Search results for: Density Functional Theory (DFT)

Authors: Martin Juckel

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Probably no other field of inorganic chemistry has undergone such a rapid development in the past two decades than the low oxidation state chemistry of main group elements. This rapid development has only been possible by the development of new bulky ligands. In case of our research group, super-bulky monodentate amido ligands and β-diketiminate ligands have been used to a great success. We first synthesized the unprecedented magnesium(I) dimer [ᴹᵉˢNacnacMg]₂ (ᴹᵉˢNacnac = [(ᴹᵉˢNCMe)₂CH]-; Mes = mesityl, which has since been used both as reducing agent and also for the synthesis of new metal-magnesium bonds. In case of the zinc bromide precursor [L*ZnBr] (L*=(N(Ar*)(SiPri₃); (Ar* = C₆H₂{C(H)Ph₂}₂Me-2,6,4, the reduction with [ᴹᵉˢNacnacMg]₂ led to such a metal-magnesium bond. This [L*ZnMg(ᴹᵉˢNacnac)] compound can be seen as an ‘inorganic Grignard reagent’, which can be used to transfer the metal fragment onto other functional groups or other metal centers; just like the conventional Grignard reagent. By simple addition of (TBoN)GeCl (TBoN = N(SiMe₃){B(DipNCH)₂) to the aforesaid compound, we were able to transfer the amido-zinc fragment to the Ge center of the germylene starting material and to synthesize the first example of a germanium(II)-zinc bond: [:Ge(TBoN)(ZnL*)]. While these reactions typically led to complex product mixture, [:Ge(TBoN)(ZnL*)] could be isolated as dark blue crystals in a good yield. This new compound shows interesting reactivity towards small molecules, especially dihydrogen gas. This is of special interest as dihydrogen is one of the more difficult small molecules to activate, due to its strong (BDE = 108 kcal/mol) and non-polar bond. In this context, the interaction between H₂ σ-bond with the tetrelylene p-Orbital (LUMO), with concomitant donation of the tetrelylene lone pair (HOMO) into the H₂ σ* orbital are responsible for the activation of dihydrogen gas. Accordingly, the narrower the HOMO-LUMO gap of tertelylene, the more reactivity towards H₂ it typically is. The aim of a narrow HOMO-LUMO gap was reached by transferring electropositive substituents respectively metal substituents with relatively low Pauling electronegativity (zinc: 1.65) onto the Ge center (here: the zinc-amido fragment). In consideration of the unprecedented reactivity of [:Ge(TBoN)(ZnL*)], a computational examination of its frontier orbital energies was undertaken. The energy separation between the HOMO, which has significant Ge lone pair character, and the LUMO, which has predominantly Ge p-orbital character, is narrow (40.8 kcal/mol; cf.∆S-T= 24.8 kcal/mol), and comparable to the HOMO-LUMO gaps calculated for other literature known complexes). The calculated very narrow HOMO-LUMO gap for the [:Ge(TBoN)(ZnL*)] complex is consistent with its high reactivity, and is remarkable considering that it incorporates a π-basic amide ligand, which are known to raise the LUMO of germylenes considerably.

Keywords: activation of dihydrogen gas, narrow HOMO-LUMO gap, first germanium(II)-zinc bond, inorganic Grignard reagent

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Authors: Dharshini S.

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India is currently experiencing a shift in wage discrimination from gender, caste and religion to different age groups in both formal and informal sectors. In this milieu, this study examines wage discrimination in the informal labour market between young people (15-29 years) and middle-aged people (30-59 years) among regular and casual employees in the Indian informal sector. The data was collected using periodic labour force (PLFS), and the original data was extracted from the National Sample Survey Office (NSSO) under the Ministry of Statistics and Programme Implementation (MOSPI), Government of India. The OLS regression model explores the determinants of wages for both regular and casual employees. Moreover, the Blinder Oaxaca decomposition method is used to explore the explained and unexplained components of this wage discrimination. The younger people (regular and casual employees) get lower wages as compared to middle-aged employees in the informal sector. The regression result follows the human capital theory, where education, job experience and higher occupation help to raise the wage rate of middle-aged people more than young-aged people in regular work. Furthermore, we found the rising trend of wage discrimination between the above groups over the years from 2017-18 to 2022-23. Unexplained factors (discrimination effects) contribute more to the wage differentiation between the young and middle age groups. It indicates that wage discrimination persists among regular and casual employees in the informal labour market, which is not a good sign for the economy. For the betterment of workers who face discrimination for age, the policies and programs should be implemented like other countries such as the U.S.A to stop age discrimination due to stereotypes in India.

Keywords: wage discrimination, young workers, middle workers, Informal sector, blinder oaxaca decomposition, PLFS.

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Authors: Fereydoon Bondarian, Samira Shaygan

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Today, many nutritionists recommend the consumption of plants, fruits, and vegetables to provide the antioxidants needed by the body because the use of plant antioxidants usually causes fewer side effects and better treatment. Natural antioxidants increase the power of plasma antioxidants and reduce the incidence of some diseases, such as cancer. Bad lifestyles and environmental factors play an important role in increasing the incidence of cancer. In this study, different extracts of white teas taken from two types of tea available in Iran (clone 100 and Chinese hybrid) due to the presence of a hydroxyl functional group in their structure to inhibit free radicals and anticancer properties, using 3 aqueous, methanolic and aqueous-methanolic methods were used. The total polyphenolic content was calculated using the Folin-Ciocalcu method, and the percentage of inhibition and trapping of free radicals in each of the extracts was calculated using the DPPH method. With the help of high-performance liquid chromatography, a small amount of each catechin in the tea samples was obtained. Clone 100 white tea was found to be the best sample of tea in terms of all the examined attributes (total polyphenol content, antioxidant properties, and individual amount of each catechin). The results showed that aqueous and aqueous-methanolic extracts of Clone 100 white tea have the highest total polyphenol content with 27.59±0.08 and 36.67±0.54 (equivalent gallic acid per gram dry weight of leaves), respectively. Due to having the highest level of different groups of catechin compounds, these extracts have the highest property of inhibiting and trapping free radicals with 66.61±0.27 and 71.74±0.27% (mg/l) of the extracted sample against ascorbic acid). Using the MTT test, the inhibitory effect of clone 100 white tea extract in inhibiting the growth of HCT-116 colon cancer cells was investigated and the best time and concentration treatments were 500, 150 and 1000 micrograms in 8, 16 and 24 hours, respectively. To investigate gene expression changes, selected genes, including tumorigenic genes, proto-oncogenes, tumor suppressors, and genes involved in apoptosis, were selected and analyzed using the real-time PCR method and in the presence of concentrations obtained for white tea. White tea extract at a concentration of 1000 μg/ml 3 times 16, 8, and 24 hours showed the highest growth inhibition in cancer cells with 53.27, 55.8, and 86.06%. The concentration of 1000 μg/ml aqueous extract of white tea under 24-hour treatment increased the expression of tumor suppressor genes compared to the normal sample.

Keywords: catechin, gene expression, suppressor genes, colon cell line

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Authors: Tess Hartland, Moitree Banerjee, Sue Churchill, Antonina Pereira, Ian Tyndall, Ruth Lowry

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Background: Sexual health services and policies for middle-aged and older adults are underdeveloped, while global sexually transmitted infections in this age group are on the rise. The Interreg cross-Europe Sexual Health In Over 45s (SHIFT) project aims to increase participation in sexual health services and improve sexual health and wellbeing in people aged over 45, with an additional focus on disadvantaged groups. Methods: A two-pronged mixed-methodology is being used to develop a model for good service provision in sexual health for over 45s. (1) Following PRISMA-ScR guidelines, a scoping review is being conducted, using the databases PsychINFO, Web of Science, ERIC and PubMed. A key search strategy using terms around sexual health, good practice, over 45s and disadvantaged groups. The initial search for literature yielded 7914 results. (2) Surveys (n=1000) based on the Theory of Planned Behaviour are being administered across the UK, Belgium and Netherlands to explore current sexual health knowledge, awareness and attitudes. Expected results: It is expected that sexual health needs and potential gaps in service provision will be identified in order to inform good practice for sexual health services for the target population. Results of the scoping review are being analysed, while focus group and survey data is being gathered. Preliminary analysis of the survey data highlights barriers to access such as limited risk awareness and stigma. All data analysis will be completed by the time of the conference. Discussion: Findings will inform the development of a model to improve sexual health and wellbeing for among over 45s, a population which is often missed in sexual health policy improvement.

Keywords: adult health, disease prevention, health promotion, over 45s, sexual health

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Authors: Said Ahmed Zohairy

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Significant shifts in the theory and practice of teaching vocabulary affect teachers’ decisions about learning materials’ design. Relevant literature supports teaching specialised, authentic, and multi-word lexical items rather than focusing on single-word vocabulary lists. Corpora, collections of texts stored in a database, presents a reliable source of teaching and learning materials. Although corpus-informed studies provided guidance for teachers to identify useful language chunks and phraseological units, there is a scarcity in the literature discussing the use of corpora in teaching English for academic and specific purposes (EASP). The aim of this study is to improve teaching practices and provide a description of the pedagogical choices and procedures of an EASP tutor in an attempt to offer guidance for novice corpus users. It draws on the researcher’s experience of utilising corpus linguistic tools to design vocabulary learning activities without focusing on students’ learning outcomes. Hence, it adopts a self-study research methodology which is based on five methodological components suggested by other self-study researchers. The findings of the study noted that designing specialised and corpus-informed vocabulary learning activities could be challenging for teachers, as they require technical knowledge of how to navigate corpora and utilise corpus analysis tools. Findings also include a description of the researcher’s approach to building and analysing a specialised corpus for the benefit of novice corpus users; they should be able to start their own journey of designing corpus-based activities.

Keywords: corpora, corpus linguistics, corpus-informed, English for academic and specific purposes, agribusiness, vocabulary, phraseological units, materials design

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Authors: Jakub Zembrzuski, Bartosz Sobczyk, Mikołaj MIśkiewicz

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Besides designing new constructions, engineers all over the world must face another problem – maintenance, repairs, and assessment of the technical condition of existing bridges. To solve more complex issues, it is necessary to be familiar with the theory of finite element method and to have access to the software that provides sufficient tools which to enable create of sometimes significantly advanced numerical models. The paper includes a brief assessment of the technical condition, a description of the in situ non-destructive testing carried out and the FEM models created for global and local analysis. In situ testing was performed using strain gauges and displacement sensors. Numerical models were created using various software and numerical modeling techniques. Particularly noteworthy is the method of modeling riveted joints of the crossbeam of the viaduct. It is a simplified method that consists of the use of only basic numerical tools such as beam and shell finite elements, constraints, and simplified boundary conditions (fixed support and symmetry). The results of the numerical analyses were presented and discussed. It is clearly explained why the structure did not fail, despite the fact that the weld of the deck plate completely failed. A further research problem that was solved was to determine the cause of the rapid increase in values on the stress diagram in the cross-section of the transverse section. The problems were solved using the solely mentioned, simplified method of modeling riveted joints, which demonstrates that it is possible to solve such problems without access to sophisticated software that enables to performance of the advanced nonlinear analysis. Moreover, the obtained results are of great importance in the field of assessing the operation of bridge structures with an orthotropic plate.

Keywords: bridge, diagnostics, FEM simulations, failure, NDT, in situ testing

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Authors: Daniel Asiamah Ameyaw

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This research attempts to investigate how lecturer evaluation makes a difference in enhancing higher education teaching and learning processes. The research questions to guide this research work states first as, “What are the perspectives on the difference made by evaluating academic teachers in order to enhance higher education teaching and learning processes?” and second, “What are the implications of the findings for Policy and Practice?” Data for this research was collected mainly through interviewing and partly documents review. Data analysis was conducted under the framework of grounded theory. The findings showed that for individual lecturer level, lecturer evaluation provides a continuous improvement of teaching strategies, and serves as source of data for research on teaching. At the individual student level, it enhances students learning process; serving as source of information for course selection by students; and by making students feel recognised in the educational process. At the institutional level, it noted that lecturer evaluation is useful in personnel and management decision making; it assures stakeholders of quality teaching and learning by setting up standards for lecturers; and it enables institutions to identify skill requirement and needs as a basis for organising workshops. Lecturer evaluation is useful at national level in terms of guaranteeing the competencies of graduates who then provide the needed manpower requirement of the nation. Besides, it mentioned that resource allocation to higher educational institution is based largely on quality of the programmes being run by the institution. The researcher concluded, that the findings have implications for policy and practice, therefore, higher education managers are expected to ensure that policy is implemented as planned by policy-makers so that the objectives can successfully be achieved.

Keywords: academic quality, higher education, lecturer evaluation, teaching and learning processes

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Authors: M. Alsharqawi, T. Zayed, S. Abu Dabous

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To ensure safety and serviceability of bridge infrastructure, accurate condition assessment and rating methods are needed to provide basis for bridge Maintenance, Repair and Replacement (MRR) decisions. In North America, the common practices to assess condition of bridges are through visual inspection. These practices are limited to detect surface defects and external flaws. Further, the thresholds that define the severity of bridge deterioration are selected arbitrarily. The current research discusses the main deteriorations and defects identified during visual inspection and Non-Destructive Evaluation (NDE). NDE techniques are becoming popular in augmenting the visual examination during inspection to detect subsurface defects. Quality inspection data and accurate condition assessment and rating are the basis for determining appropriate MRR decisions. Thus, in this paper, a novel method for bridge condition assessment using the Quality Function Deployment (QFD) theory is utilized. The QFD model is designed to provide an integrated condition by evaluating both the surface and subsurface defects for concrete bridges. Moreover, an integrated condition rating index with four thresholds is developed based on the QFD condition assessment model and using K-means clustering technique. Twenty case studies are analyzed by applying the QFD model and implementing the developed rating index. The results from the analyzed case studies show that the proposed threshold model produces robust MRR recommendations consistent with decisions and recommendations made by bridge managers on these projects. The proposed method is expected to advance the state of the art of bridges condition assessment and rating.

Keywords: concrete bridge decks, condition assessment and rating, quality function deployment, k-means clustering technique

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Authors: Ebru Dural, M. Zulfu Asık

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Laminated glass is a kind of safety glass, which is made by 'sandwiching' two glass sheets and a polyvinyl butyral (PVB) interlayer in between them. When the glass is broken, the interlayer in between the glass sheets can stick them together. Because of this property, the hazards of sharp projectiles during natural and man-made disasters reduces. They can be widely applied in building, architecture, automotive, transport industries. Laminated glass can easily undergo large displacements even under their own weight. In order to explain their true behavior, they should be analyzed by using large deflection theory to represent nonlinear behavior. In this study, a nonlinear mathematical model is developed for the analysis of laminated glass cylindrical shell which is free in radial directions and restrained in axial directions. The results will be verified by using the results of the experiment, carried out on laminated glass cylindrical shells. The behavior of laminated composite cylindrical shell can be represented by five partial differential equations. Four of the five equations are used to represent axial displacements and radial displacements and the fifth one for the transverse deflection of the unit. Governing partial differential equations are derived by employing variational principles and minimum potential energy concept. Finite difference method is employed to solve the coupled differential equations. First, they are converted into a system of matrix equations and then iterative procedure is employed. Iterative procedure is necessary since equations are coupled. Problems occurred in getting convergent sequence generated by the employed procedure are overcome by employing variable underrelaxation factor. The procedure developed to solve the differential equations provides not only less storage but also less calculation time, which is a substantial advantage in computational mechanics problems.

Keywords: laminated glass, mathematical model, nonlinear behavior, PVB

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Authors: Vanja Skoric

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The paper examines whether the impacts of artificial intelligence (AI) can be meaningfully addressed through the rights-based approach to AI design, investigating in particular how the inclusive, participatory process of assessing the AI impact would make this viable. There is a significant gap between envisioning rights-based AI systems and their practical application. Plausibly, internalizing human rights approach within AI design process might be achieved through identifying and assessing implications of AI features human rights, especially considering the case of vulnerable individuals and communities. However, there is no clarity or consensus on how such an instrument should be operationalised to usefully identify the impact, mitigate harms and meaningfully ensure relevant stakeholders’ participation. In practice, ensuring the meaningful inclusion of those individuals, groups, or entire communities who are affected by the use of the AI system is a prerequisite for a process seeking to assess human rights impacts and risks. Engagement in the entire process of the impact assessment should enable those affected and interested to access information and better understand the technology, product, or service and resulting impacts, but also to learn about their rights and the respective obligations and responsibilities of developers and deployers to protect and/or respect these rights. This paper will provide an overview of the study and practice of the participatory design process for AI, including inclusive impact assessment, its main elements, propose a framework, and discuss the lessons learned from the existing theory. In addition, it will explore pathways for enhancing and promoting individual and group rights through such engagement by discussing when, how, and whom to include, at which stage of the process, and what are the pre-requisites for meaningful and engaging. The overall aim is to ensure using the technology that works for the benefit of society, individuals, and particular (historically marginalised) groups.

Keywords: rights-based design, AI impact assessment, inclusion, harm mitigation

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Authors: Daniel Bülz, Franziska Lüttich, Sreetama Banerjee, Georgeta Salvan, Dietrich R. T. Zahn

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For the development of electronics, organic semiconductors are of great interest due to their adjustable optical and electrical properties. Especially for spintronic applications they are interesting because of their weak spin scattering, which leads to longer spin life times compared to inorganic semiconductors. It was shown that some organic materials change their resistance if an external magnetic field is applied. Pentacene is one of the materials which exhibit the so called photoinduced magnetoresistance which results in a modulation of photocurrent when varying the external magnetic field. Also the soluble derivate of pentacene, the 6,13-bis (triisopropylsilylethynyl)-pentacene (TIPS-pentacene) exhibits the same negative magnetoresistance. Aiming for simpler fabrication processes, in this work, we compare TIPS-pentacene organic field effect transistors (OFETs) made from solution with those fabricated by thermal evaporation. Because of the different processing, the TIPS-pentacene thin films exhibit different morphologies in terms of crystal size and homogeneity of the substrate coverage. On the other hand, the interface treatment is known to have a high influence on the threshold voltage, eliminating trap states of silicon oxide at the gate electrode and thereby changing the electrical switching response of the transistors. Therefore, we investigate the influence of interface treatment using octadecyltrichlorosilane (OTS) or using a simple cleaning procedure with acetone, ethanol, and deionized water. The transistors consist of a prestructured OFET substrates including gate, source, and drain electrodes, on top of which TIPS-pentacene dissolved in a mixture of tetralin and toluene is deposited by drop-, spray-, and spin-coating. Thereafter we keep the sample for one hour at a temperature of 60 °C. For the transistor fabrication by thermal evaporation the prestructured OFET substrates are also kept at a temperature of 60 °C during deposition with a rate of 0.3 nm/min and at a pressure below 10-6 mbar. The OFETs are characterized by means of optical microscopy in order to determine the overall quality of the sample, i.e. crystal size and coverage of the channel region. The output and transfer characteristics are measured in the dark and under illumination provided by a white light LED in the spectral range from 450 nm to 650 nm with a power density of (8±2) mW/cm2.

Keywords: organic field effect transistors, solution processed, surface treatment, TIPS-pentacene

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Authors: Mostafa Mjahed

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This paper concerns the control of a nonlinear system using two different methods, reference model and genetic algorithm. The quadcopter is a nonlinear unstable system, which is a part of aerial robots. It is constituted by four rotors placed at the end of a cross. The center of this cross is occupied by the control circuit. Its motions are governed by six degrees of freedom: three rotations around 3 axes (roll, pitch and yaw) and the three spatial translations. The control of such system is complex, because of nonlinearity of its dynamic representation and the number of parameters, which it involves. Numerous studies have been developed to model and stabilize such systems. The classical PID and LQ correction methods are widely used. If the latter represent the advantage to be simple because they are linear, they reveal the drawback to require the presence of a linear model to synthesize. It also implies the complexity of the established laws of command because the latter must be widened on all the domain of flight of these quadcopter. Note that, if the classical design methods are widely used to control aeronautical systems, the Artificial Intelligence methods as genetic algorithms technique receives little attention. In this paper, we suggest comparing two PID design methods. Firstly, the parameters of the PID are calculated according to the reference model. In a second phase, these parameters are established using genetic algorithms. By reference model, we mean that the corrected system behaves according to a reference system, imposed by some specifications: settling time, zero overshoot etc. Inspired from the natural evolution of Darwin's theory advocating the survival of the best, John Holland developed this evolutionary algorithm. Genetic algorithm (GA) possesses three basic operators: selection, crossover and mutation. We start iterations with an initial population. Each member of this population is evaluated through a fitness function. Our purpose is to correct the behavior of the quadcopter around three axes (roll, pitch and yaw) with 3 PD controllers. For the altitude, we adopt a PID controller.

Keywords: quadcopter, genetic algorithm, PID, fitness, model, control, nonlinear system

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Authors: Fareena Alladin

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In the Caribbean, issues of food security, health and taste are intricately linked, seen most clearly in the increasing incidence of lifestyle diseases among children coupled with a taste for high calorie and Westernized diets. In order to fully appreciate this link, the role of nutrition environments must be examined. To this end, the present study incorporates tenets of Bourdieu’s social constructivist theory with the Community Nutrition Environment Model. The aim of this study was to examine the relationships between availability of and access to healthy/unhealthy foods within nutrition environments, namely the household and school, and the development of taste preferences for healthy/unhealthy foods among primary school children in a selected educational district in Trinidad and Tobago. A cross-sectional survey of 400 children between the ages of 9 and 11 years was conducted. Data analysis was conducted using SPSS 24. Results indicated that availability of healthy food at home was positively correlated with preference for vegetables, and negatively correlated with preference for salty snacks and fast food. The availability of unhealthy food within the home was found to be negatively correlated with preference for vegetables and positively correlated with preference for salty snacks. Access to unhealthy foods at school had a positive correlation with preference for fast food. These findings highlight the role of the food environment in shaping taste preferences, and point to the need for interrogating the centrality of food security concerns in emerging health concerns of Caribbean countries. Such interrogations are a necessary part of the development of research agendas, and policy formulation and implementation.

Keywords: food security, nutrition environment, taste preference, Trinidad and Tobago

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Authors: Samira Essabari

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What, unfortunately, governs the Moroccan educational philosophy and policy today is a concerning neoliberal discourse with its obsession with market logics and individualism. Critical education has been advocated to resist the neoliberal hegemony since it holds the promise to reclaim the social function of education. Significantly, the mounting forms of sexism and discrimination against women combined with hegemonic educational practices are jeopardizing the social function of teaching and learning, hence the relevance of feminist critical pedagogy. A substantial body of research worldwide has explored the ways in which feminist pedagogy can develop feminist consciousness and examine power relations in different educational contexts. In Morocco, however, the feasibility of feminist pedagogy has not been researched despite the overwhelming interest in gender issues in different educational settings. The research on critical pedagogies in Morocco remains very promising. Yet, most studies were conducted in contexts which are already engaged with issues of theory, discourse, and discourse analysis. The field of ESP ( English for Specific Purposes) is pragmatic by nature, and priority in research has been given to questions that adhere to the mainstream concerns of need analysis and study skills and ignore issues of power, gender power relations, and intersectional forms of oppression. To address these gaps in the existing literature, this participatory action research seeks to investigate the feasibility of Feminist pedagogy in ESP higher education and how it can foster feminist critical consciousness among ESP students without compromising their language learning needs. The findings of this research will contribute to research on critical applied linguistics and critical ESP more specifically and add to the practice of critical pedagogies in Moroccan higher education by providing in-depth insights into the enablers and barriers to the implementation of feminist critical pedagogy, which is still feeling its way into the educational scene in Morocco.

Keywords: feminist pedagogy, critical pedagogy, power relations, gender, ESP, intersectionality

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Authors: Mary Rosa Espinosa-Ochoa

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The study of overgeneralization in inflectional morphology provides evidence for understanding how a child's mind works when applying linguistic patterns in a novel way. High-frequency inflectional forms in the input cause inappropriate use in contexts related to lower-frequency forms. Children learn verbs as lexical items and new forms develop only gradually, around their second year: most of the utterances that children produce are closely related to what they have previously produced. Spanish has a complex verbal system that inflects for person, mood, and tense. Approximately 200 verbs are irregular, and bare roots always require an inflected form, which represents a challenge for the memory. The aim of this research is to investigate i) what kinds of overgeneralization errors children make in verb production, ii) to what extent these errors are related to verb forms previously produced, and iii) whether the overgeneralized verb components are also frequent in children’s linguistic inventory. It consists of a high-density longitudinal study of a middle-class girl (1;11,24-2;02,24) from Mexico City, whose utterances were recorded almost daily for three months to compile a unique corpus in the Spanish language. Of the 358 types of inflected verbs produced by the child, 9.11% are overgeneralizations. Not only are inflected forms (verbal and pronominal clitics) overgeneralized, but also verbal roots. Each of the forms can be traced to previous utterances, and they show that the child is detecting morphological patterns. Neither verbal roots nor inflected forms are associated with high frequency patterns in her own speech. For example, the child alternates the bare roots of an irregular verb, cáye-te* and cáiga-te* (“fall down”), to express the imperative of the verb cá-e-te (fall down.IMPERATIVE-PRONOMINAL.CLITIC), although cay-ó (PAST.PERF.3SG) is the most frequent form of her previous complete inventory, and the combined frequency of caer (INF), cae (PRES.INDICATIVE.3SG), and caes (PRES.INDICATIVE.2SG) is the same as that of as caiga (PRES.SUBJ.1SG and 3SG). These results provide evidence that a) two forms of the same verb compete in the child’s memory, and b) although the child uses her own inventory to create new forms, these forms are not necessarily frequent in her memory storage, which means that her mind is more sensitive to external stimuli. Language acquisition is a developing process, given the sensitivity of the human mind to linguistic interaction with the outside world.

Keywords: inflection, morphology, child language acquisition, Spanish

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Authors: Cristina Lavilla, Andreas Heise

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The synthesis of sequence-controlled polymers has received increasing attention in the last years. Well-defined polyacrylates, polyacrylamides and styrene-maleimide copolymers have been synthesized by sequential or kinetic addition of comonomers. However this approach has not yet been introduced to the synthesis of polypeptides, which are in fact polymers developed by nature in a sequence-controlled way. Polypeptides are natural materials that possess the ability to self-assemble into complex and highly ordered structures. Their folding and properties arise from precisely controlled sequences and compositions in their constituent amino acid monomers. So far, solid-phase peptide synthesis is the only technique that allows preparing short peptide sequences with excellent sequence control, but also requires extensive protection/deprotection steps and it is a difficult technique to scale-up. A new strategy towards sequence control in the synthesis of polypeptides is introduced, based on the sequential addition of α-amino acid-N-carboxyanhydrides (NCAs). The living ring-opening process is conducted to full conversion and no purification or deprotection is needed before addition of a new amino acid. The length of every block is predefined by the NCA:initiator ratio in every step. This method yields polypeptides with a specific sequence and controlled molecular weights. A series of polypeptides with varying block sequences have been synthesized with the aim to identify structure-property relationships. All of them are able to adopt secondary structures similar to natural polypeptides, and display properties in the solid state and in solution that are characteristic of the primary structure. By design the prepared polypeptides allow selective modification of individual block sequences, which has been exploited to introduce functionalities in defined positions along the polypeptide chain. Poly(ethylene glycol)(PEG) was the functionality chosen, as it is known to favor hydrophilicity and also yield thermoresponsive materials. After PEGylation, hydrophilicity of the polypeptides is enhanced, and their thermal response in H2O has been studied. Noteworthy differences in the behavior of the polypeptides having different sequences have been found. Circular dichroism measurements confirmed that the α-helical conformation is stable over the examined temperature range (5-90 °C). It is concluded that PEG units are the main responsible of the changes in H-bonding interactions with H2O upon variation of temperature, and the position of these functional units along the backbone is a factor of utmost importance in the resulting properties of the α-helical polypeptides.

Keywords: α-amino acid N-carboxyanhydrides, multiblock copolymers, poly(ethylene glycol), polypeptides, ring-opening polymerization, sequence control

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Authors: A. S. V. Carvalho, J. Luis, L. S. O. Pires, J. M. Oliveira

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Additive manufacturing technologies (AM) experienced a remarkable growth in the latest years due to the development and diffusion of a wide range of three-dimensional (3D) printing techniques. Nowadays we can find techniques available for non-industrial users, like fused filament fabrication, but techniques like 3D printing, polyjet, selective laser sintering and stereolithography are mainly spread in the industry. Robocasting (R3D) shows a great potential due to its ability to shape materials with a wide range of viscosity. Industrial porcelain compositions showing different rheological behaviour can be prepared and used as candidate materials to be processed by R3D. The use of this AM technique in industry is very residual. In this work, a specific porcelain composition with suitable rheological properties will be processed by R3D, and a systematic study of the printing parameters tuning will be shown. The porcelain composition was formulated based on an industrial spray dried porcelain powder. The powder particle size and morphology was analysed. The powders were mixed with water and an organic binder on a ball mill at 200 rpm/min for 24 hours. The batch viscosity was adjusted by the addition of an acid solution and mixed again. The paste density, viscosity, zeta potential, particle size distribution and pH were determined. In a R3D system, different speed and pressure settings were studied to access their impact on the fabrication of porcelain models. These models were dried at 80 °C, during 24 hours and sintered in air at 1350 °C for 2 hours. The stability of the models, its walls and surface quality were studied and their physical properties were accessed. The microstructure and layer adhesion were observed by SEM. The studied processing parameters have a high impact on the models quality. Moreover, they have a high impact on the stacking of the filaments. The adequate tuning of the parameters has a huge influence on the final properties of the porcelain models. This work contributes to a better assimilation of AM technologies in ceramic industry. Acknowledgments: The RoboCer3D project – project of additive rapid manufacturing through 3D printing ceramic material (POCI-01-0247-FEDER-003350) financed by Compete 2020, PT 2020, European Regional Development Fund – FEDER through the International and Competitive Operational Program (POCI) under the PT2020 partnership agreement.

Keywords: additive manufacturing, porcelain, robocasting, R3D

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Authors: Ivan Sosa Gomez

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Digitalization has impacted the entire insurance value chain, and the growing movement towards P2P platforms and the collaborative economy is also beginning to have a significant impact. P2P insurance is defined as innovation, enabling policyholders to pool their capital, self-organize, and self-manage their own insurance. In this context, new InsurTech start-ups are emerging as peer-to-peer (P2P) providers, based on a model that differs from traditional insurance. As a result, although P2P platforms do not change the fundamental basis of insurance, they do enable potentially more efficient business models to be established in terms of ensuring the coverage of risk. It is therefore relevant to determine whether p2p innovation can have substantial effects on the future of the insurance sector. For this purpose, it is considered necessary to develop P2P innovation from a business perspective, as well as to build a comparison between a traditional model and a P2P model from an actuarial perspective. Objectives: The objectives are (1) to represent P2P innovation in the business model compared to the traditional insurance model and (2) to establish a comparison between a traditional model and a P2P model from an actuarial perspective. Methodology: The research design is defined as action research in terms of understanding and solving the problems of a collectivity linked to an environment, applying theory and best practices according to the approach. For this purpose, the study is carried out through the participatory variant, which involves the collaboration of the participants, given that in this design, participants are considered experts. For this purpose, prolonged immersion in the field is carried out as the main instrument for data collection. Finally, an actuarial model is developed relating to the calculation of premiums that allows for the establishment of projections of future scenarios and the generation of conclusions between the two models. Main Contributions: From an actuarial and business perspective, we aim to contribute by developing a comparison of the two models in the coverage of risk in order to determine whether P2P innovation can have substantial effects on the future of the insurance sector.

Keywords: Insurtech, innovation, business model, P2P, insurance

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Authors: Karolina Mazur, Stanislaw Kuciel

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Polylactides (PLA) and polyhydroxyalkanoates (PHA) are the two groups of biodegradable and biocompatible thermoplastic polymers most commonly utilised in medicine and rehabilitation. The aim of this work is to determine the changes in the strength properties and the microstructures taking place in biodegradable polymer composites during their long-term storage in a highly cooled environment (i.e. a freezer at -24ºC) and to initially assess the durability of such biocomposites when used as single-use elements of rehabilitation or medical equipment. It is difficult to find any information relating to the feasibility of long-term storage of technical products made of PLA or PHA, but nonetheless, when using these materials to make products such as casings of hair dryers, laptops or mobile phones, it is safe to assume that without storing in optimal conditions their degradation time might last even several years. SEM images and the assessment of the strength properties (tensile, bending and impact testing) were carried out and the density and water sorption of two polymers, PLA and PHA (NaturePlast PLE 001 and PHE 001), filled with cellulose fibres (corncob grain – Rehofix MK100, Rettenmaier&Sohne) up to 10 and 20% mass were determined. The biocomposites had been stored at a temperature of -24ºC for 4 years. In order to find out the changes in the strength properties and the microstructure taking place after such a long time of storage, the results of the assessment have been compared with the results of the same research carried out 4 years before. Results shows a significant change in the manner of fractures – from ductile with developed surface for the PHA composite with corncob grain when the tensile testing was performed directly after the injection into a more brittle state after 4 years of storage, which is confirmed by the strength tests, where a decrease of deformation is observed at point of fracture. The research showed that there is a way of storing medical devices made out of PLA or PHA for a reasonably long time, as long as the required temperature of storage is met. The decrease of mechanical properties found during tensile testing and bending for PLA was less than 10% of the tensile strength, while the modulus of elasticity and deformation at fracturing slightly rose, which may implicate the beginning of degradation processes. The strength properties of PHA are even higher after 4 years of storage, although in that case the decrease of deformation at fracturing is significant, reaching even 40%, which suggests its degradation rate is higher than that of PLA. The addition of natural particles in both cases only slightly increases the biodegradation.

Keywords: biocomposites, PLA, PHA, storage

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Authors: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is the generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups, and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contains four obvious stages, and the main decomposition reaction occurred in the range of 200-600°C. The Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2, and 3 were in the range of 6.67-20.37 kJ for SS; 1.51-6.87 kJ for HZSM5; and 2.29-9.17 kJ for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1, and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with AC and HZSM5 were in the total range of C4-C17, with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds, while with the presence of AC and HZSM5 dropped to 13.02% and 7.3%, respectively. Meanwhile, the generation of benzene, toluene, and xylene (BTX) compounds was significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR, and TGA techniques. Overall, this research demonstrated AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: catalytic pyrolysis, sewage sludge, activated char, HZSM5, bio-oil

Procedia PDF Downloads 179

Authors: Xiaofei Li, Zhiwei Zhong, Deli Wang

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Large herbivores affect plant growth not only through their direct, consumptive effects, but also through indirect effects that alter species interactions. Indirect effects can be either positive or negative, therefore having the potential to mitigate or enhance the direct impacts of herbivores. However, until recently, we know considerably less about the indirect effects than the direct effects of large herbivores on plants, and few studies have explored multiple indirect pathways simultaneously. Here, we investigated how large domestic herbivores, cattle (Bos taurus), can shape population growth of an intermediately preferred forb species, Artemsisa scoparia, through diverse pathways in a temperate grassland of northeast China. We found that, although exposure to direct consumption of cattle, A. scoparia growth was not inhibited, but rather showed a significant increase in the grazed than ungrazed areas. This unexpected result was due to grazing-induced multiple indirect, positive effects overwhelmed the direct, negative consumption effects of cattle on plant growth. The much more intensive consumption on the dominant Leymus chinensis grass, ground litter removal, and increases in ant nest abundance induced by cattle, exerted significant indirect, positive effects on A. scoparia growth. These pathways benefited A.scoparia growth by lessening interspecific competition, mitigating negative effects of litter accumulation, and increasing soil nutrient availability, respectively. Our results highlight the need to integrate indirect effects into the traditional food web theory, which is based primary on direct, trophic linkages, to fully understand community organization and dynamics. Large herbivores are important conservation and management targets, our results suggest that these mammals should be managed with the understanding that they can affect primary producers through diverse paths.

Keywords: grasslands, large herbivores, plant growth, indirect effects

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Authors: Tomoya Oshiro, Hiroko Ono

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Japan's aging population is increasing due to the decrease in birthrate. It causes various problems like the decrease in the gross domestic product of the country. The reason is why the local government of Japan has been on the way to a sustainable city recently. Then it is essential to get control of an urban structure to make the compact city successful. There are many kinds of paper about the compact city; however, the paper about a compact city of the island-type city is less. The purpose of this study is to clarify difference of urban structure between an island-type and a general city type. The method which has conducted in this research has two steps. First of all, by using evaluation indexes in the handbook, we evaluated the urban structures among each same -population-class cities from 50,000 to 100,000 people. Next, to clear the difference about the urban structure and feature between island-type and general-type cities compare the radar chart which is composed with each evaluation indexes of urban structure. Moreover, in order to clarify the relationship between evaluation indexes and the place of residence by using GIS software to show up population density on the map. As a result of this research, the management of local government and the local economy in evaluation indexes are indicated to be negative point in comparison of island-type cities with general cities. However, evaluation indexes of safety/security and low-carbon/energy are proved to be positive point. The research to find the difference features of the island-type of urban structure proves that the management of local government or the local economy is negative point in these island-type cities. In addition, the public transportation coverage in Miyako Island, Sado Island, and Amakusa Island show low value compare with other islands and average value. Relationship between evaluation indexes of an urban structure and the place of residence prove that the place of residence is related to public transportation coverage. If the place of residence is spread out, the public transportation coverage will be decreased. The results of this research reveal that the finances in island-type cities are negative point compare to general cities. This problem is caused by declining population. In addition, the place of residence is related to the public transportation coverage. Even though, it needs a much money to increase the public transportation coverage. It is possibly to cause other problems furthermore the aspect of finance is influenced by that as well. The conclusion in this research suggests that it is important for creating the compact city in island-type cities that we first need to address solving the problems about the management of local government and the local economy.

Keywords: sustainable city, comparative analysis, geographic information system, urban structure

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Authors: Stephen McCarthy, Joanne Gray, Esther Carr, Gerard Danjoux, Paul Baker, Rhiannon Hackett

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Background: The Go Well Health (GWH) platform is a web-based programme that allows patients to access personalised care plans and resources, aimed at prehabilitation prior to surgery. The online digital platform delivers essential patient education and support for patients prior to undergoing total hip replacements (THR) and total knee replacements (TKR). This study evaluated the impact of an online digital platform (ODP) in terms of functional health outcomes, health related quality of life and hospital length of stay following surgery. Methods: A retrospective cohort study comparing a cohort of patients who used the online digital platform (ODP) to deliver patient education and support (PES) prior to undergoing THR and TKR surgery relative to a cohort of patients who did not access the ODP and received usual care. Routinely collected Patient Reported Outcome Measures (PROMs) data was obtained on 2,406 patients who underwent a knee replacement (n=1,160) or a hip replacement (n=1,246) between 2018 and 2019 in a single surgical centre in the United Kingdom. The Oxford Hip and Knee Score and the European Quality of Life Five-Dimensional tool (EQ5D-5L) was obtained both pre-and post-surgery (at 6 months) along with hospital LOS. Linear regression was used to compare the estimate the impact of GWH on both health outcomes and negative binomial regressions were used to impact on LOS. All analyses adjusted for age, sex, Charlson Comorbidity Score and either pre-operative Oxford Hip/Knee scores or pre-operative EQ-5D scores. Fractional polynomials were used to represent potential non-linear relationships between the factors included in the regression model. Findings: For patients who underwent a knee replacement, GWH had a statistically significant impact on Oxford Knee Scores and EQ5D-5L utility post-surgery (p=0.039 and p=0.002 respectively). GWH did not have a statistically significant impact on the hospital length of stay. For those patients who underwent a hip replacement, GWH had a statistically significant impact on Oxford Hip Scores and EQ5D-5L utility post (p=0.000 and p=0.009 respectively). GWH also had a statistically significant reduction in the hospital length of stay (p=0.000). Conclusion: Health Outcomes were higher for patients who used the GWH platform and underwent THR and TKR relative to those who received usual care prior to surgery. Patients who underwent a hip replacement and used GWH also had a reduced hospital LOS. These findings are important for health policy and or decision makers as they suggest that prehabilitation via an ODP can maximise health outcomes for patients following surgery whilst potentially making efficiency savings with reductions in LOS.

Keywords: digital prehabilitation, online digital platform, orthopaedics, surgery

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Authors: Davood Vatankhah, Reza Mokhtari Malekabadi, Mohsen Saghaei

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Function of urban transportation systems depends on the existence of the required infrastructures, appropriate placement of different components, and the cooperation of these components with each other. Establishing various neighboring parking spaces in city neighborhood in order to prevent long-term and inappropriate parking of cars in the allies is one of the most effective operations in reducing the crowding and density of the neighborhoods. Every place with a certain application attracts a number of daily travels which happen throughout the city. A large percentage of the people visiting these places go to these travels by their own cars; therefore, they need a space to park their cars. The amount of this need depends on the usage function and travel demand of the place. The study aims at investigating the spatial distribution of the public parking spaces, determining the effective factors in locating, and their combination in GIS environment in Khomeinishahr of Isfahan city. Ultimately, the study intends to create an appropriate pattern for locating parking spaces, determining the request for parking spaces of the traffic areas, choosing the proper places for providing the required public parking spaces, and also proposing new spots in order to promote quality and quantity aspects of the city in terms of enjoying public parking spaces. Regarding the method, the study is based on applied purpose and regarding nature, it is analytic-descriptive. The population of the study includes people of the center of Khomeinishahr which is located on Northwest of Isfahan having about 5000 hectares of geographic area and the population of 241318 people are in the center of Komeinishahr. In order to determine the sample size, Cochran formula was used and according to the population of 26483 people of the studied area, 231 questionnaires were used. Data analysis was carried out by usage of SPSS software and after estimating the required space for parking spaces, initially, the effective criteria in locating the public parking spaces are weighted by the usage of Analytic Hierarchical Process in the Arc GIS software. Then, appropriate places for establishing parking spaces were determined by fuzzy method of Order Weighted Average (OWA). The results indicated that locating of parking spaces in Khomeinishahr have not been carried out appropriately and per capita of the parking spaces is not desirable in relation to the population and request; therefore, in addition to the present parking lots, 1434 parking lots are needed in the area of the study for each day; therefore, there is not a logical proportion between parking request and the number of parking lots in Khomeinishahr.

Keywords: GIS, locating, parking, khomeinishahr

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Authors: Akbar Jamali

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Many scholars consider Hegel’s philosophy of art as the greatest theory of aesthetics since Aristotle’s Poetics. ‘Freedom’ distinguishes modern, especially German Idealism with Greek philosophy. Therefore, introducing and contemplating on Hegel’s Aesthetics as a whole, freedom as the essence of art, Hegel’s controversial claim on the end of art, and the relation of art and state is the main theme of this study. Hegel’s aesthetics is to be understood in his whole system. According to Hegel’s speculative philosophy, being is to be understood as self-determining Reason or Idea. The self-determining Reason actualizes and realizes himself in the course of history. Idea in the process of self-actualization becomes more and more rational. It first actualizes itself in matter, then in non-conscious life, finally in conscious and self-conscious life. Self-conscious life is the most rational stage of development of Idea in which the subject can think and imagine, use language and exercise freedom. Hegel calls this self-conscious life Spirit (Geist). Therefore, emergence of human being is an essential moment in the process of self-determination of Reason. It is not accidental rather a necessity. The essence of spirit is freedom. Since the history is the process of the self-actualization if spirit, humankind becomes more and more, free. Spirit in its ‘Absolute’ form manifests itself into three forms; Art, Religion and philosophy. Art is the first stage in which Spirit understands itself. In fact, Art is the expression of human spirit, which is comprehended by our senses. Beauty is defined as the sensuous expression of free Spirit. The purpose of art is, therefore, to express, enjoy and contemplate on our freedom. State belongs to the realm of Objective spirit, while Art along with Religion and philosophy belong to the realm of Absolute Spirit. Absolute spirit is superior to Objective Spirit; therefore, state must not interfere in the realm of art. Limitation on art by state directly violates freedom and prevents development of national spirit. Genuine art leads us to freedom and richness of (national) Spirit. Using Hegel’s philosophy of art, we can comprehend why totalitarian states try to limit art and, why artists are the enemy of totalitarian states. In this philosophical system, we contemplate on art as a way to freedom and emancipation.

Keywords: aesthetics, freedom, spirit, state

Procedia PDF Downloads 291

Authors: Vilma Sasyte, Vilma Viliene, Agila Dauksiene, Asta Raceviciute-Stupeliene, Romas Gruzauskas, Saulius Alijosius

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The eight-week feeding trial was conducted involving 27-wk-old Isa brown laying hens to study the effect of dry extrusion processing on partial reduction in total glucosinolates content of locally produced rapeseed and on productivity and eggs quality parameters of laying hens. Thirty-six hens were randomly assigned one of three treatments (CONTR, AERS and HERS), each comprising 12, individual caged layers. The main composition of the diets was the same, but extruded soya bean seed were replaced with 2.5% of the extruded rapeseed in the AERS group and 4.5 % in the HERS group. Rapeseed was extruded together with faba beans. Due to extrusion process the glucosinolates content was reduced by 7.83 µmol/g of rapeseed. The results of conducted trial shows, that during all experimental period egg production parameters, such as the average feed intake (6529.17 vs. 6257 g/hen/14 day; P < 0.05) and laying intensity (94.35% vs. 89.29; P < 0.05) were statistically different for HERS and CONTR laying hens respectively. Only the feed conversion ratio to produce 1 kg of eggs, kg in AERS group was by 11 % lower compared to CONTR group (P < 0.05). By analysing the effect of extruded rapeseed on egg mass, the statistical differences between treatments were no determined. The dietary treatments did not affect egg weight, albumen height, haugh units, albumen and yolk pH. However, in the HERS group were get eggs with the more intensive yolk color, higher redness (a) and yellowness (b) values. The inclusion of full-fat extruded rapeseed had no effect on egg shell quality parameters, i.e. shell breaking strength, shell weight with and without coat and shell index, but in the experimental groups were get eggs with the thinner shell (P < 0.05). The internal egg quality analysis showed that with higher content of extruded rapeseed (4.5 %) level in the diet, the total cholesterol in the eggs yolk decreased by 1.92 mg/g in comparison with CONTR group (P < 0.05). Eggs laid by hens fed the diet containing 2.5% and 4.5% had increasing ∑PNRR/∑SRR ratio and decreasing ∑(n-6)/∑(n-3) ratio values of eggs yolk fatty acids than in CONTR group. Eggs of hens fed different amount of extruded rapeseed presented an n-6 : n-3 ratio changed from 5.17 to 4.71. The analysis of the relationship between hypocholesteremia/ hypercholesterolemia fatty acids (H/H), which is based on the functional properties of fatty acids, found that the value of it ratio is significant higher in laying hens fed diets supplemented with 4.5% extruded rapeseed than the CONTR group, demonstrating the positive effects of extruded rapeseed on egg quality. The results of trial confirmed that extruded full fat rapeseed to the 4.5% are suitable to replace soyabean in the compound feed of laying hens.

Keywords: egg quality, extruded full-fat rapeseed, laying hens, productivity

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Authors: Kyohei Yoshino, Masahiko Matsumiya, Yuji Sasaki

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Recently, studies have been conducted on Au(III) extraction using ionic liquids (ILs) as extractants or diluents. ILs such as piperidinium, pyrrolidinium, and pyridinium have been studied as extractants for noble metal extractions. Furthermore, the polarity, hydrophobicity, and solvent miscibility of these ILs can be adjusted depending on their intended use. Therefore, the unique properties of ILs make them functional extraction media. The extraction mechanism of Au(III) using phosphonium-based ILs and relevant thermodynamic studies are yet to be reported. In the present work, we focused on the mechanism of Au(III) extraction and related thermodynamic analyses using phosphonium-based ILs. Triethyl-n-pentyl, triethyl-n-octyl, and triethyl-n-dodecyl phosphonium bis(trifluoromethyl-sulfonyl)amide, [P₂₂₂ₓ][NTf₂], (X = 5, 8, and 12) were investigated for Au(III) extraction. The IL–Au complex was identified as [P₂₂₂₅][AuCl₄] using UV–Vis–NIR and Raman spectroscopic analyses. The extraction behavior of Au(III) was investigated with a change in the [P₂₂₂ₓ][NTf₂]IL concentration from 1.0 × 10–4 to 1.0 × 10–1 mol dm−3. The results indicate that Au(III) can be easily extracted by the anion-exchange reaction in the [P₂₂₂ₓ][NTf₂]IL. The slope range 0.96–1.01 on the plot of log D vs log[P₂₂₂ₓ][NTf2]IL indicates the association of one mole of IL with one mole of [AuCl4−] during extraction. Consequently, [P₂₂₂ₓ][NTf₂] is an anion-exchange extractant for the extraction of Au(III) in the form of anions from chloride media. Thus, this type of phosphonium-based IL proceeds via an anion exchange reaction with Au(III). In order to evaluate the thermodynamic parameters on the Au(III) extraction, the equilibrium constant (logKₑₓ’) was determined from the temperature dependence. The plot of the natural logarithm of Kₑₓ’ vs the inverse of the absolute temperature (T–1) yields a slope proportional to the enthalpy (ΔH). By plotting T–1 vs lnKₑₓ’, a line with a slope range 1.129–1.421 was obtained. Thus, the result indicated that the extraction reaction of Au(III) using the [P₂₂₂ₓ][NTf₂]IL (X=5, 8, and 12) was exothermic (ΔH=-9.39〜-11.81 kJ mol-1). The negative value of TΔS (-4.20〜-5.27 kJ mol-1) indicates that microscopic randomness is preferred in the [P₂₂₂₅][NTf₂]IL extraction system over [P₂₂₂₁₂][NTf₂]IL. The total negative alternation in Gibbs energy (-5.19〜-6.55 kJ mol-1) for the extraction reaction would thus be relatively influenced by the TΔS value on the number of carbon atoms in the alkyl side length, even if the efficiency of ΔH is significantly influenced by the total negative alternations in Gibbs energy. Electrochemical analysis revealed that extracted Au(III) can be reduced in two steps: (i) Au(III)/Au(I) and (ii) Au(I)/Au(0). The diffusion coefficients of the extracted Au(III) species in [P₂₂₂ₓ][NTf₂] (X = 5, 8, and 12) were evaluated from 323 to 373 K using semi-integral and semi-differential analyses. Because of the viscosity of the IL medium, the diffusion coefficient of the extracted Au(III) increases with increasing alkyl chain length. The 4f7/2 spectrum based on X-ray photoelectron spectroscopy revealed that the Au electrodeposits obtained after 10 cycles of continuous extraction and electrodeposition were in the metallic state.

Keywords: au(III), electrodeposition, phosphonium-based ionic liquids, solvent extraction

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Authors: A. M. Merino-Lechuga, A. González-Caro, D. Suescum-Morales, E. Fernández-Ledesma, J. R. Jiménez, J. M. Fernández-Rodriguez

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Since the mid-19th century, the boom in the economy and industry has grown exponentially. This has led to an increase in pollution due to rising Greenhouse Gas (GHG) emissions and the accumulation of waste, leading to an increasingly imminent future scarcity of raw materials and natural resources. Carbon dioxide (CO₂) is one of the primary greenhouse gases, accounting for up to 55% of Greenhouse Gas (GHG) emissions. The manufacturing of construction materials generates approximately 73% of CO₂ emissions, with Portland cement production contributing to 41% of this figure. Hence, there is scientific and social alarm regarding the carbon footprint of construction materials and their influence on climate change. Carbonation of concrete is a natural process whereby CO₂ from the environment penetrates the material, primarily through pores and microcracks. Once inside, carbon dioxide reacts with calcium hydroxide (Ca(OH)2) and/or CSH, yielding calcium carbonates (CaCO3) and silica gel. Consequently, construction materials act as carbon sinks. This research investigated the effect of accelerated carbonation on the physical, mechanical, and chemical properties of two types of non-structural vibrated concrete pavers (conventional and draining) made from natural aggregates and two types of recycled aggregates from construction and demolition waste (CDW). Natural aggregates were replaced by recycled aggregates using a volumetric substitution method, and the CO₂ capture capacity was calculated. Two curing environments were utilized: a carbonation chamber with 5% CO₂ and a standard climatic chamber with atmospheric CO₂ concentration. Additionally, the effect of curing times of 1, 3, 7, 14, and 28 days on concrete properties was analyzed. Accelerated carbonation in-creased the apparent dry density, reduced water-accessible porosity, improved compressive strength, and decreased setting time to achieve greater mechanical strength. The maximum CO₂ capture ratio was achieved with the use of recycled concrete aggregate (52.52 kg/t) in the draining paver. Accelerated carbonation conditions led to a 525% increase in carbon capture compared to curing under atmospheric conditions. Accelerated carbonation of cement-based products containing recycled aggregates from construction and demolition waste is a promising technology for CO₂ capture and utilization, offering a means to mitigate the effects of climate change and promote the new paradigm of circular economy.

Keywords: accelerated carbonation, CO₂ curing, CO₂ uptake and construction and demolition waste., circular economy

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Authors: A. G. Back

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In the context of global climate change, extreme weather events are increasingly intense and frequent, challenging the adaptability of urban space. In this sense, urban planning is a relevant instrument for addressing, in a systemic manner, various sectoral policies capable of linking the urban agenda to the reduction of social and environmental risks. The Master Plan of the Municipality of Sao Paulo, 2014, presents innovations capable of promoting the transition to sustainability in the urban space. Among such innovations, the following stand out: i) promotion of density in the axes of mass transport involving mixture of commercial, residential, services, and leisure uses (principles related to the compact city); ii) vulnerabilities reduction based on housing policies, including regular sources of funds for social housing and land reservation in urbanized areas; iii) reserve of green areas in the city to create parks and environmental regulations for new buildings focused on reducing the effects of heat island and improving urban drainage. However, long-term implementation involves distributive conflicts and may change in different political, economic, and social contexts over time. Thus, the central objective of this paper is to identify which factors limit or support the implementation of these policies. That is, to map the challenges and interests of converging and/or divergent urban actors in the sustainable urban development agenda and what resources they mobilize to support or limit these actions in the city of Sao Paulo. Recent proposals to amend the urban zoning law undermine the implementation of the Master Plan guidelines. In this context, three interest groups with different views of the city come into dispute: the real estate market, upper middle class neighborhood associations ('not in my backyard' movements), and social housing rights movements. This paper surveys the different interests and visions of these groups taking into account their convergences, or not, with the principles of sustainable urban development. This approach seeks to fill a gap in the international literature on the causes that underpin or hinder the continued implementation of policies aimed at the transition to urban sustainability in the medium and long term.

Keywords: adaptation, ecosystem-based adaptation, interest groups, urban planning, urban transition to sustainability

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Authors: Hong Je Kang, Young Chae Choi, Jin Sung Park, Isac Kim

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Purpose: Osteoporotic fractures are an important among postmenopausal women. When osteoporotic distal radial fractures occur, osteoporosis must be treated to prevent the hip and spine fractures. Intravenous injection of Zoledronic acid is expected to improve preventing osteoporotic fractures. Many articles reported the effect of intravenous Zoledronic acid to BMD of the hip and spine fracture or non-fracture patients with low BMD. However, that with distal radial fractures has rarely been reported. Therefore, the authors decided to study the effect of Zoledronic acid in BMD score, bone union, and bone turnover markers in the patients who underwent volar plating due to osteoporotic distal radial fractures. Materials: From April 2018 to May 2022, postmenopausal women aged 55 years or older who had osteoporotic distal radial fractures and who underwent surgical treatment using volar plate fixation were included. Zoledronic acid (5mg) was injected intravenously between 3 and 5 days after surgery. BMD scores after 1 year of operation were compared with the initial scores. Bone turnover markers were measured before surgery, after 3 months, and after 1 year. Radiological follow-up was performed every 2 weeks until the bone union and at 1 year postoperatively. Clinical outcome indicators were measured one year after surgery, and the occurrence of side effects was observed. Result: Total of 23 patients were included, with a lumbar BMD T score of -2.89±0.2 before surgery to -2.27±0.3 one year after surgery (p=0.012) and a femoral neck BMD T score of -2.45±0.3 before surgery to -2.36±0.3 (p=0.041) after one year, and all were statistically significant. Measured as bone resorption markers, serum CTX-1 was 337.43±10.4 pg/mL before surgery, 160.86±8.7 pg/mL (p=0.022) after three months, and 250.12±12.7 pg/mL (p=0.031) after one year. Urinary NTX-1 was 39.24±2.2 ng/mL before surgery, 24.46±1.2 ng/mL (p=0.014) after three months and 30.35±1.6 ng/mL (p=0.042) after one year. Measured as bone formation markers, serum osteocalcin was 13.04±1.1 ng/mL before surgery, 8.84±0.7 ng/mL (p=0.037) after 3 months and 11.1±0.4 ng/mL (p=0.026) after one year. Serum bone-specific ALP was 11.24±0.9 IU/L before surgery, 8.25±0.9 IU/L (p=0.036) after three months, and 10.2±0.9 IU/L (p=0.027) after one year. All were statistically significant. All cases showed bone union within an average of 6.91±0.3 weeks without any signs of failure. Complications were found in 5 out of 23 cases (21.7%), such as headache, nausea, muscle pain, and fever. Conclusion: When Zoledronic acid was used, BMD was improved in both the spine and femoral neck. This may reduce the likelihood and subsequent morbidity of additional osteoporotic fractures. This study is meaningful in that there was no difference in the duration of bone union and radiological characteristics in patients with distal radial fractures administrated with intravenous BP early after the fractures, and improvement in BMD and bone turnover indicators was measured.

Keywords: zeoldreonic acid, BMD, osteoporosis, distal radius

Procedia PDF Downloads 115