Search results for: protein secondary structure prediction
Commenced in January 2007
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Edition: International
Paper Count: 14388

Search results for: protein secondary structure prediction

2568 Influence of Laser Excitation on SERS of Silicon Nanocrystals

Authors: Khamael M. Abualnaja, Lidija Šiller, Ben R. Horrocks

Abstract:

Surface enhanced Raman spectroscopy (SERS) of Silicon nano crystals (SiNCs) were obtained using two different laser excitations: 488 nm and 514.5 nm. Silver nano particles were used as plasmonics metal nano particles due to a robust SERS effect that observed when they mixed with SiNCs. SiNCs have been characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It is found that the SiNCs are crystalline with an average diameter of 65 nm and FCC lattice. Silver nano particles (AgNPs) of two different sizes were synthesized using photo chemical reduction of AgNO3 with sodium dodecyl sulfate (SDS). The synthesized AgNPs have a polycrystalline structure with an average particle diameter of 100 nm and 30 nm, respectively. A significant enhancement in the SERS intensity was observed for AgNPs100/SiNCs and AgNPs30/SiNCs mixtures increasing up to 9 and 3 times respectively using 488 nm intensity; whereas the intensity of the SERS signal increased up to 7 and 2 times respectively, using 514.5 nm excitation source. The enhancement in SERS intensities occurs as a result of the coupling between the excitation laser light and the plasmon bands of AgNPs; thus this intense field at AgNPs surface couples strongly to SiNCs. The results provide good consensus between the wavelength of the laser excitation source and surface plasmon resonance absorption band of silver nano particles consider to be an important requirement in SERS experiments.

Keywords: silicon nanocrystals (SiNCs), silver nanoparticles (AgNPs), surface enhanced raman spectroscopy (SERS)

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2567 Middle School as a Developmental Context for Emergent Citizenship

Authors: Casta Guillaume, Robert Jagers, Deborah Rivas-Drake

Abstract:

Civically engaged youth are critical to maintaining and/or improving the functioning of local, national and global communities and their institutions. The present study investigated how school climate and academic beliefs (academic self-efficacy and school belonging) may inform emergent civic behaviors (emergent citizenship) among self-identified middle school youth of color (African American, Multiracial or Mixed, Latino, Asian American or Pacific Islander, Native American, and other). Study aims: 1) Understand whether and how school climate is associated with civic engagement behaviors, directly and indirectly, by fostering a positive sense of connection to the school and/or engendering feelings of self-efficacy in the academic domain. Accordingly, we examined 2) The association of youths’ sense of school connection and academic self-efficacy with their personally responsible and participatory civic behaviors in school and community contexts—both concurrently and longitudinally. Data from two subsamples of a larger study of social/emotional development among middle school students were used for longitudinal and cross sectional analysis. The cross-sectional sample included 324 6th-8th grade students, of which 43% identified as African American, 20% identified as Multiracial or Mixed, 18% identified as Latino, 12% identified as Asian American or Pacific Islander, 6% identified as Other, and 1% identified as Native American. The age of the sample ranged from 11 – 15 (M = 12.33, SD = .97). For the longitudinal test of our mediation model, we drew on data from the 6th and 7th grade cohorts only (n =232); the ethnic and racial diversity of this longitudinal subsample was virtually identical to that of the cross-sectional sample. For both the cross-sectional and longitudinal analyses, full information maximum likelihood was used to deal with missing data. Fit indices were inspected to determine if they met the recommended thresholds of RMSEA below .05 and CFI and TLI values of at least .90. To determine if particular mediation pathways were significant, the bias-corrected bootstrap confidence intervals for each indirect pathway were inspected. Fit indices for the latent variable mediation model using the cross-sectional data suggest that the hypothesized model fit the observed data well (CFI = .93; TLI =. 92; RMSEA = .05, 90% CI = [.04, .06]). In the model, students’ perceptions of school climate were significantly and positively associated with greater feelings of school connectedness, which were in turn significantly and positively associated with civic engagement. In addition, school climate was significantly and positively associated with greater academic self-efficacy, but academic self-efficacy was not significantly associated with civic engagement. Tests of mediation indicated there was one significant indirect pathway between school climate and civic engagement behavior. There was an indirect association between school climate and civic engagement via its association with sense of school connectedness, indirect association estimate = .17 [95% CI: .08, .32]. The aforementioned indirect association via school connectedness accounted for 50% (.17/.34) of the total effect. Partial support was found for the prediction that students’ perceptions of a positive school climate are linked to civic engagement in part through their role in students’ sense of connection to school.

Keywords: civic engagement, early adolescence, school climate, school belonging, developmental niche

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2566 Evaluation of Corrosion Behaviour of Austenitic Steel 08Cr18Ni10Ti Exposed to Supercritical Water

Authors: Monika Šípová, Daniela Marušáková, Claudia Aparicio

Abstract:

New sources and ways of producing energy are still seeking, and one of the sustainable ways is Generation IV nuclear reactors. The supercritical water-cooled reactor is one of the six nuclear reactors of Generation IV, and as a consequence of the development of light water, reactors seem to be the most perspective. Thus, materials usually used in light water reactors are also tested under the expected operating conditions of the supercritical water-cooled reactor. Austenitic stainless steel 08Cr18Ni10Ti is widely used in the eastern types of light water nuclear power plants. Therefore, specimens of 08Cr18Ni10Ti were exposed to conditions close to the pseudo-critical point of water and high-temperature supercritical water. The description and evaluation of the corrosion behaviour of austenitic stainless steel have been done based on the results of X-ray diffraction in combination with energy dispersive spectroscopy and electron backscatter diffraction. Thus, significant differences have been found in the structure and composition of oxides formed depending on the temperature of exposure. The high temperature of supercritical water resulted in localised form of corrosion in contrast to the thin oxide layer of 1 µm present on the surface of specimens exposed close to the pseudo-critical point of water. The obtained results are important for further research as the supercritical water can be successfully used as a coolant for small modular reactors, which are currently of interest.

Keywords: localised corrosion, supercritical water, stainless steel, electron backscatter diffraction

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2565 Live Concert Performances in Preschool: Requirements of a Successful Concert for Young Children

Authors: Mei-Ying Liao

Abstract:

The main purpose of this study was to examine the requirements of a successful concert for young children in preschool in Taiwan. This study reports a case study of a preschool’s experience which undertook ten concerts for young children. The main audiences were young children who were two to six years of age. The performers, including children’s family, amateurs and professional performers, were invited to perform music instruments or singing twice a week. The performers participated in these concerts separately, as a solo or ensemble performance. There were totally ten concerts. The structure of concert included the performance, musical activities, questions and answers, song requests, and exploration of instruments. Data collection included interviews with children, teachers and performers, concert observations, and footnotes. Results showed that the requirements of a successful and meaningful concert for young children were suggested to include concert preparation, concert, and post activities. The concert organizer, host and classroom teachers played vital roles for a successful concert. The organizer had to organize the programs and prepared for the concerts based on the needs and interests of their audience of young children, engage their attention and offer the potential to expand their musical worlds. The hosts had to build a bridge between performers and young children who had to know how they could delight and educate children. Concerts combined games, storytelling, instrument exploration and great music had great effects. Finally, the classroom teachers had to do the extension activities after the concerts so that the children will involve more and get more enthusiasm in concerts.

Keywords: case study, concert, music education, performance

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2564 Effect of Manganese Doping on Ferrroelectric Properties of (K0.485Na0.5Li0.015)(Nb0.98V0.02)O3 Lead-Free Piezoceramic

Authors: Chongtham Jiten, Radhapiyari Laishram, K. Chandramani Singh

Abstract:

Alkaline niobate (Na0.5K0.5)NbO3 ceramic system has attracted major attention in view of its potential for replacing the highly toxic but superior lead zirconate titanate (PZT) system for piezoelectric applications. Recently, a more detailed study of this system reveals that the ferroelectric and piezoelectric properties are optimized in the Li- and V-modified system having the composition (K0.485Na0.5Li0.015)(Nb0.98V0.02)O3. In the present work, we further study the pyroelectric behaviour of this composition along with another doped with Mn4+. So, (K0.485Na0.5Li0.015)(Nb0.98V0.02)O3 + x MnO2 (x = 0, and 0.01 wt. %) ceramic compositions were synthesized by conventional ceramic processing route. X-ray diffraction study reveals that both the undoped and Mn4+-doped ceramic samples prepared crystallize into a perovskite structure having orthorhombic symmetry. Dielectric study indicates that Mn4+ doping has little effect on both the Curie temperature (Tc) and tetragonal-orthorhombic phase transition temperature (Tot). The bulk density, room-temperature dielectric constant (εRT), and room-c The room-temperature coercive field (Ec) is observed to be lower in Mn4+ doped sample. The detailed analysis of the P-E hysteresis loops over the range of temperature from about room temperature to Tot points out that enhanced ferroelectric properties exist in this temperature range with better thermal stability for the Mn4+ doped ceramic. The study reveals that small traces of Mn4+ can modify (K0.485Na0.5Li0.015)(Nb0.98V0.02)O3 system so as to improve its ferroelectric properties with good thermal stability over a wide range of temperature.

Keywords: ceramics, dielectric properties, ferroelectric properties, lead-free, sintering, thermal stability

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2563 Investigating Citizens’ Perceptions and Attitudes toward China’s National Determined Contribution's Energy Restructuring Plan in Linfen City

Authors: Yuan Zhao, Phimsupha Kokchang

Abstract:

As a responsible nation, China has outlined its Nationally Determined Contributions (NDCs) of reaching peak carbon by 2030 and carbon neutrality by 2060. Peak and carbon neutrality are tough goals to achieve, and China must undertake a shift to green energy. In contrast, China's existing energy consumption structure is unsustainable and heavily dependent on coal supplies. China must revise its energy mix planning in order to strengthen energy security and satisfy the requirement for low-carbon energy generation to mitigate climate change. Shanxi Province is one of China's most important coal-producing regions, and Linfen is one of the province's key economic towns. However, Shanxi Province's economic development is severely hampered by the region's high levels of pollution and energy consumption. The purpose of this study is to investigate Linfen citizens' perceptions and attitudes toward China's NDC's energy restructuring plan through questionnaires. The majority of respondents were aware of China's NDCs, as indicated by 402 valid responses to an online questionnaire. Furthermore, respondents' perceptions and attitudes toward renewable energy initiatives are growing. To ensure that the results were dependable and consistent, reliability and validity were examined. According to the findings, the majority of Linfen's citizens believe that renewable energy projects such as solar and wind, which are consistent with China's NDCs, may improve their quality of life, public health, and the nation's economy.

Keywords: China’s NDC, perceptions, attitudes, Linfen, energy restructuring

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2562 Identification and Characterization of Small Peptides Encoded by Small Open Reading Frames using Mass Spectrometry and Bioinformatics

Authors: Su Mon Saw, Joe Rothnagel

Abstract:

Short open reading frames (sORFs) located in 5’UTR of mRNAs are known as uORFs. Characterization of uORF-encoded peptides (uPEPs) i.e., a subset of short open reading frame encoded peptides (sPEPs) and their translation regulation lead to understanding of causes of genetic disease, proteome complexity and development of treatments. Existence of uORFs within cellular proteome could be detected by LC-MS/MS. The ability of uORF to be translated into uPEP and achievement of uPEP identification will allow uPEP’s characterization, structures, functions, subcellular localization, evolutionary maintenance (conservation in human and other species) and abundance in cells. It is hypothesized that a subset of sORFs are translatable and that their encoded sPEPs are functional and are endogenously expressed contributing to the eukaryotic cellular proteome complexity. This project aimed to investigate whether sORFs encode functional peptides. Liquid chromatography-mass spectrometry (LC-MS) and bioinformatics were thus employed. Due to probable low abundance of sPEPs and small in sizes, the need for efficient peptide enrichment strategies for enriching small proteins and depleting the sub-proteome of large and abundant proteins is crucial for identifying sPEPs. Low molecular weight proteins were extracted using SDS-PAGE from Human Embryonic Kidney (HEK293) cells and Strong Cation Exchange Chromatography (SCX) from secreted HEK293 cells. Extracted proteins were digested by trypsin to peptides, which were detected by LC-MS/MS. The MS/MS data obtained was searched against Swiss-Prot using MASCOT version 2.4 to filter out known proteins, and all unmatched spectra were re-searched against human RefSeq database. ProteinPilot v5.0.1 was used to identify sPEPs by searching against human RefSeq, Vanderperre and Human Alternative Open Reading Frame (HaltORF) databases. Potential sPEPs were analyzed by bioinformatics. Since SDS PAGE electrophoresis could not separate proteins <20kDa, this could not identify sPEPs. All MASCOT-identified peptide fragments were parts of main open reading frame (mORF) by ORF Finder search and blastp search. No sPEP was detected and existence of sPEPs could not be identified in this study. 13 translated sORFs in HEK293 cells by mass spectrometry in previous studies were characterized by bioinformatics. Identified sPEPs from previous studies were <100 amino acids and <15 kDa. Bioinformatics results showed that sORFs are translated to sPEPs and contribute to proteome complexity. uPEP translated from uORF of SLC35A4 was strongly conserved in human and mouse while uPEP translated from uORF of MKKS was strongly conserved in human and Rhesus monkey. Cross-species conserved uORFs in association with protein translation strongly suggest evolutionary maintenance of coding sequence and indicate probable functional expression of peptides encoded within these uORFs. Translation of sORFs was confirmed by mass spectrometry and sPEPs were characterized with bioinformatics.

Keywords: bioinformatics, HEK293 cells, liquid chromatography-mass spectrometry, ProteinPilot, Strong Cation Exchange Chromatography, SDS-PAGE, sPEPs

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2561 Optimizing Agricultural Packaging in Fiji: Strategic Barrier Analysis Using Interpretive Structural Modeling and Cross-Impact Matrix Multiplication Applied to Classification

Authors: R. Ananthanarayanan, S. B. Nakula, D. R. Seenivasagam, J. Naua, B. Sharma

Abstract:

Product packaging is a critical component of production, trade, and marketing, playing numerous vital roles that often go unnoticed by consumers. Packaging is essential for maintaining the shelf life, quality assurance, and safety of both manufactured and agricultural products. For example, harvested produce or processed foods can quickly lose quality and freshness, making secure packaging crucial for preservation and safety throughout the food supply chain. In Fiji, agricultural packaging has primarily been managed by local companies for international trade, with gradual advancements in these practices. To further enhance the industry’s performance, this study examines the challenges and constraints hindering the optimization of agricultural packaging practices in Fiji. The study utilizes Multi-Criteria Decision Making (MCDM) tools, specifically Interpretive Structural Modeling (ISM) and Cross-Impact Matrix Multiplication Applied to Classification (MICMAC). ISM analyzes the hierarchical structure of barriers, categorizing them from the least to the most influential, while MICMAC classifies barriers based on their driving and dependence power. This approach helps identify the interrelationships between barriers, providing valuable insights for policymakers and decision-makers to propose innovative solutions for sustainable development in the agricultural packaging sector, ultimately shaping the future of packaging practices in Fiji.

Keywords: agricultural packaging, barriers, ISM, MICMAC

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2560 Genetics of Pharmacokinetic Drug-Drug Interactions of Most Commonly Used Drug Combinations in the UK: Uncovering Unrecognised Associations

Authors: Mustafa Malki, Ewan R. Pearson

Abstract:

Tools utilized by health care practitioners to flag potential adverse drug reactions secondary to drug-drug interactions ignore individual genetic variation, which has the potential to markedly alter the severity of these interactions. To our best knowledge, there have been limited published studies on the impact of genetic variation on drug-drug interactions. Therefore, our aim in this project is the discovery of previously unrecognized, clinically important drug-drug-gene interactions (DDGIs) within the list of most commonly used drug combinations in the UK. The UKBB database was utilized to identify the top most frequently prescribed drug combinations in the UK with at least one route of interaction (over than 200 combinations were identified). We have recognised 37 common and unique interacting genes considering all of our drug combinations. Out of around 600 potential genetic variants found in these 37 genes, 100 variants have met the selection criteria (common variant with minor allele frequency ≥ 5%, independence, and has passed HWE test). The association between these variants and the use of each of our top drug combinations has been tested with a case-control analysis under the log-additive model. As the data is cross-sectional, drug intolerance has been identified from the genotype distribution as presented by the lower percentage of patients carrying the risky allele and on the drug combination compared to those free of these risk factors and vice versa with drug tolerance. In GoDARTs database, the same list of common drug combinations identified by the UKBB was utilized here with the same list of candidate genetic variants but with the addition of 14 new SNPs so that we have a total of 114 variants which have met the selection criteria in GoDARTs. From the list of the top 200 drug combinations, we have selected 28 combinations where the two drugs in each combination are known to be used chronically. For each of our 28 combinations, three drug response phenotypes have been identified (drug stop/switch, dose decrease, or dose increase of any of the two drugs during their interaction). The association between each of the three phenotypes belonging to each of our 28 drug combinations has been tested against our 114 candidate genetic variants. The results show replication of four findings between both databases : (1) Omeprazole +Amitriptyline +rs2246709 (A > G) variant in CYP3A4 gene (p-values and ORs with the UKBB and GoDARTs respectively = 0.048,0.037,0.92,and 0.52 (dose increase phenotype)) (2) Simvastatin + Ranitidine + rs9332197 (T > C) variant in CYP2C9 gene (0.024,0.032,0.81, and 5.75 (drug stop/switch phenotype)) (3) Atorvastatin + Doxazosin + rs9282564 (T > C) variant in ABCB1 gene (0.0015,0.0095,1.58,and 3.14 (drug stop/switch phenotype)) (4) Simvastatin + Nifedipine + rs2257401 (C > G) variant in CYP3A7 gene (0.025,0.019,0.77,and 0.30 (drug stop/switch phenotype)). In addition, some other non-replicated, but interesting, significant findings were detected. Our work also provides a great source of information for researchers interested in DD, DG, or DDG interactions studies as it has highlighted the top common drug combinations in the UK with recognizing 114 significant genetic variants related to drugs' pharmacokinetic.

Keywords: adverse drug reactions, common drug combinations, drug-drug-gene interactions, pharmacogenomics

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2559 Development of a Biomaterial from Naturally Occurring Chloroapatite Mineral for Biomedical Applications

Authors: H. K. G. K. D. K. Hapuhinna, R. D. Gunaratne, H. M. J. C. Pitawala

Abstract:

Hydroxyapatite is a bioceramic which can be used for applications in orthopedics and dentistry due to its structural similarity with the mineral phase of mammalian bones and teeth. In this study, it was synthesized, chemically changing natural Eppawala chloroapatite mineral as a value-added product. Sol-gel approach and solid state sintering were used to synthesize products using diluted nitric acid, ethanol and calcium hydroxide under different conditions. Synthesized Eppawala hydroxyapatite powder was characterized using X-ray Fluorescence (XRF), X-ray Powder Diffraction (XRD), Fourier-transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) in order to find out its composition, crystallinity, presence of functional groups, bonding type, surface morphology, microstructural features, and thermal dependence and stability, respectively. The XRD results reflected the formation of a hexagonal crystal structure of hydroxyapatite. Elementary composition and microstructural features of products were discussed based on the XRF and SEM results of the synthesized hydroxyapatite powder. TGA and DSC results of synthesized products showed high thermal stability and good material stability in nature. Also, FTIR spectroscopy results confirmed the formation of hydroxyapatite from apatite via the presence of hydroxyl groups. Those results coincided with the FTIR results of mammalian bones including human bones. The study concludes that there is a possibility of producing hydroxyapatite using commercially available Eppawala chloroapatite in Sri Lanka.

Keywords: dentistry, Eppawala chlorapatite, hydroxyapatite, orthopedics

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2558 The Effect of Foreign Owned Firms and Licensed Manufacturing Agreements on Innovation: Case of Pharmaceutical Firms in Developing Countries

Authors: Ilham Benali, Nasser Hajji, Nawfal Acha

Abstract:

Given the fact that the pharmaceutical industry is a commonly studied sector in the context of innovation, the majority of innovation research is devoted to the developed markets known by high research and development (R&D) assets and intensive innovation. In contrast, in developing countries where R&D assets are very low, there is relatively little research to mention in the area of pharmaceutical sector innovation, characterized mainly by two principal elements which are the presence of foreign-owned firms and licensed manufacturing agreements between local firms and multinationals. With the scarcity of research in this field, this paper attempts to study the effect of these two elements on the firms’ innovation tendencies. Other traditional factors that influence innovation, which are the age and the size of the firm, the R&D activities and the market structure, revealed in the literature review, will be included in the study in order to try to make this work more exhaustive. The study starts by examining innovation tendency in pharmaceutical firms located in developing countries before analyzing the effect of foreign-owned firms and licensed manufacturing agreements between local firms and multinationals on technological, organizational and marketing innovation. Based on the related work and on the theoretical framework developed, there is a probability that foreign-owned firms and licensed manufacturing agreements between local firms and multinationals have a negative influence on technological innovation. The opposite effect is possible in the case of organizational and marketing innovation.

Keywords: developing countries, foreign owned firms, innovation, licensed manufacturing agreements, pharmaceutical industry

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2557 Non-Invasive Techniques for Management of Carious Primary Dentition Using Silver Diamine Fluoride and Moringa Extract as a Modification of the Hall Technique

Authors: Rasha F. Sharaf

Abstract:

Treatment of dental caries in young children is considered a great challenge for all dentists, especially with uncooperative children. Recently non-invasive techniques have been highlighted as they alleviate the need for local anesthesia and other painful procedures during management of carious teeth and, at the same time, increase the success rate of the treatment done. Silver Diamine Fluoride (SDF) is one of the most effective cariostatic materials that arrest the progression of carious lesions and aid in remineralizing the demineralized tooth structure. Both fluoride and silver ions proved to have an antibacterial action and aid in the precipitation of an insoluble layer that prevents further decay. At the same time, Moringa proved to have an effective antibacterial action against different types of bacteria, therefore, it can be used as a non-invasive technique for the management of caries in children. One of the important theories for the control of caries is by depriving the cariogenic bacteria from nutrients causing their starvation and death, which can be achieved by applying stainless steel crown on primary molars with carious lesions which are not involving the pulp, and this technique is known as Hall technique. The success rate of the Hall technique can be increased by arresting the carious lesion using either SDF or Moringa and gaining the benefit of their antibacterial action. Multiple clinical cases with 1 year follow up will be presented, comparing different treatment options, and using various materials and techniques for non-invasive and non-painful management of carious primary teeth.

Keywords: SDF, hall technique, carious primary teeth, moringa extract

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2556 The Determinants of Female Participation to the Labour Force in Turkey

Authors: Zeynep Karacor, Rahime Hulya Ozturk

Abstract:

Located in developing countries but with the successful performance in recent years have shown in emerging economies , the labor factor has undoubtedly an important place in Turkish economy. The theorists have emphasized the importance of labor and human capital factors for many years. The importance of human capital is emerging in the process of determining the labor force participation rate. It is relatively easy to employ qualified labor force but employment of unskilled labor is particularly difficult. Another factor affecting the gender differences are employment opportunities in the labor force. In our country, the employment conditions of men and women differ. Factors causing these differentials are inherent job requirements, the social structure of society, women's point of view, working hours, working conditions. Crisis in our country in recent years have significantly affect the labor force participation rates. In particular, women's labor force participation rates have shown a decrease in crisis.In crisis female laborforce leave their job and go their home. It is the sole provider of social perception of men so in crisis period it is considered that woman lost their job. In the first part of this study the current situation in the world of female participation in the labor force in Turkey will examine. In the second part of the study literature will be examined. In the third and last part of the study factors of determinants of female labor force participation rate analysis will done by Granger Causality Analysis.

Keywords: female labour force, employment, labor force, Turkey

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2555 Household Socioeconomic Factors Associated with Teenage Pregnancies in Kigali City, Rwanda

Authors: Dieudonne Uwizeye, Reuben Muhayiteto

Abstract:

Teenage pregnancy is a challenging problem for sustainable development due to restrictions it poses to socioeconomic opportunities for young mothers, their children and families. Being unable to take appropriate economic and social responsibilities, teen mothers get trapped into poverty and become economic burden to their family and country. Besides, teenage pregnancy is also a health problem because children born to very young mothers are vulnerable with greater risk of illnesses and deaths, and teenage mothers are more likely to be exposed to greater risk of maternal mortality and to other health and psychological problems. In Kigali city, in Rwanda, teenage pregnancy rate is currently high and its increase in recent years is worrisome. However, only individual factors influencing the teenage pregnancy tend to be the basis of interventions. It is important to understand the important socioeconomic factors at the household level that are associated with teenage pregnancy to help government, parents, and other stakeholders to appropriately address the problem with sustainable measures. This study analyzed secondary data from the Fifth Rwanda Demographic and Health Survey (RDHS-V 2014-2015) conducted by the National Institute of Statistics of Rwanda (NISR). The aim was to examine household socio-economic factors that are associated with incidence of teenage pregnancies in Kigali city. In addition to descriptive analysis, Pearson’s Chi Square and Binary Logistic Regression were used in the analysis. Findings indicate that marital status and age of household head, number of members in a household, number of rooms used for sleeping, educational level of the household head and household's wealth are significantly associated with teenage pregnancy in Rwanda ( p< 0.05). It was found that teenagers living with parents, those having parents with higher education and those from richer families are less likely to become pregnant. Age of household head was pinpointed as factor to teenage pregnancy, with teenage-headed households being more vulnerable. The findings also revealed that household composition correlates with the probability of teenage pregnancy (p < 0.05) with teenagers from households with less number of members being more vulnerable. Regarding the size of the house, the study suggested that the more rooms available in households, the less incidences of teenage pregnancy are likely to be observed (p < 0.05). However, teenage pregnancy was not significantly associated with physical violence among parents (p = 0.65) and sex of household heads (p = 0.52), except in teen-headed households of which female are predominantly heads. The study concludes that teenage pregnancy remains a serious social, economic and health problem in Rwanda. The study informs government officials, parents and other stakeholders to take interventions and preventive measures through community sex education, policies and strategies to foster effective parental guidance, care and control of young girls through meeting their necessary social and financial needs within households.

Keywords: household socio-economic factors, Rwanda, Rwanda demographic and health survey, teenage pregnancy

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2554 The Strategic Entering Time of a Commerce Platform

Authors: Chia-li Wang

Abstract:

The surge of service and commerce platforms, such as e-commerce and internet-of-things, have rapidly changed our lives. How to avoid the congestion and get the job done in the platform is now a common problem that many people encounter every day. This requires platform users to make decisions about when to enter the platform. To that end, we investigate the strategic entering time of a simple platform containing random numbers of buyers and sellers of some item. Upon a trade, the buyer and the seller gain respective profits, yet they pay the cost of waiting in the platform. To maximize their expected payoffs from trading, both buyers and sellers can choose their entering times. This creates an interesting and practical framework of a game that is played among buyers, among sellers, and between them. That is, a strategy employed by a player is not only against players of its type but also a response to those of the other type, and, thus, a strategy profile is composed of strategies of buyers and sellers. The players' best response, the Nash equilibrium (NE) strategy profile, is derived by a pair of differential equations, which, in turn, are used to establish its existence and uniqueness. More importantly, its structure sheds valuable insights of how the entering strategy of one side (buyers or sellers) is affected by the entering behavior of the other side. These results provide a base for the study of dynamic pricing for stochastic demand-supply imbalances. Finally, comparisons between the social welfares (the sum of the payoffs incurred by individual participants) obtained by the optimal strategy and by the NE strategy are conducted for showing the efficiency loss relative to the socially optimal solution. That should help to manage the platform better.

Keywords: double-sided queue, non-cooperative game, nash equilibrium, price of anarchy

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2553 Tectono-Stratigraphic Architecture, Depositional Systems and Salt Tectonics to Strike-Slip Faulting in Kribi-Campo-Cameroon Atlantic Margin with an Unsupervised Machine Learning Approach (West African Margin)

Authors: Joseph Bertrand Iboum Kissaaka, Charles Fonyuy Ngum Tchioben, Paul Gustave Fowe Kwetche, Jeannette Ngo Elogan Ntem, Joseph Binyet Njebakal, Ribert Yvan Makosso-Tchapi, François Mvondo Owono, Marie Joseph Ntamak-Nida

Abstract:

Located in the Gulf of Guinea, the Kribi-Campo sub-basin belongs to the Aptian salt basins along the West African Margin. In this paper, we investigated the tectono-stratigraphic architecture of the basin, focusing on the role of salt tectonics and strike-slip faults along the Kribi Fracture Zone with implications for reservoir prediction. Using 2D seismic data and well data interpreted through sequence stratigraphy with integrated seismic attributes analysis with Python Programming and unsupervised Machine Learning, at least six second-order sequences, indicating three main stages of tectono-stratigraphic evolution, were determined: pre-salt syn-rift, post-salt rift climax and post-rift stages. The pre-salt syn-rift stage with KTS1 tectonosequence (Barremian-Aptian) reveals a transform rifting along NE-SW transfer faults associated with N-S to NNE-SSW syn-rift longitudinal faults bounding a NW-SE half-graben filled with alluvial to lacustrine-fan delta deposits. The post-salt rift-climax stage (Lower to Upper Cretaceous) includes two second-order tectonosequences (KTS2 and KTS3) associated with the salt tectonics and Campo High uplift. During the rift-climax stage, the growth of salt diapirs developed syncline withdrawal basins filled by early forced regression, mid transgressive and late normal regressive systems tracts. The early rift climax underlines some fine-grained hangingwall fans or delta deposits and coarse-grained fans from the footwall of fault scarps. The post-rift stage (Paleogene to Neogene) contains at least three main tectonosequences KTS4, KTS5 and KTS6-7. The first one developed some turbiditic lobe complexes considered as mass transport complexes and feeder channel-lobe complexes cutting the unstable shelf edge of the Campo High. The last two developed submarine Channel Complexes associated with lobes towards the southern part and braided delta to tidal channels towards the northern part of the Kribi-Campo sub-basin. The reservoir distribution in the Kribi-Campo sub-basin reveals some channels, fan lobes reservoirs and stacked channels reaching up to the polygonal fault systems.

Keywords: tectono-stratigraphic architecture, Kribi-Campo sub-basin, machine learning, pre-salt sequences, post-salt sequences

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2552 Intelligence Failures and Infiltration: The Case of the Ethiopian Army 1977-1991

Authors: Fantahun Ibrahim

Abstract:

The Ethiopian army was one of the largest and most heavily armed ground forces in Africa between 1974 and 1991. It scored a decisive victory over Somalia’s armed forces in March 1978. It, however, failed to withstand the combined onslaught of the northern insurgents from Tigray and Eritrea and finally collapsed in 1991. At the heart of the problem was the army’s huge intelligence failure. The northern insurgents, on the other hand, had a cutting edge in intelligence gathering. Among other things they infiltrated the army high command and managed to get top secrets about the army. Commanders who had fallen into the hands of the insurgents in several battles were told to send letters to their colleagues in the command structure and persuade them to work secretly for the insurgents. Some commanders did work for the insurgents and played a great role in the undoing of military operations. Insurgent commanders were able to warn their fighters about air strikes before jet fighters took off from airfields in the northern theatre. It was not uncommon for leaders of insurgents to get the full details of military operations days before their implementation. Such intelligence failures led to major military disasters like the fall of Afabet (March, 1988), Enda Sellase (February, 1989), Massawa and Debre Tabor (February, 1990), Karra Mishig, Meragna and Alem Ketema (June, 1990). This paper, therefore, seeks to investigate the army’s intelligence failures using untapped archival documents kept at the Ministry of National Defence in Addis Ababa and interviewing key former commanders of the army and ex-leaders of the insurgents.

Keywords: Ethiopian army, intelligence, infiltration, insurgents

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2551 Replica-Exchange Metadynamics Simulations of G-Quadruplex DNA Structures Under Substitution of K+ by Na+ Ions

Authors: Juan Antonio Mondragon Sanchez, Ruben Santamaria

Abstract:

The DNA G-quadruplex is a four-stranded DNA structure conformed by stacked planes of four base paired guanines (G-quartet). The guanine rich DNA sequences are present in many sites of genomic DNA and can potentially lead to the formation of G-quadruplexes, especially at the 3'-terminus of the human telomeric DNA with many TTAGGG repeats. The formation and stabilization of a G-quadruplex by small ligands at the telomeric region can inhibit the telomerase activity. In turn, the ligands can be used to regulate oncogene expression making the G-quadruplex an attractive target for anticancer therapy. Clearly, the G-quadruplex structured in the telomeric DNA is of fundamental importance for rational drug design. In this context, we investigate two G-quadruplex structures, the first follows from the sequence TTAGGG(TTAGGG)3TT (HUT1), and the second from AAAGGG(TTAGGG)3AA (HUT2), both in a K+ solution. We determine the free energy surfaces of the HUT1 and HUT2 structures and investigate their conformations using replica-exchange metadynamics simulations. The carbonyl-carbonyl distances belonging to different guanines residues are selected as the main collective variables to determine the free energy surfaces. The surfaces exhibit two main local minima, compatible with experiments on the conformational transformations of HUT1 and HUT2 under substitution of the K+ ions by the Na+ ions. The conformational transitions are not observed in short MD simulations without the use of the metadynamics approach. The results of this work should be of help to understand the formation and stability of human telomeric G-quadruplex in environments including the presence of K+ and Na+ ions.

Keywords: g-quadruplex, metadynamics, molecular dynamics, replica-exchange

Procedia PDF Downloads 341
2550 Effect of Architecture and Operating Conditions of Vehicle on Bulb Lifetime in Automotive

Authors: Hatice Özbek, Caner Çil, Ahmet Rodoplu

Abstract:

Automotive lighting is the leading function in the configuration of vehicle architecture. Especially headlights and taillights from external lighting functions are among the structures that determine the stylistic character of the vehicle. At the same time, the fact that lighting functions are related to many other functions brings along difficulties in design. Customers expect maximum quality from the vehicle. In these circumstances, it is necessary to make designs that aim to keep the performance of bulbs with limited working lives at the highest level. With this study, the factors that influence the working lives of filament lamps were examined and bulb explosions that can occur sooner than anticipated in the future were prevented while the vehicle was still in the design phase by determining the relations with electrical, dynamical and static variables. Especially the filaments of the bulbs used in the front lighting of the vehicle are deformed in a shorter time due to the high voltage requirement. In addition to this, rear lighting lamps vibrate as a result of the tailgate opening and closing and cause the filaments to be exposed to high stress. With this study, the findings that cause bulb explosions were evaluated. Among the most important findings: 1. The structure of the cables to the lighting functions of the vehicle and the effect of the voltage values are drawn; 2. The effect of the vibration to bulb throughout the life of the vehicle; 3 The effect of the loads carried to bulb while the vehicle doors are opened and closed. At the end of the study, the maximum performance was established in the bulb lifetimes with the optimum changes made in the vehicle architecture based on the findings obtained.

Keywords: vehicle architecture, automotive lighting functions, filament lamps, bulb lifetime

Procedia PDF Downloads 149
2549 SPBAC: A Semantic Policy-Based Access Control for Database Query

Authors: Aaron Zhang, Alimire Kahaer, Gerald Weber, Nalin Arachchilage

Abstract:

Access control is an essential safeguard for the security of enterprise data, which controls users’ access to information resources and ensures the confidentiality and integrity of information resources [1]. Research shows that the more common types of access control now have shortcomings [2]. In this direction, to improve the existing access control, we have studied the current technologies in the field of data security, deeply investigated the previous data access control policies and their problems, identified the existing deficiencies, and proposed a new extension structure of SPBAC. SPBAC extension proposed in this paper aims to combine Policy-Based Access Control (PBAC) with semantics to provide logically connected, real-time data access functionality by establishing associations between enterprise data through semantics. Our design combines policies with linked data through semantics to create a "Semantic link" so that access control is no longer per-database and determines that users in each role should be granted access based on the instance policy, and improves the SPBAC implementation by constructing policies and defined attributes through the XACML specification, which is designed to extend on the original XACML model. While providing relevant design solutions, this paper hopes to continue to study the feasibility and subsequent implementation of related work at a later stage.

Keywords: access control, semantic policy-based access control, semantic link, access control model, instance policy, XACML

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2548 Electrical Properties of Nanocomposite Fibres Based On Cellulose and Graphene Nanoplatelets Prepared Using Ionic Liquids

Authors: Shaya Mahmoudian, Mohammad Reza Sazegar, Nazanin Afshari

Abstract:

Graphene, a single layer of carbon atoms in a hexagonal lattice, has recently attracted great attention due to its unique mechanical, thermal and electrical properties. The high aspect ratio and unique surface features of graphene resulted in significant improvements of the nano composites properties. In this study, nano composite fibres made of cellulose and graphene nano platelets were wet spun from solution by using ionic liquid, 1-ethyl-3-methylimidazolium acetate (EMIMAc) as solvent. The effect of graphene loading on the thermal and electrical properties of the nanocomposite fibres was investigated. The nano composite fibres characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. XRD analysis revealed a cellulose II crystalline structure for regenerated cellulose and the nano composite fibres. SEM images showed a homogenous morphology and round cross section for the nano composite fibres along with well dispersion of graphene nano platelets in regenerated cellulose matrix. The incorporation of graphene into cellulose matrix generated electrical conductivity. At 6 wt. % of graphene, the electrical conductivity was 4.7 × 10-4 S/cm. The nano composite fibres also showed considerable improvements in thermal stability and char yield compared to pure regenerated cellulose fibres. This work provides a facile and environmentally friendly method of preparing nano composite fibres based on cellulose and graphene nano platelets that can find several applications in cellulose-based carbon fibres, conductive fibres, apparel, etc.

Keywords: nanocomposite, graphene nanoplatelets, regenerated cellulose, electrical properties

Procedia PDF Downloads 345
2547 Mapping of Solar Radiation Anomalies Based on Climate Change

Authors: Elison Eduardo Jardim Bierhals, Claudineia Brazil, Francisco Pereira, Elton Rossini

Abstract:

The use of alternative energy sources to meet energy demand reduces environmental damage. To diversify an energy matrix and to minimize global warming, a solar energy is gaining space, being an important source of renewable energy, and its potential depends on the climatic conditions of the region. Brazil presents a great solar potential for a generation of electric energy, so the knowledge of solar radiation and its characteristics are fundamental for the study of energy use. Due to the above reasons, this article aims to verify the climatic variability corresponding to the variations in solar radiation anomalies, in the face of climate change scenarios. The data used in this research are part of the Intercomparison of Interconnected Models, Phase 5 (CMIP5), which contributed to the preparation of the fifth IPCC-AR5 report. The solar radiation data were extracted from The Australian Community Climate and Earth System Simulator (ACCESS) model using the RCP 4.5 and RCP 8.5 scenarios that represent an intermediate structure and a pessimistic framework, the latter being the most worrisome in all cases. In order to allow the use of solar radiation as a source of energy in a given location and/or region, it is important, first, to determine its availability, thus justifying the importance of the study. The results pointed out, for the 75-year period (2026-2100), based on a pessimistic scenario, indicate a drop in solar radiation of the approximately 12% in the eastern region of Rio Grande do Sul. Factors that influence the pessimistic prospects of this scenario should be better observed by the responsible authorities, since they can affect the possibility to produce electricity from solar radiation.

Keywords: climate change, energy, IPCC, solar radiation

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2546 Deep Well Grounded Magnetite Anode Chains Retrieval and Installation for Raslanuf Complex Impressed Current Cathodic Protection System Rectification

Authors: Mohamed Ahmed Khali

Abstract:

Numbers of deep well anode ground beds (GBs) have been retrieved due to un operated anode chains. New identical magnetite anode chains(MAC) have been installed at Raslanuf complex impressed current Cathodic protection(ICCP) system, distributed at different plants(Utility, ethylene and polyethylene). All problems associated with retrieving and installation of MACs have been discussed, rectified and presented. All GB associated severely corroded wellhead casings were well maintained and/ or replaced by new fabricated and modified ones. The main cause of wellhead casings internal corrosion was discussed, and the conducted remedy action to overcome future corrosion problem is presented. All GB connected anode junction boxes (AJBs) and shunts were closely inspected, maintained, and necessary replacement/and or modification were carried out on shunts. All damaged GB concrete foundations (CF) have been inspected and completely replaced. All GB associated Transformer-Rectifiers units (TRUs) were subjected to through inspection, and necessary maintenance has been performed on each individual TRU. After completion of all MACs and TRU maintenance activities, each cathodic protection station (CPS) has been re-operated. An alternative current (AC), direct current (DC), voltage and structure to soil potential (S/P) measurements have been conducted, recorded, and all obtained test results are presented. DC current outputs has been adjusted, and DC current outputs of each MAC has been recorded for each GB AJB.

Keywords: magnatite anode, deep well, ground bed, cathodic protection, transformer rectifies, impreced current, junction box

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2545 Rural-Urban Partnership for Balanced Spatial Development in Latvia

Authors: Zane Bulderberga

Abstract:

Spatial dimension in development planning is becoming more topical in 21st century as a result of changes in population structure. Sustainable spatial development focuses on identifying and using territorial advantages to foster the harmonized development of the entire country, reducing negative effects of population concentration, increasing availability and mobility. EU and national development planning documents state polycentrism as main tool for balance spatial development, including investment concentration in growth centres. If mutual cooperation of growth centres as well as urban-rural cooperation is not fostered, then territorial differences can deepen and create unbalanced development. The aim of research: to evaluate the urban-rural interaction, elaborating spatial development scenarios in framework of Latvian regional policy. To perform the research monographic, comparison, abstract-logical method, synthesis and analysis will be used when studying the theoretical aspects of research aiming at collecting the ideas of scientists from different countries, concepts, regulations as well as to create meaningful scientific discussion. Hierarchy analysis process (AHP) will be used to state further scenarios of spatial development in Latvia. Experts from various institutions recognized urban-rural interaction and co-operation as an essential tool for the development. The most important factors for balanced spatial development in Latvia are availability of public transportation and improvement of service availability. Evaluating the three alternative scenarios, it was concluded that the urban-rural partnership will ensure a balanced development in Latvian regions.

Keywords: rural-urban interaction, rural-urban cooperation, spatial development, AHP

Procedia PDF Downloads 300
2544 Crystallized Colored Towels Obtained by Special Coloration of Yarns

Authors: Hasan Eskin, Gizem Özmen, A. Nazmi Çeler

Abstract:

When we examine the home textile development process, it follows a parallel line with the other textile products especially in the garment fabrics in terms of raw materials, production technologies and pattern characteristics. As a result, the expectations of people regarding textile, comfort, pattern (texture) and color properties are increasing. One of the places where comfort is most sought after is bath, pool, sea and baths. In addition to the material and technique that make up the physical structure in woven fabrics, color has an impressive importance with its strong effects. Color is the most prominent element in the fabric, and the color and texture are visually reinforcing. Evaluation of color in fabric is a personal phenomenon. Factors that determine color determination in fabric are the amount of color used, color ratio and its relationship with other colors. In this project; Considering the effect of color dimensions on human, we are talking about the crystallized colored towel that we developed in terms of comfort and texture properties. The basis of the effect created in the towel; It is formed by bending the yarn from its own special blend and the harmonious appearance of the natural crystallized rainbow colors with the pattern effect it determines on the warp yarns by using the weft yarns in the weaving. In addition, by using different weaving techniques and colors, alternatives can be created and personalized patterns can be created. One side of the towel determines the properties related to color, while the pile part determines the comfort characteristics with its soft touch and water absorbency.

Keywords: color effect, comfort, towel, weaving technique

Procedia PDF Downloads 149
2543 Preserving Digital Arabic Text Integrity Using Blockchain Technology

Authors: Zineb Touati Hamad, Mohamed Ridda Laouar, Issam Bendib

Abstract:

With the massive development of technology today, the Arabic language has gained a prominent position among the languages most used for writing articles, expressing opinions, and also for citing in many websites, defying its growing sensitivity in terms of structure, language skills, diacritics, writing methods, etc. In the context of the spread of the Arabic language, the Holy Quran represents the most prevalent Arabic text today in many applications and websites for citation purposes or for the reading and learning rituals. The Quranic verses / surahs are published quickly and without cost, which may cause great concern to ensure the safety of the content from tampering and alteration. To protect the content of texts from distortion, it is necessary to refer to the original database and conduct a comparison process to extract the percentage of distortion. The disadvantage of this method is that it takes time, in addition to the lack of any guarantee on the integrity of the database itself as it belongs to one central party. Blockchain technology today represents the best way to maintain immutable content. Blockchain is a distributed database that stores information in blocks linked to each other through encryption, where the modification of each block can be easily known. To exploit these advantages, we seek in this paper to justify the use of this technique in preserving the integrity of Arabic texts sensitive to change by building a decentralized framework to authenticate and verify the integrity of the digital Quranic verses/surahs spread on websites.

Keywords: arabic text, authentication, blockchain, integrity, quran, verification

Procedia PDF Downloads 155
2542 Bacterial Cellulose: A New Generation Antimicrobial Wound Dressing Biomaterial

Authors: Bhavana V. Mohite, Satish V. Patil

Abstract:

Bacterial cellulose (BC) is an alternative for plant cellulose (PC) that prevents global warming leads to preservation of nature. Although PC and BC have the same chemical structure, BC is superior with its properties like its size, purity, porosity, degree of polymerization, crystallinity and water holding capacity, thermal stability etc. On this background the present study focus production and applications of BC as antimicrobial wound dressing material. BC was produced by Gluconoacetobacter hansenii (strain NCIM 2529) under shaking condition and statistically enhanced upto 7.2 g/l from 3.0 g/l. BC was analyzed for its physico mechanical, structural and thermal characteristics. BC produced at shaking condition exhibits more suitable properties in support to its high performance applications. The potential of nano silver impregnated BC was determined for sustained release modern antimicrobial wound dressing material by swelling ratio, mechanical properties and antimicrobial activity against Staphylococcus aureus. BC in nanocomposite form with other synthetic polymer like PVA shows improvement in its properties such as swelling ratio (757% to 979%) and sustainable release of antibacterial agent. The high drug loading and release potential of BC was evidenced in support to its nature as antimicrobial wound dressing material. The nontoxic biocompatible nature of BC was confirmed by MTT assay on human epidermal cells with 90% cell viability that allows its application as a regenerative biomaterial. Thus, BC as a promising new generation antimicrobial wound dressing material was projected.

Keywords: agitated culture, biopolymer, gluconoacetobacter hansenii, nanocomposite

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2541 Effective Slab Width for Beam-End Flexural Strength of Composite Frames with Circular-Section Columns

Authors: Jizhi Zhao, Qiliang Zhou, Muxuan Tao

Abstract:

The calculation of the ultimate loading capacity of composite frame beams is an important step in the design of composite frame structural systems. Currently, the plastic limit theory is mainly used for this calculation in the codes adopted by many countries; however, the effective slab width recommended in most codes is based on the elastic theory, which does not accurately reflect the complex stress mechanism at the beam-column joints in the ultimate loading state. Therefore, the authors’ research group put forward the Compression-on-Column-Face mechanism and Tension-on-Transverse-Beam mechanism to explain the mechanism in the ultimate loading state. Formulae are derived for calculating the effective slab width in composite frames with rectangular/square-section columns under ultimate lateral loading. Moreover, this paper discusses the calculation method of the effective slab width for the beam-end flexural strength of composite frames with circular-section columns. The proposed design formula is suitable for exterior and interior joints. Finally, this paper compares the proposed formulae with available formulae in other literature, current design codes, and experimental results, providing the most accurate results to predict the effective slab width and ultimate loading capacity.

Keywords: composite frame structure, effective slab width, circular-section column, design formulae, ultimate loading capacity

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2540 The Influence of Brands in E-Sports Spectators

Authors: Rene Kasper, Hyago Ribeiro, Marcelo Curth

Abstract:

Electronic sports, or just e-sports, boast an exponential growth in the interest of the public and large investors. The e-sports teams are equal to classic sports teams, like football, since in their structure they have, besides the athletes, administrators, coaches and even doctors. The concept of team games arises with a very strong social interaction, as it is perceived that users interact with real peers rather than competing with intelligent software. In this sense, electronic games are established as a sociocultural phenomenon and as multidimensional media. Thus, the research aims to identify the profile of users and the importance of brands in the Brazilian electronic sports scene, as well as the relationship of consumers (called fans) with the products and services that occupy the media spaces of the transmissions of sports championships. The research used descriptive quantitative methodology, applied in different e-sports communities, with 160 respondents. The data collection instrument was a survey containing seven questions, which addressed the profile of the participants and their perception on the proposed theme in research. Regarding the profile, the age ranged from 17 to 31 years, of which 93.3% were male and 6.7% female. It was found that 93.3% of the participants had contact with the Brazilian electronic sports scene for at least 2 years, of which 26.7% played between 6 and 12 hours a week and 46.7% played more than 12 hours a week. In addition, it was noticed that income was not a deciding factor to enjoy electronic sports games, because the percentage distribution of participants ranged from 1 to 3 minimum wages (33.3%) and greater than 6 salaries (46.7 %). Regarding the brands, 85.6% emphasized that brands should support the scenario through sponsorship and publicity and 28.6% are attracted to consume brands that advertise in e-sports championships.

Keywords: brands, consumer behavior, e-sports, virtual games

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2539 Macrocycles Enable Tuning of Uranyl Electrochemistry by Lewis Acids

Authors: Amit Kumar, Davide Lionetti, Victor Day, James Blakemore

Abstract:

Capture and activation of the water-soluble uranyl dication (UO22+) remains a challenging problem, as few rational approaches are available for modulating the reactivity of this species. Here, we report the divergent synthesis of heterobimetallic complexes in which UO22+ is held in close proximity to a range of redox-inactive metals by tailored macrocyclic ligands. Crystallographic and spectroscopic studies confirm assembly of homologous UVI(μ-OAr)2Mn+ cores with a range of mono-, di-, and trivalent Lewis acids (Mn+). X-ray diffraction (XRD) and cyclic voltammetry (CV) data suggest preferential binding of K+ in an 18-crown-6-like cavity and Na+ in a 15-crown-5-like cavity, both appended to Schiff-base type sites that selectively bind UO22+. CV data demonstrate that the UVI/UV reduction potential in these complexes shifts positive and the rate of electron transfer decreases with increasing Lewis acidity of the incorporated redox-inactive metals. Moreover, spectroelectrochemical studies confirm the formation of [UV] species in the case of monometallic UO22+ complex, consistent with results from prior studies. However, unique features were observed during spectroelectrochemical studies in the presence of the K+ ion, suggesting new insights into electronic structure may be accessible with the heterobimetallic complexes. Overall, these findings suggest that interactions with Lewis acids could be effectively leveraged for rational tuning of the electronic and thermochemical properties of the 5f elements, reminiscent of strategies more commonly employed with 3d transition metals.

Keywords: electrochemistry, Lewis acid, macrocycle, uranyl

Procedia PDF Downloads 135