical properties, lithium ion batteries, cyclic voltammetry

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Authors: Sercan Altundemir, Pinar Eribol, A. Kerem Uguz

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Microfluidics systems allow many-large scale laboratory applications to be miniaturized on a single device in order to reduce cost and advance fluid control. Moreover, such systems enable to generate and control droplets which have a significant role on improved analysis for many chemical and biological applications. For example, they can be employed as the model for cells in microfluidic systems. In this work, the interfacial instability of two immiscible Newtonian liquids flowing in a microchannel is investigated. When two immiscible liquids are in laminar regime, a flat interface is formed between them. If a direct current electric field is applied, the interface may deform, i.e. may become unstable and it may be ruptured and form micro-droplets. First, the effect of thickness ratio, total flow rate, viscosity ratio of the silicone oil and ethylene glycol liquid couple on the critical voltage at which the interface starts to destabilize is investigated. Then the droplet sizes are measured under the effect of these parameters at various voltages. Moreover, the effect of total flow rate on the time elapsed for the interface to be ruptured to form droplets by hitting the wall of the channel is analyzed. It is observed that an increase in the viscosity or the thickness ratio of the silicone oil to the ethylene glycol has a stabilizing effect, i.e. a higher voltage is needed while the total flow rate has no effect on it. However, it is observed that an increase in the total flow rate results in shortening of the elapsed time for the interface to hit the wall. Moreover, the droplet size decreases down to 0.1 μL with an increase in the applied voltage, the viscosity ratio or the total flow rate or a decrease in the thickness ratio. In addition to these observations, two empirical models for determining the critical electric number, i.e., the dimensionless voltage and the droplet size and another model which is a combination of both models, for determining the droplet size at the critical voltage are established.

Keywords: droplet formation, electrohydrodynamics, microfluidics, two-phase flow

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Authors: Debabrata Adhikari, Mikhail Matveev, Louise Brown, Jan Kočí, Andy Long

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Resin transfer molding (RTM) is increasingly used for manufacturing high-quality composite structures due to its additional advantages over prepregs of low-cost out-of-autoclave processing. However, to retain the advantages, it is critical to reduce the void content during the injection. Reinforcements commonly used in RTM, such as woven fabrics, have dual-scale porosity with mesoscale pores between the yarns and the micro-scale pores within the yarns. Due to the fabric geometry and the nature of the dual-scale flow, the flow front during injection creates a complicated fingering formation which leads to void formation. Analytical modeling of void formation for woven fabrics has been widely studied elsewhere. However, there is scope for improvement to the reduction in void formation in 3D fabrics wherein the in-plane yarn layers are confined by additional through-thickness binder yarns. In the present study, the structural morphology of the tortuous pore spaces in the 3D fabric has been studied and implemented using open-source software TexGen. An analytical model for the void and the fingering formation has been implemented based on an idealized unit cell model of the 3D fabric. Since the pore spaces between the yarns are free domains, the region is treated as flow-through connected channels, whereas intra-yarn flow has been modeled using Darcy’s law with an additional term to account for capillary pressure. Later the void fraction has been characterised using the criterion of void formation by comparing the fill time for inter and intra yarn flow. Moreover, the dual-scale two-phase flow of resin with air has been simulated in the commercial CFD solver OpenFOAM/ANSYS to predict the probable location of voids and validate the analytical model. The use of an idealised unit cell model will give the insight to optimise the mesoscale geometry of the reinforcement and injection parameters to minimise the void content during the LCM process.

Keywords: 3D fiber, void formation, RTM, process modelling

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Authors: Mohammed Alasel, Michael Keusgen

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Gold is a noble metal; in its nano-scale level (e.g. spherical nanoparticles), the conduction electrons are triggered to collectively oscillate with a resonant frequency when certain wavelengths of electromagnetic radiation interact with its surface; this phenomenon is known as surface plasmon resonance (SPR). SPR is responsible for giving the gold nanoparticles its intense red color depending mainly on its size, shape and distance between nanoparticles. A decreased distance between gold nanoparticles results in aggregation of them causing a change in color from red to blue. This aggregation enables gold nanoparticles to serve as a sensitive biosensoric indicator. In the proposed work, gold nanoparticles were modified with two proteins: i) Borrelia antigen, variable lipoprotein surface-exposed protein (VlsE), and ii) protein A. VlsE antigen induces a strong antibody response against Lyme disease and can be detected from early to late phase during the disease in humans infected with Borrelia. In addition, it shows low cross-reaction with the other non-pathogenic Borrelia strains. The high specificity of VlsE antigen to anti-Borrelia antibodies, combined simultaneously with the high specificity of protein A to the Fc region of all IgG human antibodies, was utilized to develop a rapid test for serological point of care diagnosis of borreliosis in human serum. Only in the presence of anti-Borrelia antibodies in the serum probe, an aggregation of gold nanoparticles can be observed, which is visible by a concentration-dependent colour shift from red (low IgG) to blue (high IgG). Experiments showed it is clearly possible to distinguish between positive and negative sera samples using a simple suspension of the two-protein modified gold nanoparticles in a very short time (30 minutes). The proposed work showed the potential of using such modified gold nanoparticles generally for serological diagnosis. Improved specificity and reduced assay time can be archived in applying increased salt concentrations combined with decreased pH values (pH 5).

Keywords: gold nanoparticles, gold aggregation, serological diagnosis, protein A, lyme borreliosis

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

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

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

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Authors: Kalpana Goel

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Australian social work schools are finding it difficult to find appropriate placements for the increasing number of international students enrolled in their Master of Social Work qualifying (MSWQ) programs. Anecdotally, it has been noticed that fewer social work students are ready to work with older people whose numbers are rising globally. An innovative and unique placement for international students enrolled in the MSWQ at one Australian university was organised in partnership with a community-based service working with older clients to meet two objectives: increasing the number of suitable placements for international students and preparing social work students to work with older people. Creative activities and projects were designed to provide meaningful engagement and experience in working with older people in the community. Students participated in a number of projects that were matched with their interest and capability in a 500-hour placement. The students were asked to complete an online survey after all work for the placement had been completed. The areas of assessment were: self-perceived change in perception towards age and older people, valued field placement experiences including reflective practice, knowledge and skill development, and constraints and challenges experienced in the placement. Findings revealed students’ increased level of confidence in applying social work theory to practice, developing effective communication and interpersonal skills, and use of innovation and creativity in preparing well-being plans with older adults. Challenges and constraints related to their limited English language ability and lack of cultural knowledge of the host society. It was recognised that extra support for these students and more planning in the beginning phase of placement are vital to placement success. Caution in matching students with clients of similar cultural background must be exercised to ensure that there is equity in task allocation and opportunities for wider experiences.

Keywords: field placement, international students, older people, social work

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Authors: Adriano Losso, Birgit Dämon, Stefan Mayr

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In vascular plants, water flows from roots to leaves in a metastable state, and even a small perturbation of the system can lead a sudden transition from the liquid to the vapor phase, resulting in xylem embolism (cavitation). Xylem embolism, induced by drought stress and/or freezing stress is caused by the aspiration of gaseous bubbles into xylem conduits from adjacent gas-filled compartments through pit membrane pores (‘air seeding’). At water potentials less negative than the threshold for air seeding, the surface tension (γ) stabilizes the air-water interface and thus prevents air from passing the pit pores. This hold is probably also true for conifers, where this effect occurs at the edge of the sealed torus. Accordingly, it was experimentally demonstrated that γ influences air seeding, but information on the relevance of this effect under field conditions is missing. In this study, we analyzed seasonal changes in γ of the xylem sap in two conifers growing at the alpine timberline (Picea abies and Pinus mugo). In addition, cut branches were perfused (40 min perfusion at 0.004 MPa) with different γ solutions (i.e. distilled and degassed water, 2, 5 and 15% (v/v) ethanol-water solution corresponding to a γ of 74, 65, 55 and 45 mN m-1, respectively) and their vulnerability to drought-induced embolism analyzed via the centrifuge technique (Cavitron). In both species, xylem sap γ changed considerably (ca. 53-67 and ca. 50-68 mN m-1 in P. abies and P. cembra, respectively) over the season. Branches perfused with low γ solutions showed reduced resistance against drought-induced embolism in both species. A significant linear relationship (P < 0.001) between P12, P50 and P88 (i.e. water potential at 12, 50 and 88% of the loss of conductivity) and xylem sap γ was found. Based on this correlation, a variation in P50 between -3.10 and -3.83 MPa (P. abies) and between -3.21 and -4.11 MPa (P. mugo) over the season could be estimated. Results demonstrate that changes in γ of the xylem sap can considerably influence a tree´s resistance to drought-induced embolism. They indicate that vulnerability analyses, normally conducted at a γ near that of pure water, might often underestimate vulnerabilities under field conditions. For studied timberline conifers, seasonal changes in γ might be especially relevant in winter, when frost drought and freezing stress can lead to an excessive embolism.

Keywords: conifers, Picea abies, Pinus mugo, timberline

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Authors: Taekyun Hur, Yoonyoung Kim, Junkyu Lim

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Previous works on leisure activities had been categorizing activities arbitrarily and subjectively while focusing on a single dimension (e.g. active-passive, individual-group). To overcome these problems, this study proposed a Korean leisure activities’ matrix model that considered multidimensional features of leisure activities, which was comprised of 3 main factors and 6 sub factors: (a) Active (physical, mental), (b) Relational (quantity, quality), (c) Expert (entry barrier, possibility of improving). We developed items for measuring the degree of each dimension for every leisure activity. Using the developed Leisure Activities Dimensions (LAD) questionnaire, we investigated the presented dimensions of a total of 78 leisure activities which had been enjoyed by most Koreans recently (e.g. watching movie, taking a walk, watching media). The study sample consisted of 1348 people (726 men, 658 women) ranging in age from teenagers to elderlies in their seventies. This study gathered 60 data for each leisure activity, a total of 4860 data, which were used for statistical analysis. First, this study compared 3-factor model (Activity, Relation, Expertise) fit with 6-factor model (physical activity, mental activity, relational quantity, relational quality, entry barrier, possibility of improving) fit by using confirmatory factor analysis. Based on several goodness-of-fit indicators, the 6-factor model for leisure activities was a better fit for the data. This result indicates that it is adequate to take account of enough dimensions of leisure activities (6-dimensions in our study) to specifically apprehend each leisure attributes. In addition, the 78 leisure activities were cluster-analyzed with the scores calculated based on the 6-factor model, which resulted in 8 leisure activity groups. Cluster 1 (e.g. group sports, group musical activity) and Cluster 5 (e.g. individual sports) had generally higher scores on all dimensions than others, but Cluster 5 had lower relational quantity than Cluster 1. In contrast, Cluster 3 (e.g. SNS, shopping) and Cluster 6 (e.g. playing a lottery, taking a nap) had low scores on a whole, though Cluster 3 showed medium levels of relational quantity and quality. Cluster 2 (e.g. machine operating, handwork/invention) required high expertise and mental activity, but low physical activity. Cluster 4 indicated high mental activity and relational quantity despite low expertise. Cluster 7 (e.g. tour, joining festival) required not only moderate degrees of physical activity and relation, but low expertise. Lastly, Cluster 8 (e.g. meditation, information searching) had the appearance of high mental activity. Even though clusters of our study had a few similarities with preexisting taxonomy of leisure activities, there was clear distinctiveness between them. Unlike the preexisting taxonomy that had been created subjectively, we assorted 78 leisure activities based on objective figures of 6-dimensions. We also could identify that some leisure activities, which used to belong to the same leisure group, were included in different clusters (e.g. filed ball sports, net sports) because of different features. In other words, the results can provide a different perspective on leisure activities research and be helpful for figuring out what various characteristics leisure participants have.

Keywords: leisure, dimensional model, activity, relationship, expertise

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Authors: Pierre van Tonder, Dinesh Muthoo, Kim twiname

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Many existing and newly built structures are constructed on the design basis of the engineer and the workmanship of the construction company. However, when considering larger structures where more people are exposed to the building, its structural integrity is of great importance considering the safety of its occupants (Raghu, 2013). But how can the structural integrity of a building be monitored efficiently and effectively. This is where the fourth industrial revolution step in, and with minimal human interaction, data can be collected, analysed, and stored, which could also give an indication of any inconsistencies found in the data collected, this is where the Fibre Bragg Grating (FBG) monitoring system is introduced. This paper illustrates how data can be collected and converted to develop stress – strain behaviour and to produce bending moment diagrams for the utilisation and prediction of the structure’s integrity. Embedded fibre optic sensors were used in this study– fibre Bragg grating sensors in particular. The procedure entailed making use of the shift in wavelength demodulation technique and an inscription process of the phase mask technique. The fibre optic sensors considered in this report were photosensitive and embedded in the slab and beams for data collection and analysis. Two sets of fibre cables have been inserted, one purposely to collect temperature recordings and the other to collect strain and temperature. The data was collected over a time period and analysed used to produce bending moment diagrams to make predictions of the structure’s integrity. The data indicated the fibre Bragg grating sensing system proved to be useful and can be used for structural health monitoring in any environment. From the experimental data for the slab and beams, the moments were found to be64.33 kN.m, 64.35 kN.m and 45.20 kN.m (from the experimental bending moment diagram), and as per the idealistic (Ultimate Limit State), the data of 133 kN.m and 226.2 kN.m were obtained. The difference in values gave room for an early warning system, in other words, a reserve capacity of approximately 50% to failure.

Keywords: fibre bragg grating, structural health monitoring, fibre optic sensors, beams

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Authors: Sarmistha Baruah, Akshai Kumar, Nageswara Rao Peela

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The global energy crisis due to the dependence on fossil fuels and its limited reserves as well as environmental pollution are key concerns to the research communities. However, the implementation of alcohol-based fuel cells such as methanol is anticipated as a reliable source of future energy technology due to their high energy density, environment friendliness, ease of storage, transportation, etc. To drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), an active and long-lasting catalyst is necessary for efficient energy conversion from methanol. Recently, transition metal-zeolite-based materials have been considered versatile catalysts for a variety of industrial and lab-scale processes. Large specific surface area, well-organized micropores, and adjustable acidity/basicity are characteristics of zeolites that make them excellent supports for immobilizing small-sized and highly dispersed metal species. Significant advancement in the production and characterization of well-defined metal clusters encapsulated within zeolite matrix has substantially expanded the library of materials available, and consequently, their catalytic efficacy. In this context, we developed bimetallic Ni-Co catalysts encapsulated within LTA (also known as 4A) zeolite via a method combined with the in-situ encapsulation of metal species using hydrothermal treatment followed by a chemical reduction process. The prepared catalyst was characterized using advanced characterization techniques, such as X-ray diffraction (XRD), field emission transmission electron microscope (FETEM), field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of the catalyst for MOR was carried out in an alkaline medium at room temperature using techniques such as cyclic voltammetry (CV), and chronoamperometry (CA). The resulting catalyst exhibited better catalytic activity of 12.1 mA cm-2 at 1.12 V vs Ag/AgCl and retained remarkable stability (~77%) even after 1000 cycles CV test for the electro-oxidation of methanol in alkaline media without any significant microstructural changes. The high surface area, better Ni-Co species integration in the zeolite, and the ample amount of surface hydroxyl groups contribute to highly dispersed active sites and quick analyte diffusion, which provide notable MOR kinetics. Thus, this study will open up new possibilities to develop a noble metal-free zeolite-based electrocatalyst due to its simple synthesis steps, large-scale fabrication, improved stability, and efficient activity for DMFC application.

Keywords: alkaline media, bimetallic, encapsulation, methanol oxidation reaction, LTA zeolite.

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Authors: Elaine Lima Da Fonseca, Eliomar Pereira Da Silva Filho

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The modeling of areas susceptible to soil loss by hydro erosive processes consists of a simplified instrument of reality with the purpose of predicting future behaviors from the observation and interaction of a set of geoenvironmental factors. The models of potential areas for soil loss will be obtained through binary logistic regression, artificial neural networks, and support vector machines. The choice of the municipality of Colorado do Oeste in the south of the western Amazon is due to soil degradation due to anthropogenic activities, such as agriculture, road construction, overgrazing, deforestation, and environmental and socioeconomic configurations. Initially, a soil erosion inventory map constructed through various field investigations will be designed, including the use of remotely piloted aircraft, orbital imagery, and the PLANAFLORO/RO database. 100 sampling units with the presence of erosion will be selected based on the assumptions indicated in the literature, and, to complement the dichotomous analysis, 100 units with no erosion will be randomly designated. The next step will be the selection of the predictive parameters that exert, jointly, directly, or indirectly, some influence on the mechanism of occurrence of soil erosion events. The chosen predictors are altitude, declivity, aspect or orientation of the slope, curvature of the slope, composite topographic index, flow power index, lineament density, normalized difference vegetation index, drainage density, lithology, soil type, erosivity, and ground surface temperature. After evaluating the relative contribution of each predictor variable, the erosion susceptibility model will be applied to the municipality of Colorado do Oeste - Rondônia through the SPSS Statistic 26 software. Evaluation of the model will occur through the determination of the values of the R² of Cox & Snell and the R² of Nagelkerke, Hosmer and Lemeshow Test, Log Likelihood Value, and Wald Test, in addition to analysis of the Confounding Matrix, ROC Curve and Accumulated Gain according to the model specification. The validation of the synthesis map resulting from both models of the potential risk of soil erosion will occur by means of Kappa indices, accuracy, and sensitivity, as well as by field verification of the classes of susceptibility to erosion using drone photogrammetry. Thus, it is expected to obtain the mapping of the following classes of susceptibility to erosion very low, low, moderate, very high, and high, which may constitute a screening tool to identify areas where more detailed investigations need to be carried out, applying more efficient social resources.

Keywords: modeling, susceptibility to erosion, artificial intelligence, Amazon

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Authors: Ime R. Udotong, Justina I. R. Udotong, Ofonime U. M. John

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Brass terminal, one of the several crude oil and petroleum products storage/handling facilities in the Niger Delta was built in the 1980s. Activities at this site, over the years, released crude oil into this 3 m-deep, 1500 m-long canal lying adjacent to the terminal with oil floating on it and its sediment heavily polluted. To ensure effective clean-up, three major activities were planned: Site characterization, bioremediation pilot plant construction and testing and full-scale bioremediation of contaminated sediment/bank soil by land farming. The canal was delineated into 12 lots and each characterized, with reference to the floating oily phase, contaminated sediment and canal bank soil. As a result of site characterization, a pilot plant for on-site bioremediation was designed and a treatment basin constructed for carrying out pilot bioremediation test. Following a designed sampling protocol, samples from this pilot plant were collected for analysis at two laboratories as a quality assurance/quality control check. Results showed that Brass Canal upstream is contaminated with dark, thick and viscous oily film with characteristic hydrocarbon smell while downstream, thin oily film interspersed with water were observed. Sediments were observed to be dark with mixture of brownish sandy soil with TPH ranging from 17,800 mg/kg in Lot 1 to 88,500 mg/kg in Lot 12 samples. Brass Canal bank soil was observed to be sandy from ground surface to 3m, below ground surface (bgs) it was silty-sandy and brownish while subsurface soil (4-10m bgs) was sandy-clayey and whitish/grayish with typical hydrocarbon smell. Preliminary results obtained so far have been very promising but were proprietary. This project is considered, to the best of technical literature knowledge, the first large-scale on-site bioremediation project in the Niger Delta region, Nigeria.

Keywords: bioremediation, contaminated sediment, land farming, oily sludge, oil terminal

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Authors: M. Abuziarov

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The designed complex is intended for the numerical simulation of fast dynamic processes of interaction of heterogeneous environments susceptible to the significant formability. The main challenges in solving such problems are associated with the construction of the numerical meshes. Currently, there are two basic approaches to solve this problem. One is using of Lagrangian or Lagrangian Eulerian grid associated with the boundaries of media and the second is associated with the fixed Eulerian mesh, boundary cells of which cut boundaries of the environment medium and requires the calculation of these cut volumes. Both approaches require the complex grid generators and significant time for preparing the code’s data for simulation. In this codes these problems are solved using two grids, regular fixed and mobile local Euler Lagrange - Eulerian (ALE approach) accompanying the contact and free boundaries, the surfaces of shock waves and phase transitions, and other possible features of solutions, with mutual interpolation of integrated parameters. For modeling of both liquids and gases, and deformable solids the Godunov scheme of increased accuracy is used in Lagrangian - Eulerian variables, the same for the Euler equations and for the Euler- Cauchy, describing the deformation of the solid. The increased accuracy of the scheme is achieved by using 3D spatial time dependent solution of the discontinuity problem (3D space time dependent Riemann's Problem solver). The same solution is used to calculate the interaction at the liquid-solid surface (Fluid Structure Interaction problem). The codes does not require complex 3D mesh generators, only the surfaces of the calculating objects as the STL files created by means of engineering graphics are given by the user, which greatly simplifies the preparing the task and makes it convenient to use directly by the designer at the design stage. The results of the test solutions and applications related to the generation and extension of the detonation and shock waves, loading the constructions are presented.

Keywords: fluid structure interaction, Riemann's solver, Euler variables, 3D codes

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Authors: Tarek Duzan

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Fractures are a fundamental property of most reservoirs. Despite their abundance, they remain difficult to detect and quantify. The most effective characterization of fractured reservoirs is accomplished by integrating geological, geophysical, and engineering data. Detection of fractures and defines their relative contribution is crucial in the early stages of exploration and later in the production of any field. Because fractures could completely change our thoughts, efforts, and planning to produce a specific field properly. From the structural point of view, all reservoirs are fractured to some point of extent. North Gialo field is thought to be a naturally fractured reservoir to some extent. Historically, natural fractured reservoirs are more complicated in terms of their exploration and production efforts, and most geologists tend to deny the presence of fractures as an effective variable. Our aim in this paper is to determine the degree of fracturing, and consequently, our evaluation and planning can be done properly and efficiently from day one. The challenging part in this field is that there is no enough data and straightforward well testing that can let us completely comfortable with the idea of fracturing; however, we cannot ignore the fractures completely. Logging images, available well testing, and limited core studies are our tools in this stage to evaluate, model, and predict possible fracture effects in this reservoir. The aims of this study are both fundamental and practical—to improve the prediction and diagnosis of natural-fracture attributes in N. Gialo hydrocarbon reservoirs and accurately simulate their influence on production. Moreover, the production of this field comes from 2-phase plan; a self depletion of oil and then gas injection period for pressure maintenance and increasing ultimate recovery factor. Therefore, well understanding of fracturing network is essential before proceeding with the targeted plan. New analytical methods will lead to more realistic characterization of fractured and faulted reservoir rocks. These methods will produce data that can enhance well test and seismic interpretations, and that can readily be used in reservoir simulators.

Keywords: natural fracture, sandstone reservoir, geological, geophysical, and engineering data

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Authors: Samiyah Tasleem, Muhammad Abdul Haq, Syed Baqir Shyum Naqvi, Muhammad Abid Husnain, Sajjad Haider Naqvi

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The objective of the present study was: a) to investigate the antimicrobial activity of honey samples of different floral sources of Pakistan, b) to recover the phenolic acids in them as a possible contributing factor of antimicrobial activity. Six honey samples from different floral sources, namely: Trachysperm copticum, Acacia species, Helianthus annuus, Carissa opaca, Zizyphus and Magnifera indica were used. The antimicrobial activity was investigated by the disc diffusion method against eight freshly isolated clinical isolates (Staphylococci aureus, Staphylococci epidermidis, Streptococcus faecalis, Pseudomonas aeruginosa, Klebsiella pneumonia, Escherichia coli, Proteus vulgaris and Candida albicans). Antimicrobial activity of honey was compared with five commercial antibiotics, namely: doxycycline (DO-30ug/mL), oxytetracycline (OT-30ug/mL), clarithromycin (CLR–15ug/mL), moxifloxacin (MXF-5ug/mL) and nystatin (NT – 100 UT). The fractions responsible for antimicrobial activity were extracted using ethyl acetate. Solid phase extraction (SPE) was used to recover the phenolic acids of honey samples. Identification was carried out via High-Performance Liquid Chromatography (HPLC). The results indicated that antimicrobial activity was present in all honey samples and found comparable to the antibiotics used in the study. In the microbiological assay, the ethyl acetate honey extract was found to exhibit a very promising antimicrobial activity against all the microorganisms tested, indicating the existence of phenolic compounds. Six phenolic acids, namely: gallic, caffeic, ferulic, vanillic, benzoic and cinnamic acids were identified besides some unknown substance by HPLC. In conclusion, Pakistani honey samples showed a broad spectrum antibacterial and promising antifungal activity. Identification of six different phenolic acids showed that Pakistani honey samples are rich sources of phenolic compounds that could be the contributing factor of antimicrobial activity.

Keywords: Pakistani honey, antimicrobial activity, Phenolic acids eg.gallic, caffeic, ferulic, vanillic, benzoic and cinnamic acids

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Authors: Alessandro Suardi, Rodolfo Picchio, Domenico Coaloa, Maria Bonaventura Forleo, Nadia Palmieri, Luigi Pari

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The reconversion process of the Italian sugar supply chain to bio-energy supply chains, as a result of the 2006 Sugar CMO reform, have involved research to define the best logistics, the most adapted energy crops for the Italian territory and their sustainability. Rapeseed (Brassica napus L.), Giant reed (Arundo donax L.) and Poplar (Poplar ssp.) are energy crops considered strategic for the development of Italian energy supply-chains. This study analyzed the environmental and the economic impacts on the farm level of these three energy crops. The environmental assessment included six farming units, two per crop, which were extracted from a sample of 251 rapeseed farm units (2751 ha), 7 giant reed farm units (7.8 ha), and 91 poplar farm units (440 ha) using a statistical multivariate analysis. Life Cycle Assessment (LCA) research method has been used to evaluate and compare the sustainability of the agricultural phases of the crops studied. The impact analyses have been performed at mid-point and end-point levels. The results of the analysis shown that the fertilization, is the major source of environmental impact of the agricultural phase due to the production of the fertilizers and the soil emissions of GHG following the treatment. The perennial energy crops studied (Arundo donax L., Poplar ssp.) were environmentally more sustainable if compared with the annual crop (Brassica napus L.) for all the impact categories at mid-point and end-point levels analyzed. The most relevant impact category influenced by the agricultural process result the fossil depletion, mainly due to the fossil fuels consumed during the mineral fertilizers production (urea). Human health was the most affected damage category at the end point level. Poplar result the energy crop with the best environmental performance for the Italian territory, in the distribution areas most suitable for its cultivation.

Keywords: LCA, energy crops, rapeseed, giant reed, poplar

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Authors: Rafael Santos, Clara Pimenta Do Vale, Barbara Bogoni, Poul Henning Kirkegaard

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In the last decades, the relevance of hand drawing has decreased in the scope of architectural education. However, some schools continue to recognize its decisive role, not only in the architectural design teaching, but in the whole of architectural training. With this paper it is intended to present the results of a research developed on the following problem: the practise of hand drawing as a premier form of representation in architectural design teaching. The research had as its object the educational model of the Faculty of Architecture of the University of Porto (FAUP) and was led by three main objectives: to identify the circumstance that promoted hand drawing as a form of representation in FAUP's model; to characterize the types of hand drawing and their role in that model; to determine the particularities of hand drawing as a premier form of representation in architectural design teaching. Methodologically, the research was conducted according to a qualitative embedded single-case study design. The object – i.e., the educational model – was approached in FAUP case considering its Context and three embedded unities of analysis: the educational Purposes, Principles and Practices. In order to guide the procedures of data collection and analysis, a Matrix for the Characterization (MCC) was developed. As a methodological tool, the MCC allowed to relate the three embedded unities of analysis with the three main sources of evidence where the object manifests itself: the professors, expressing how the model is Assumed; the architectural design classes, expressing how the model is Achieved; and the students, expressing how the model is Acquired. The main research methods used were the naturalistic and participatory observation, in-person-interview and documentary and bibliographic review. The results reveal that the educational model of FAUP – following the model of the former Porto School – was largely due to the methodological foundations created with the hand drawing teaching-learning processes. In the absence of a culture of explicit theoretical elaboration or systematic research, hand drawing was the support for the continuity of the school, an expression of a unified thought about what should be the reflection and practice of architecture. As a form of representation, hand drawing plays a transversal role in the entire educational model, since its purposes are not limited to the conception of architectural design – it is also a means for perception, analysis and synthesis. Regarding the architectural design teaching, there seems to be an understanding of three complementary dimensions of didactics: the instrumental, methodological and propositional dimension. At FAUP, hand drawing is recognized as the common denominator among these dimensions, according to the idea of "globality of drawing". It is expected that the knowledge base developed in this research may have three main contributions: to contribute to the maintenance and valorisation of FAUP’s model; through the precise description of the methodological procedures, to contribute by transferability to similar studies; through the critical and objective framework of the problem underlying the hand drawing in architectural design teaching, to contribute to the broader discussion concerning the contemporary challenges on architectural education.

Keywords: architectural design teaching, architectural education, forms of representation, hand drawing

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Authors: Victoria I. Michailova, Denitsa B. Momekova, Hristiana A. Velichkova, Evgeni H. Ivanov

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The aim of this work is to design and develop thermo-responsive nanosized drug delivery systems based on poly(N-isopropylacrylamide)-g-poly(ethylene oxide) (PNIPAM-g-PEO) double hydrophilic graft copolymers. The PNIPAM-g-PEO copolymers are able to self-assemble in water into nanoparticles above the LCST of the thermo-responsive PNIPAM backbone and to disassemble and rapidly release the entrapped drugs upon cooling. However, their drug delivery applications are often hindered by their low loading capacity as the drugs to be encapsulated do not dissolve in water. In order to overcome this limitation, here we applied a low-temperature procedure with ethanol as an alternative route to the formation and loading a model hydrophobic drug, Indomethacin (IMC), into PNIPAM-g-PEO nanoparticles. The rationale for this approach was that ethanol dissolves both IMC and the copolymer and its mixing with water may induce micellization of PNIPAM-g-PEO at temperatures lower than the LCST. The influence of the volume fraction of ethanol and the temperature on the aggregation characteristics of PNIPAM-g-PEO copolymers (2.7 mol% PEO) was investigated by means of DLS, TEM and rheological dynamic oscillatory tests. The studies showed rich phase behavior at T < LCST, incl. the formation of highly solvated 500-1000 nm complex structures, 30-70 nm micelles and polymersomes as well as giant polymersomes, as the fraction of added ethanol increased. We believe that the PNIPAM-g-PEO self-assembly is favored due to the different solvation of its constituting blocks in ethanol-water mixtures. The incorporation of IMC led to alteration of the physicochemical and morphological characteristics of the blank nanoparticles. In this case, only monodisperse polymersomes and micelles were observed in the solutions with an average diameter less than 65 nm and substantial drug loading (DLC ~117 – 146 wt%). Indomethacin release from the nanoparticles was responsive to temperature changes, being much faster at a temperature of 42oC compared to that of 37oC under otherwise the same conditions. The results obtained suggest that these PNIPAM-g-PEO nanoparticles could be potential in mild hyper-thermic delivery of nonsteroidal anti-inflammatory drugs.

Keywords: drug delivery, nanoparticles, poly(N-isopropylacryl amide)-g-poly(ethylene oxide), thermo-responsive

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Authors: Shalini Arora, Sri Sivakumar

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The deep removal of high molecular weight sulphur compounds (e.g., 4,6, dimethyl dibenzothiophene) is challenging due to their steric hindrance. Hydrogenation desulfurization (HYD) pathway is the main pathway to remove these sulfur compounds, and it is mainly governed by the number of type 2 sites. The formation of type 2 sites can be enhanced by modulating the pore structure and the interaction between the active metal and support. To this end, we report the enhanced HDS catalytic activity of ultrasmall NiMo supported on amorphous alumina (A-Al₂O₃) catalysts by one pot colloidal synthesis method followed by calcination and sulfidation. The amorphous alumina (A-Al₂O₃) was chosen as the support due to its lower surface energy, better physicochemical properties, and enhanced acidic sites (due to the dominance of tetra and penta coordinated [Al] sites) than crystalline alumina phase. At 20% metal oxide composition, NiMo supported on A-Al₂O₃ catalyst showed 1.4 and 1.2 times more reaction rate constant and turn over frequency (TOF) respectively than the conventional catalyst (wet impregnated NiMo catalysts) for HDS reaction of dibenzothiophene reactant molecule. A-Al₂O₃ supported catalysts represented enhanced type 2 sites formation (because this catalystpossesses higher sulfidation degree (80%) and NiMoS sites (19.3 x 10¹⁷ sites/mg) with desired optimum stacking degree (2.5) than wet impregnated catalyst at same metal oxide composition 20%) along with higher active metal dispersion, Mo edge site fraction. The experimental observations were also supported by DFT simulations. Lower heat of adsorption (< 4.2 ev for MoS2 interaction and < 3.15 ev for Ni doped MoS2 interaction) values for A-Al₂O₃ confirmed the presence of weaker metal-support interaction in A-Al₂O₃ in contrast to crystalline ℽ-Al₂O3. The weak metal-support interaction for prepared catalysts clearly suggests the higher formation of type 2 sites which leads to higher catalytic activity for HDS reaction.

Keywords: amorphous alumina, colloidal, desulfurization, metal-support interaction

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Authors: K. Sahithya, I. Balasundar, Pritapant, T. Raghua

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Ni-based superalloy with a nominal composition Ni-14% Cr-11% Co-5.8% Mo-2.4% Ti-2.4% Nb-2.8% Al-0.26 % Fe-0.032% Si-0.069% C (all in wt %) is used as turbine discs in a variety of aero engines. Like any other superalloy, the primary processing of the as-cast superalloy poses a major challenge due to its complex alloy chemistry. The challenge was circumvented by characterizing the different phases present in the material, optimizing the homogenization treatment, identifying a suitable thermomechanical processing window using dynamic materials modeling. The as-cast material was subjected to homogenization at 1200°C for a soaking period of 8 hours and quenched using different media. Water quenching (WQ) after homogenization resulted in very fine spherical γꞌ precipitates of sizes 30-50 nm, whereas furnace cooling (FC) after homogenization resulted in bimodal distribution of precipitates (primary gamma prime of size 300nm and secondary gamma prime of size 5-10 nm). MC type primary carbides that are stable till the melting point of the material were found in both WQ and FC samples. Deformation behaviour of both the materials below (1000-1100°C) and above gamma prime solvus (1100-1175°C) was evaluated by subjecting the material to series of compression tests at different constant true strain rates (0.0001/sec-1/sec). An in-detail examination of the precipitate dislocation interaction mechanisms carried out using TEM revealed precipitate shearing and Orowan looping as the mechanisms governing deformation in WQ and FC, respectively. Incoherent/semi coherent gamma prime precipitates in the case of FC material facilitates better workability of the material, whereas the coherent precipitates in WQ material contributed to higher resistance to deformation of the material. Both the materials exhibited discontinuous dynamic recrystallization (DDRX) above gamma prime solvus temperature. The recrystallization kinetics was slower in the case of WQ material. Very fine grain boundary carbides ( ≤ 300 nm) retarded the recrystallisation kinetics in WQ. Coarse carbides (1-5 µm) facilitate particle stimulated nucleation in FC material. The FC material was cogged (primary hot working) 1120˚C, 0.03/sec resulting in significant grain refinement, i.e., from 3000 μm to 100 μm. The primary processed material was subjected to intensive thermomechanical deformation subsequently by reducing the temperature by 50˚C in each processing step with intermittent heterogenization treatment at selected temperatures aimed at simultaneous coarsening of the gamma prime precipitates and refinement of the gamma matrix grains. The heterogeneous annealing treatment carried out, resulted in gamma grains of 10 μm and gamma prime precipitates of 1-2 μm. Further thermo mechanical processing of the material was carried out at 1025˚C to increase the homogeneity of the obtained micro-duplex structure.

Keywords: superalloys, dynamic material modeling, nickel alloys, dynamic recrystallization, superplasticity

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Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

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Authors: R. Meier, M. Pander

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In accordance with the industry 4.0 concept, manufacturing process steps as well as the materials themselves are going to be more and more digitalized within the next years. The “digital twin” representing the simulated and measured dataset of the (semi-finished) product can be used to control and optimize the individual processing steps and help to reduce costs and expenditure of time in product development, manufacturing, and recycling. In the present work, two material characterization methods based on Lamb waves were evaluated and compared. For demonstration purpose, both methods were shown at a standard industrial product - copper ribbons, often used in photovoltaic modules as well as in high-current microelectronic devices. By numerical approximation of the Rayleigh-Lamb dispersion model on measured phase velocities second order elastic constants (Young’s modulus, Poisson’s ratio) were determined. Furthermore, the effective third order elastic constants were evaluated by applying elastic, “non-destructive”, mechanical stress on the samples. In this way, small microstructural variations due to mechanical preconditioning could be detected for the first time. Both methods were compared with respect to precision and inline application capabilities. Microstructure of the samples was systematically varied by mechanical loading and annealing. Changes in the elastic ultrasound transport properties were correlated with results from microstructural analysis and mechanical testing. In summary, monitoring the elastic material properties of plate-like structures using Lamb waves is valuable for inline and non-destructive material characterization and manufacturing process control. Second order elastic constants analysis is robust over wide environmental and sample conditions, whereas the effective third order elastic constants highly increase the sensitivity with respect to small microstructural changes. Both Lamb wave based characterization methods are fitting perfectly into the industry 4.0 concept.

Keywords: lamb waves, industry 4.0, process control, elasticity, acoustoelasticity, microstructure

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