Search results for: Alzheimer’s related quality of life
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 22808

Search results for: Alzheimer’s related quality of life

1118 Influence of Laser Treatment on the Growth of Sprouts of Different Wheat Varieties

Authors: N. Bakradze, T. Dumbadze, N. Gagelidze, L. Amiranashvili, A. D. L. Batako

Abstract:

Cereals are considered as a strategic product in human life and it demand is increasing with the growth of world population. There is always shortage of cereals in various areas of the globe. For example, Georgia own production meets only 15-20% of the demand for grain, despite the fact that the country is considered one of the main centers of wheat origin. In Georgia, there are 14 types of wheat and more than 150 subspecies, and 40 subspecies of common wheat. Increasing wheat production is important for the country. One of the ways to solve the problem is to develop and implement new, environmentally and economically acceptable technologies. Such technologies include pre-sowing treatment of seed with a laser and associative nitrogen-fixing of the Azospirillum brasilensse bacteria. In the region there are Dika and Lomtagora which are among the most common in Georgia. Dika is a frost-resistant wheat, with a high ability to adapt to the environment, resistant to falling and it is sown in highlands. Dicka excellent properties are due to its strong immunity to fungal diseases; Dicka grains are rich in protein and lysine. Lomtagora 126 differs with its winter and drought resistance, and, it has a great ability to germinate. Lomtagora is characterized by a strong root system and a high budding capacity. It is an early variety, fall-resistant, easy to thresh and suitable for mechanized harvesting with large and red grains. The plant is moderately resistant to fungal diseases. This paper presents some preliminary experimental results where, a continuous CO2 laser at a power of 25-40 W/cm2 was used to radiate grains at a flow rate of 10-15 cm/sec. The treatment was carried out on grains of the Triticum aestivum L. var. of Lutescens (local variety name - Lomtagora 126), and Triticum carthlicum Nevski (local variety name - Dika). Here the grains were treated with Azospirillum brasilensse isolate (108-109 CFU / ml), which was isolated from the rhizosphere of wheat. It was observed that the germination of the wheat was not significantly influenced by either laser or bacteria treatment. In the case of the variety Lomtagora 126, when irradiated at an angle of 90°, it slightly improved the growth within 38 days of sawing, and in the case of irradiation at an angle of 90°+1, by 23%. The treatment of seeds with Azospirillum brazilense in both irradiated and non-irradiated variants led to an improvement in the growth of ssprouts. However, in the case of treatment with azospiril alone - by 22%, and with joint treatment of seeds with azospiril and irradiation - by 29%. In the case of the Dika wheat, the irradiation only led to an increase in growth by 8-9%, and the combine treatment of seeds with azospiril and irradiation - by 10-15%, in comparison with the control. Thus, the combine treatment of wheat of different varieties provided the best effect on the growth. Acknowledgment: This work was supported by Shota Rustaveli National Science Foundation of Georgia (SRNSFG) (Grant number CARYS 19-573)

Keywords: laser treatment, Azospirillum brasilensse, seeds, wheat varieties, Lomtagora, Dika

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1117 Experimental Investigation of Absorbent Regeneration Techniques to Lower the Cost of Combined CO₂ and SO₂ Capture Process

Authors: Bharti Garg, Ashleigh Cousins, Pauline Pearson, Vincent Verheyen, Paul Feron

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The presence of SO₂ in power plant flue gases makes flue gas desulfurization (FGD) an essential requirement prior to post combustion CO₂ (PCC) removal facilities. Although most of the power plants worldwide deploy FGD in order to comply with environmental regulations, generally the achieved SO₂ levels are not sufficiently low for the flue gases to enter the PCC unit. The SO₂ level in the flue gases needs to be less than 10 ppm to effectively operate the PCC installation. The existing FGD units alone cannot bring down the SO₂ levels to or below 10 ppm as required for CO₂ capture. It might require an additional scrubber along with the existing FGD unit to bring the SO₂ to the desired levels. The absence of FGD units in Australian power plants brings an additional challenge. SO₂ concentrations in Australian power station flue gas emissions are in the range of 100-600 ppm. This imposes a serious barrier on the implementation of standard PCC technologies in Australia. CSIRO’s developed CS-Cap process is a unique solution to capture SO₂ and CO₂ in a single column with single absorbent which can potentially bring cost-effectiveness to the commercial deployment of carbon capture in Australia, by removing the need for FGD. Estimated savings of removing SO₂ through a similar process as CS-Cap is around 200 MMUSD for a 500 MW Australian power plant. Pilot plant trials conducted to generate the proof of concept resulted in 100% removal of SO₂ from flue gas without utilising standard limestone-based FGD. In this work, removal of absorbed sulfur from aqueous amine absorbents generated in the pilot plant trials has been investigated by reactive crystallisation and thermal reclamation. More than 95% of the aqueous amines can be reclaimed back from the sulfur loaded absorbent via reactive crystallisation. However, the recovery of amines through thermal reclamation is limited and depends on the sulfur loading on the spent absorbent. The initial experimental work revealed that reactive crystallisation is a better fit for CS-Cap’s sulfur-rich absorbent especially when it is also capable of generating K₂SO₄ crystals of highly saleable quality ~ 99%. Initial cost estimation carried on both the technologies resulted in almost similar capital expenditure; however, the operating cost is considerably higher in thermal reclaimer than that in crystalliser. The experimental data generated in the laboratory from both the regeneration techniques have been used to generate the simulation model in Aspen Plus. The simulation model illustrates the economic benefits which could be gained by removing flue gas desulfurization prior to standard PCC unit and replacing it with a CS-Cap absorber column co-capturing CO₂ and SO₂, and it's absorbent regeneration system which would be either reactive crystallisation or thermal reclamation.

Keywords: combined capture, cost analysis, crystallisation, CS-Cap, flue gas desulfurisation, regeneration, sulfur, thermal reclamation

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1116 Elevated Celiac Antibodies and Abnormal Duodenal Biopsies Associated with IBD Markers: Possible Role of Altered Gut Permeability and Inflammation in Gluten Related Disorders

Authors: Manav Sabharwal, Ruda Rai Md, Candace Parker, James Ridley

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Wheat is one of the most commonly consumed grains worldwide, which contains gluten. Nowadays, gluten intake is considered to be a trigger for GRDs, including Celiac disease (CD), a common genetic disease affecting 1% of the US population, non-celiac gluten sensitivity (NCGS) and wheat allergy. NCGS is being recognized as an acquired gluten-sensitive enteropathy that is prevalent across age, ethnic and geographic groups. The cause of this entity is not fully understood, and recent studies suggest that it is more common in participants with irritable bowel syndrome (IBS), with iron deficiency anemia, symptoms of fatigue, and has considerable overlap in symptoms with IBS and Crohn’s disease. However, these studies were lacking in availability of complete serologies, imaging tests and/or pan-endoscopy. We performed a prospective study of 745 adult patients who presented to an outpatient clinic for evaluation of chronic upper gastro-intestinal symptoms and subsequently underwent an upper endoscopic (EGD) examination as standard of care. Evaluation comprised of comprehensive celiac antibody panel, inflammatory bowel disease (IBD) serologic markers, duodenal biopsies and Small Bowel Video Capsule Endoscopy (VCE), when available. At least 6 biopsy specimens were obtained from the duodenum and proximal jejunum during EGD, and CD3+ Intraepithelial lymphocytes (IELs) and villous architecture were evaluated by a single experienced pathologist, and VCE was performed by a single experienced gastroenterologist. Of the 745 patients undergoing EGD, 12% (93/745) patients showed elevated CD3+ IELs in the duodenal biopsies. 52% (387/745) completed a comprehensive CD panel and 7.2% (28/387) were positive for at least 1 CD antibody (Tissue transglutaminase (tTG), being the most common antibody in 65% (18/28)). Of these patients, 18% (5/28) showed increased duodenal CD3+ IELs, but 0% showed villous blunting or distortion to meet criteria for CD. Surprisingly, 43% (12/28) were positive for at 1 IBD serology (ASCA, ANCA or expanded IBD panel (LabCorp)). Of these 28 patients, 29% (8/28) underwent a SB VCE, of which 100 % (8/8) showed significant jejuno-ileal mucosal lesions diagnostic for IBD. Findings of abnormal CD antibodies (7.2%, 28/387) and increased CD3+ IELs on duodenal biopsy (12%, 93/745) were observed frequently in patients with UGI symptoms undergoing EGD in an outpatient clinic. None met criteria for CD, and a high proportion (43%, 12/28) showed evidence of overlap with IBD. This suggests a potential causal link of acquired GRDs to underlying inflammation and gut mucosal barrier disruption. Further studies to investigate a role for abnormal antigen presentation of dietary gluten to gut associated lymphoid tissue as a cause are justified. This may explain a high prevalence of GRDs in the population and correlation with IBS, IBD and other gut inflammatory disorders.

Keywords: celiac, gluten sensitive enteropathy, lymphocitic enteritis, IBS, IBD

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1115 The Effect of the Construction Contract System by Simulating the Comparative Costs of Capital to the Financial Feasibility of the Construction of Toll Bali Mandara

Authors: Mas Pertiwi I. G. AG Istri, Sri Kristinayanti Wayan, Oka Aryawan I. Gede Made

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Ability of government to meet the needs of infrastructure investment constrained by the size of the budget commitments for other sectors. Another barrier is the complexity of the process of land acquisition. Public Private Partnership can help bridge the investment gap by including the amount of funding from the private sector, shifted the responsibility of financing, construction of the asset, and the operation and post-project design and care to them. In principle, a construction project implementation always requires the investor as a party to provide resources in the form of funding which it must be contained in a successor agreement in the form of a contract. In general, construction contracts consist of contracts which passed in Indonesia and contract International. One source of funding used in the implementation of construction projects comes from funding that comes from the collaboration between the government and the private sector, for example with the system: BLT (Build Lease Transfer), BOT (Build Operate Transfer), BTO (Build Transfer Operate) and BOO (Build Operate Own). And form of payment under a construction contract can be distinguished several ways: monthly payment, payments based on progress and payment after completed projects (Turn Key). One of the tools used to analyze the feasibility of the investment is to use financial models. The financial model describes the relationship between different variables and assumptions used. From a financial model will be known how the cash flow structure of the project, which includes revenues, expenses, liabilities to creditors and the payment of taxes to the government. Net cash flow generated from the project will be used as a basis for analyzing the feasibility of investment source of project financing Public Private Partnership could come from equity or debt. The proportion of funding according to its source is a comparison of a number of investment funds originating from each source of financing for a total investment cost during the construction period by selected the contract system and several alternative financing percentage ratio determined according to sources will generate cash flow structure that is different. Of the various possibilities for the structure of the cash flow generated will be analyzed by software is to test T Paired to compared the contract system used by various alternatives comparison of financing to determine the effect of the contract system and the comparison of such financing for the feasibility of investment toll road construction project for the economic life of 20 (twenty) years. In this use case studies of toll road contruction project Bali Mandara. And in this analysis only covered two systems contracts, namely Build Operate Transfer and Turn Key. Based on the results obtained by analysis of the variable investment feasibility of the NPV, BCR and IRR between the contract system Build Operate Transfer and contract system Turn Key on the interest rate of 9%, 12% and 15%.

Keywords: contract system, financing, internal rate of return, net present value

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1114 Diagnostic Yield of CT PA and Value of Pre Test Assessments in Predicting the Probability of Pulmonary Embolism

Authors: Shanza Akram, Sameen Toor, Heba Harb Abu Alkass, Zainab Abdulsalam Altaha, Sara Taha Abdulla, Saleem Imran

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Acute pulmonary embolism (PE) is a common disease and can be fatal. The clinical presentation is variable and nonspecific, making accurate diagnosis difficult. Testing patients with suspected acute PE has increased dramatically. However, the overuse of some tests, particularly CT and D-dimer measurement, may not improve care while potentially leading to patient harm and unnecessary expense. CTPA is the investigation of choice for PE. Its easy availability, accuracy and ability to provide alternative diagnosis has lowered the threshold for performing it, resulting in its overuse. Guidelines have recommended the use of clinical pretest probability tools such as ‘Wells score’ to assess risk of suspected PE. Unfortunately, implementation of guidelines in clinical practice is inconsistent. This has led to low risk patients being subjected to unnecessary imaging, exposure to radiation and possible contrast related complications. Aim: To study the diagnostic yield of CT PA, clinical pretest probability of patients according to wells score and to determine whether or not there was an overuse of CTPA in our service. Methods: CT scans done on patients with suspected P.E in our hospital from 1st January 2014 to 31st December 2014 were retrospectively reviewed. Medical records were reviewed to study demographics, clinical presentation, final diagnosis, and to establish if Wells score and D-Dimer were used correctly in predicting the probability of PE and the need for subsequent CTPA. Results: 100 patients (51male) underwent CT PA in the time period. Mean age was 57 years (24-91 years). Majority of patients presented with shortness of breath (52%). Other presenting symptoms included chest pain 34%, palpitations 6%, collapse 5% and haemoptysis 5%. D Dimer test was done in 69%. Overall Wells score was low (<2) in 28 %, moderate (>2 - < 6) in 47% and high (> 6) in 15% of patients. Wells score was documented in medical notes of only 20% patients. PE was confirmed in 12% (8 male) patients. 4 had bilateral PE’s. In high-risk group (Wells > 6) (n=15), there were 5 diagnosed PEs. In moderate risk group (Wells >2 - < 6) (n=47), there were 6 and in low risk group (Wells <2) (n=28), one case of PE was confirmed. CT scans negative for PE showed pleural effusion in 30, Consolidation in 20, atelactasis in 15 and pulmonary nodule in 4 patients. 31 scans were completely normal. Conclusion: Yield of CT for pulmonary embolism was low in our cohort at 12%. A significant number of our patients who underwent CT PA had low Wells score. This suggests that CT PA is over utilized in our institution. Wells score was poorly documented in medical notes. CT-PA was able to detect alternative pulmonary abnormalities explaining the patient's clinical presentation. CT-PA requires concomitant pretest clinical probability assessment to be an effective diagnostic tool for confirming or excluding PE. . Clinicians should use validated clinical prediction rules to estimate pretest probability in patients in whom acute PE is being considered. Combining Wells scores with clinical and laboratory assessment may reduce the need for CTPA.

Keywords: CT PA, D dimer, pulmonary embolism, wells score

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1113 Differences in Preschool Educators' and Parents' Interactive Behavior during a Cooperative Task with Children

Authors: Marina Fuertes

Abstract:

Introduction: In everyday life experiences, children are solicited to cooperate with others. Often they perform cooperative tasks with their parents (e.g., setting the table for dinner) or in school. These tasks are very significant since children may learn to turn taking in interactions, to participate as well to accept others participation, to trust, to respect, to negotiate, to self-regulate their emotions, etc. Indeed, cooperative tasks contribute to children social, motor, cognitive and linguistic development. Therefore, it is important to study what learning, social and affective experiences are provided to children during these tasks. In this study, we included parents and preschool educators. Parents and educators are both significant: educative, interactive and affective figures. Rarely parents and educators behavior have been compared in studies about cooperative tasks. Parents and educators have different but complementary styles of interaction and communication. Aims: Therefore, this study aims to compare parents and educators' (of both genders) interactive behavior (cooperativity, empathy, ability to challenge the child, reciprocity, elaboration) during a play/individualized situation involving a cooperative task. Moreover, to compare parents and educators' behavior with girls and boys. Method: A quasi-experimental study with 45 dyads educators-children and 45 dyads with parents and their children. In this study, participated children between 3 and 5 years old and with age appropriate development. Adults and children were videotaped using a variety of materials (e.g., pencils, wood, wool) and tools (e.g., scissors, hammer) to produce together something of their choice during 20-minutes. Each dyad (one adult and one child) was observed and videotaped independently. Adults and children agreed and consented to participate. Experimental conditions were suitable, pleasant and age appropriated. Results: Findings indicate that parents and teachers offer different learning experiences. Teachers were more likely to challenged children to explore new concepts and to accept children ideas. In turn, parents gave more support to children actions and were more likely to use their own example to teach children. Multiple regression analysis indicates that parent versus educator status predicts their behavior. Gender of both children and adults affected the results. Adults acted differently with girls and boys (e.g., adults worked more cooperatively with girls than boys). Male participants supported more girls participation rather than boys while female adults allowed boys to make more decisions than girls. Discussion: Taking our results and past studies, we learn that different qualitative interactions and learning experiences are offered by parents, educators according to parents and children gender. Thus, the same child needs to learn different cooperative strategies according to their interactive patterns and specific context. Yet, cooperative play and individualized activities with children generate learning opportunities and benefits children participation and involvement.

Keywords: early childhood education, parenting, gender, cooperative tasks, adult-child interaction

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1112 Kansei Engineering Applied to the Design of Rural Primary Education Classrooms: Design-Based Learning Case

Authors: Jimena Alarcon, Andrea Llorens, Gabriel Hernandez, Maritza Palma, Lucia Navarrete

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The research has funding from the Government of Chile and is focused on defining the design of rural primary classroom that stimulates creativity. The relevance of the study consists of its capacity to define adequate educational spaces for the implementation of the design-based learning (DBL) methodology. This methodology promotes creativity and teamwork, generating a meaningful learning experience for students, based on the appreciation of their environment and the generation of projects that contribute positively to their communities; also, is an inquiry-based form of learning that is based on the integration of design thinking and the design process into the classroom. The main goal of the study is to define the design characteristics of rural primary school classrooms, associated with the implementation of the DBL methodology. Along with the change in learning strategies, it is necessary to change the educational spaces in which they develop. The hypothesis indicates that a change in the space and equipment of the classrooms based on the emotions of the students will motivate better learning results based on the implementation of a new methodology. In this case, the pedagogical dynamics require an important interaction between the participants, as well as an environment favorable to creativity. Methodologies from Kansei engineering are used to know the emotional variables associated with their definition. The study is done to 50 students between 6 and 10 years old (average age of seven years), 48% of men and 52% women. Virtual three-dimensional scale models and semantic differential tables are used. To define the semantic differential, self-applied surveys were carried out. Each survey consists of eight separate questions in two groups: question A to find desirable emotions; question B related to emotions. Both questions have a maximum of three alternatives to answer. Data were tabulated with IBM SPSS Statistics version 19. Terms referred to emotions are grouped into twenty concepts with a higher presence in surveys. To select the values obtained as part of the implementation of Semantic Differential, a number expected of 'chi-square test (x2)' frequency calculated for classroom space is considered lower limit. All terms over the N expected a cut point, are included to prepare tables for surveys to find a relation between emotion and space. Statistic contrast (Chi-Square) represents significance level ≥ 0, indicator that frequencies appeared are not random. Then, the most representative terms depend on the variable under study: a) definition of textures and color of vertical surfaces is associated with emotions such as tranquility, attention, concentration, creativity; and, b) distribution of the equipment of the rooms, with emotions associated with happiness, distraction, creativity, freedom. The main findings are linked to the generation of classrooms according to diverse DBL team dynamics. Kansei engineering is the appropriate methodology to know the emotions that students want to feel in the classroom space.

Keywords: creativity, design-based learning, education spaces, emotions

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1111 Technology and the Need for Integration in Public Education

Authors: Eric Morettin

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Cybersecurity and digital literacy are pressing issues among Canadian citizens, yet formal education does not provide today’s students with the necessary knowledge and skills needed to adapt to these challenging issues within the physical and digital labor-market. Canada’s current education systems do not highlight the importance of these respective fields, aside from using technology for learning management systems and alternative methods of assignment completion. Educators are not properly trained to integrate technology into the compulsory courses within public education, to better prepare their learners in these topics and Canada’s digital economy. ICTC addresses these gaps in education and training through cross-Canadian educational programming in digital literacy and competency, cybersecurity and coding which is bridged with Canada’s provincially regulated K-12 curriculum guidelines. After analyzing Canada’s provincial education, it is apparent that there are gaps in learning related to technology, as well as inconsistent educational outcomes that do not adequately represent the current Canadian and global economies. Presently only New Brunswick, Nova Scotia, Ontario, and British Columbia offer curriculum guidelines for cybersecurity, computer programming, and digital literacy. The remaining provinces do not address these skills in their curriculum guidelines. Moreover, certain courses across some provinces not being updated since the 1990’s. The three territories respectfully take curriculum strands from other provinces and use them as their foundation in education. Yukon uses all British Columbia curriculum. Northwest Territories and Nunavut respectfully use a hybrid of Alberta and Saskatchewan curriculum as their foundation of learning. Education that is provincially regulated does not allow for consistency across the country’s educational outcomes and what Canada’s students will achieve – especially when curriculum outcomes have not been updated to reflect present day society. Through this, ICTC has aligned Canada’s provincially regulated curriculum and created opportunities for focused education in the realm of technology to better serve Canada’s present learners and teachers; while addressing inequalities and applicability within curriculum strands and outcomes across the country. As a result, lessons, units, and formal assessment strategies, have been created to benefit students and teachers in this interdisciplinary, cross-curricular, practice - as well as meeting their compulsory education requirements and developing skills and literacy in cyber education. Teachers can access these lessons and units through ICTC’s website, as well as receive professional development regarding the assessment and implementation of these offerings from ICTC’s education coordinators, whose combines experience exceeds 50 years of teaching in public, private, international, and Indigenous schools. We encourage you to take this opportunity that will benefit students and educators, and will bridge the learning and curriculum gaps in Canadian education to better reflect the ever-changing public, social, and career landscape that all citizens are a part of. Students are the future, and we at ICTC strive to ensure their futures are bright and prosperous.

Keywords: cybersecurity, education, curriculum, teachers

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1110 Embracing the Uniqueness and Potential of Each Child: Moving Theory to Practice

Authors: Joy Chadwick

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This Study of Teaching and Learning (SoTL) research focused on the experiences of teacher candidates involved in an inclusive education methods course within a four-year direct entry Bachelor of Education program. The placement of this course within the final fourteen-week practicum semester is designed to facilitate deeper theory-practice connections between effective inclusive pedagogical knowledge and the real life of classroom teaching. The course focuses on supporting teacher candidates to understand that effective instruction within an inclusive classroom context must be intentional, responsive, and relational. Diversity is situated not as exceptional but rather as expected. This interpretive qualitative study involved the analysis of twenty-nine teacher candidate reflective journals and six individual teacher candidate semi-structured interviews. The journal entries were completed at the start of the semester and at the end of the semester with the intent of having teacher candidates reflect on their beliefs of what it means to be an effective inclusive educator and how the course and practicum experiences impacted their understanding and approaches to teaching in inclusive classrooms. The semi-structured interviews provided further depth and context to the journal data. The journals and interview transcripts were coded and themed using NVivo software. The findings suggest that instructional frameworks such as universal design for learning (UDL), differentiated instruction (DI), response to intervention (RTI), social emotional learning (SEL), and self-regulation supported teacher candidate’s abilities to meet the needs of their students more effectively. Course content that focused on specific exceptionalities also supported teacher candidates to be proactive rather than reactive when responding to student learning challenges. Teacher candidates also articulated the importance of reframing their perspective about students in challenging moments and that seeing the individual worth of each child was integral to their approach to teaching. A persisting question for teacher educators exists as to what pedagogical knowledge and understanding is most relevant in supporting future teachers to be effective at planning for and embracing the diversity of student needs within classrooms today. This research directs us to consider the critical importance of addressing personal attributes and mindsets of teacher candidates regarding children as well as considering instructional frameworks when designing coursework. Further, the alignment of an inclusive education course during a teaching practicum allows for an iterative approach to learning. The practical application of course concepts while teaching in a practicum allows for a deeper understanding of instructional frameworks, thus enhancing the confidence of teacher candidates. Research findings have implications for teacher education programs as connected to inclusive education methods courses, practicum experiences, and overall teacher education program design.

Keywords: inclusion, inclusive education, pre-service teacher education, practicum experiences, teacher education

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1109 Acoustic Energy Harvesting Using Polyvinylidene Fluoride (PVDF) and PVDF-ZnO Piezoelectric Polymer

Authors: S. M. Giripunje, Mohit Kumar

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Acoustic energy that exists in our everyday life and environment have been overlooked as a green energy that can be extracted, generated, and consumed without any significant negative impact to the environment. The harvested energy can be used to enable new technology like wireless sensor networks. Technological developments in the realization of truly autonomous MEMS devices and energy storage systems have made acoustic energy harvesting (AEH) an increasingly viable technology. AEH is the process of converting high and continuous acoustic waves from the environment into electrical energy by using an acoustic transducer or resonator. AEH is not popular as other types of energy harvesting methods since sound waves have lower energy density and such energy can only be harvested in very noisy environment. However, the energy requirements for certain applications are also correspondingly low and also there is a necessity to observe the noise to reduce noise pollution. So the ability to reclaim acoustic energy and store it in a usable electrical form enables a novel means of supplying power to relatively low power devices. A quarter-wavelength straight-tube acoustic resonator as an acoustic energy harvester is introduced with polyvinylidene fluoride (PVDF) and PVDF doped with ZnO nanoparticles, piezoelectric cantilever beams placed inside the resonator. When the resonator is excited by an incident acoustic wave at its first acoustic eigen frequency, an amplified acoustic resonant standing wave is developed inside the resonator. The acoustic pressure gradient of the amplified standing wave then drives the vibration motion of the PVDF piezoelectric beams, generating electricity due to the direct piezoelectric effect. In order to maximize the amount of the harvested energy, each PVDF and PVDF-ZnO piezoelectric beam has been designed to have the same structural eigen frequency as the acoustic eigen frequency of the resonator. With a single PVDF beam placed inside the resonator, the harvested voltage and power become the maximum near the resonator tube open inlet where the largest acoustic pressure gradient vibrates the PVDF beam. As the beam is moved to the resonator tube closed end, the voltage and power gradually decrease due to the decreased acoustic pressure gradient. Multiple piezoelectric beams PVDF and PVDF-ZnO have been placed inside the resonator with two different configurations: the aligned and zigzag configurations. With the zigzag configuration which has the more open path for acoustic air particle motions, the significant increases in the harvested voltage and power have been observed. Due to the interruption of acoustic air particle motion caused by the beams, it is found that placing PVDF beams near the closed tube end is not beneficial. The total output voltage of the piezoelectric beams increases linearly as the incident sound pressure increases. This study therefore reveals that the proposed technique used to harvest sound wave energy has great potential of converting free energy into useful energy.

Keywords: acoustic energy, acoustic resonator, energy harvester, eigenfrequency, polyvinylidene fluoride (PVDF)

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1108 Life at the Fence: Lived Experiences of Navigating Cultural and Social Complexities among South Sudanese Refugees in Australia

Authors: Sabitra Kaphle, Rebecca Fanany, Jenny Kelly

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Australia welcomes significant numbers of humanitarian arrivals every year with the commitment to provide equal opportunities and the resources required for integration into the new society. Over the last two decades, more than 24,000 South Sudanese people have come to call Australia home. Most of these refugees experienced several challenges whilesettlinginto the new social structures and service systems in Australia. The aim of the research is to explore the factors influencing social and cultural integration of South Sudanese refugees who have settled in Australia. Methodology: This studyused a phenomenological approach based on in-depth interviews designed to elicit the lived experiences of South Sudanese refugees settled in Australia. It applied the principles of narrative ethnography, allowing participants an opportunity to speak about themselves and their experiences of social and cultural integration-using their own words. Twenty-six participants were recruited to the study. Participants were long-term residents (over 10 years of settlement experience)who self-identified as refugees from South Sudan. Participants were given an opportunity to speak in the language of their choice, and interviews were conducted by a bilingual interviewer in their preferred language, time, and location. Interviews were recorded and transcribed verbatim and translated to Englishfor thematic analysis. Findings: Participants’ experiences portray the complexities of integrating into a new society due tothe daily challenges that South Sudaneserefugees face. Themes emerged from narrativesindicated that South Sudanese refugees express a high level of association with a Sudanese identity while demonstrating a significant level of integration into the Australian society. Despite this identity dilemma, these refugees show a high level of consensus about the experiencesof living in Australia that is closely associated with a group identity. In the process of maintaining identity andsocial affiliation, there are significant inter-generational cultural conflicts that participants experience in adapting to Australian society. It has been elucidated that identityconflict often emerges centeringon what constitutes authentic cultural practice as well as who is entitled to claim to be a member of the South Sudanese culture. Conclusions: Results of this study suggest that the cultural identity and social affiliations of South Sudanese refugees settling into Australian society are complex and multifaceted. While there are positive elements of theirintegration into the new society, inter-generational conflictsand identity confusion require further investigation to understand the context that will assist refugees to integrate more successfully into their new society. Given the length of stay of these refugees in Australia, government and settlement agencies may benefit from developing appropriate resources and process that are adaptive to the social and cultural context in which newly arrived refugees will live.

Keywords: cultural integration, inter-generational conflict, lived experiences, refugees, South sudanese

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1107 Design Flood Estimation in Satluj Basin-Challenges for Sunni Dam Hydro Electric Project, Himachal Pradesh-India

Authors: Navneet Kalia, Lalit Mohan Verma, Vinay Guleria

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Introduction: Design Flood studies are essential for effective planning and functioning of water resource projects. Design flood estimation for Sunni Dam Hydro Electric Project located in State of Himachal Pradesh, India, on the river Satluj, was a big challenge in view of the river flowing in the Himalayan region from Tibet to India, having a large catchment area of varying topography, climate, and vegetation. No Discharge data was available for the part of the river in Tibet, whereas, for India, it was available only at Khab, Rampur, and Luhri. The estimation of Design Flood using standard methods was not possible. This challenge was met using two different approaches for upper (snow-fed) and lower (rainfed) catchment using Flood Frequency Approach and Hydro-metrological approach. i) For catchment up to Khab Gauging site (Sub-Catchment, C1), Flood Frequency approach was used. Around 90% of the catchment area (46300 sqkm) up to Khab is snow-fed which lies above 4200m. In view of the predominant area being snow-fed area, 1 in 10000 years return period flood estimated using Flood Frequency analysis at Khab was considered as Probable Maximum Flood (PMF). The flood peaks were taken from daily observed discharges at Khab, which were increased by 10% to make them instantaneous. Design Flood of 4184 cumec thus obtained was considered as PMF at Khab. ii) For catchment between Khab and Sunni Dam (Sub-Catchment, C2), Hydro-metrological approach was used. This method is based upon the catchment response to the rainfall pattern observed (Probable Maximum Precipitation - PMP) in a particular catchment area. The design flood computation mainly involves the estimation of a design storm hyetograph and derivation of the catchment response function. A unit hydrograph is assumed to represent the response of the entire catchment area to a unit rainfall. The main advantage of the hydro-metrological approach is that it gives a complete flood hydrograph which allows us to make a realistic determination of its moderation effect while passing through a reservoir or a river reach. These studies were carried out to derive PMF for the catchment area between Khab and Sunni Dam site using a 1-day and 2-day PMP values of 232 and 416 cm respectively. The PMF so obtained was 12920.60 cumec. Final Result: As the Catchment area up to Sunni Dam has been divided into 2 sub-catchments, the Flood Hydrograph for the Catchment C1 has been routed through the connecting channel reach (River Satluj) using Muskingum method and accordingly, the Design Flood was computed after adding the routed flood ordinates with flood ordinates of catchment C2. The total Design Flood (i.e. 2-Day PMF) with a peak of 15473 cumec was obtained. Conclusion: Even though, several factors are relevant while deciding the method to be used for design flood estimation, data availability and the purpose of study are the most important factors. Since, generally, we cannot wait for the hydrological data of adequate quality and quantity to be available, flood estimation has to be done using whatever data is available. Depending upon the type of data available for a particular catchment, the method to be used is to be selected.

Keywords: design flood, design storm, flood frequency, PMF, PMP, unit hydrograph

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1106 Fuzzy Availability Analysis of a Battery Production System

Authors: Merve Uzuner Sahin, Kumru D. Atalay, Berna Dengiz

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In today’s competitive market, there are many alternative products that can be used in similar manner and purpose. Therefore, the utility of the product is an important issue for the preferability of the brand. This utility could be measured in terms of its functionality, durability, reliability. These all are affected by the system capabilities. Reliability is an important system design criteria for the manufacturers to be able to have high availability. Availability is the probability that a system (or a component) is operating properly to its function at a specific point in time or a specific period of times. System availability provides valuable input to estimate the production rate for the company to realize the production plan. When considering only the corrective maintenance downtime of the system, mean time between failure (MTBF) and mean time to repair (MTTR) are used to obtain system availability. Also, the MTBF and MTTR values are important measures to improve system performance by adopting suitable maintenance strategies for reliability engineers and practitioners working in a system. Failure and repair time probability distributions of each component in the system should be known for the conventional availability analysis. However, generally, companies do not have statistics or quality control departments to store such a large amount of data. Real events or situations are defined deterministically instead of using stochastic data for the complete description of real systems. A fuzzy set is an alternative theory which is used to analyze the uncertainty and vagueness in real systems. The aim of this study is to present a novel approach to compute system availability using representation of MTBF and MTTR in fuzzy numbers. Based on the experience in the system, it is decided to choose 3 different spread of MTBF and MTTR such as 15%, 20% and 25% to obtain lower and upper limits of the fuzzy numbers. To the best of our knowledge, the proposed method is the first application that is used fuzzy MTBF and fuzzy MTTR for fuzzy system availability estimation. This method is easy to apply in any repairable production system by practitioners working in industry. It is provided that the reliability engineers/managers/practitioners could analyze the system performance in a more consistent and logical manner based on fuzzy availability. This paper presents a real case study of a repairable multi-stage production line in lead-acid battery production factory in Turkey. The following is focusing on the considered wet-charging battery process which has a higher production level than the other types of battery. In this system, system components could exist only in two states, working or failed, and it is assumed that when a component in the system fails, it becomes as good as new after repair. Instead of classical methods, using fuzzy set theory and obtaining intervals for these measures would be very useful for system managers, practitioners to analyze system qualifications to find better results for their working conditions. Thus, much more detailed information about system characteristics is obtained.

Keywords: availability analysis, battery production system, fuzzy sets, triangular fuzzy numbers (TFNs)

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1105 Facilitating Social Connections with Neurodivergent Adolescents: An Exploratory Study of Youth Experiences in a Social Group Based on Dungeons and Dragons

Authors: Jonathon Smith, Alba Agostino

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Autism, also referred to as autism spectrum disorder (ASD), is commonly associated with difficulties in social and communication skills. Other characteristics common to autistic individuals include repetitive behaviours, difficulties adhering to routine, as well as paying attention. Recent findings indicate that autism is the fastest-growing neurodevelopmental disorder in North America, yet programming aimed at improving the quality of autistic individual’s real-world social interactions is limited. Although there are social skills programs for autistic youth, participation appears to improve social knowledge, but that knowledge does not improve social competence or transfer to the participant’s daily social interactions. Peers are less likely to interact with autistic people based thin slice judgements, meaning that even when an autistic youth has successfully completed a social skills program, they most likely will still be rejected by peers and not have a social group to participate in. Recently, many researchers are exploring therapeutic interventions using Dungeon and Dragons (D&D) for conditions such as social anxiety, loneliness, and identity exploration. D&D is a table-top role-playing game (TTRPG) based on social play experience where the players must communicate, plan, negotiate, and compromise with other players to achieve a shared goal. The game encourages players to assume the role of their character and act out their play within the rules of the game with the guidance of the games dungeon master. The popularity Dungeons and Dragons has increased at a rapid rate, and many suggest that there social-emotional benefits of joining and participating in these types of gaming experiences, however this is an under researched topic and studies examining the benefits of such games is lacking in the field. The main purpose of this exploratory study is to examine the autistic youth’s experiences of participating in a D&D club. Participants of this study were four high functioning autistic youth between the ages of 14-18 (average age – 16) enrolled in a D&D Club that was specifically designed for neurodiverse youth. The youth participation with the club ranged from 4 months to 8 months. All participants completed a 30–40-minute semi-structured interview where they were able to express their perceptions as participants of the D&D club. Preliminary findings suggest that the game provided a place for the youth to engage in authentic social interactions. Additionally, preliminary results suggest that the youth report being in a positive space with other neurodivergent youth created an atmosphere where they felt confident and could connect with others. The findings from this study will aid clinicians, researchers, and educators in developing programming aimed at improving social interactions and connections for autistic youth.

Keywords: autism, social connection, dungeons and dragons, neurodivergent affirming space

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1104 Unifying RSV Evolutionary Dynamics and Epidemiology Through Phylodynamic Analyses

Authors: Lydia Tan, Philippe Lemey, Lieselot Houspie, Marco Viveen, Darren Martin, Frank Coenjaerts

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Introduction: Human respiratory syncytial virus (hRSV) is the leading cause of severe respiratory tract infections in infants under the age of two. Genomic substitutions and related evolutionary dynamics of hRSV are of great influence on virus transmission behavior. The evolutionary patterns formed are due to a precarious interplay between the host immune response and RSV, thereby selecting the most viable and less immunogenic strains. Studying genomic profiles can teach us which genes and consequent proteins play an important role in RSV survival and transmission dynamics. Study design: In this study, genetic diversity and evolutionary rate analysis were conducted on 36 RSV subgroup B whole genome sequences and 37 subgroup A genome sequences. Clinical RSV isolates were obtained from nasopharyngeal aspirates and swabs of children between 2 weeks and 5 years old of age. These strains, collected during epidemic seasons from 2001 to 2011 in the Netherlands and Belgium by either conventional or 454-sequencing. Sequences were analyzed for genetic diversity, recombination events, synonymous/non-synonymous substitution ratios, epistasis, and translational consequences of mutations were mapped to known 3D protein structures. We used Bayesian statistical inference to estimate the rate of RSV genome evolution and the rate of variability across the genome. Results: The A and B profiles were described in detail and compared to each other. Overall, the majority of the whole RSV genome is highly conserved among all strains. The attachment protein G was the most variable protein and its gene had, similar to the non-coding regions in RSV, more elevated (two-fold) substitution rates than other genes. In addition, the G gene has been identified as the major target for diversifying selection. Overall, less gene and protein variability was found within RSV-B compared to RSV-A and most protein variation between the subgroups was found in the F, G, SH and M2-2 proteins. For the F protein mutations and correlated amino acid changes are largely located in the F2 ligand-binding domain. The small hydrophobic phosphoprotein and nucleoprotein are the most conserved proteins. The evolutionary rates were similar in both subgroups (A: 6.47E-04, B: 7.76E-04 substitution/site/yr), but estimates of the time to the most recent common ancestor were much lower for RSV-B (B: 19, A: 46.8 yrs), indicating that there is more turnover in this subgroup. Conclusion: This study provides a detailed description of whole RSV genome mutations, the effect on translation products and the first estimate of the RSV genome evolution tempo. The immunogenic G protein seems to require high substitution rates in order to select less immunogenic strains and other conserved proteins are most likely essential to preserve RSV viability. The resulting G gene variability makes its protein a less interesting target for RSV intervention methods. The more conserved RSV F protein with less antigenic epitope shedding is, therefore, more suitable for developing therapeutic strategies or vaccines.

Keywords: drug target selection, epidemiology, respiratory syncytial virus, RSV

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1103 Starting the Hospitalization Procedure with a Medicine Combination in the Cardiovascular Department of the Imam Reza (AS) Mashhad Hospital

Authors: Maryamsadat Habibi

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Objective: pharmaceutical errors are avoidable occurrences that can result in inappropriate pharmaceutical use, patient harm, treatment failure, increased hospital costs and length of stay, and other outcomes that affect both the individual receiving treatment and the healthcare provider. This study aimed to perform a reconciliation of medications in the cardiovascular ward of Imam Reza Hospital in Mashhad, Iran, and evaluate the prevalence of medication discrepancies between the best medication list created for the patient by the pharmacist and the medication order of the treating physician there. Materials & Methods: The 97 patients in the cardiovascular ward of the Imam Reza Hospital in Mashhad were the subject of a cross-sectional study from June to September of 2021. After giving their informed consent and being admitted to the ward, all patients with at least one underlying condition and at least two medications being taken at home were included in the study. A medical reconciliation form was used to record patient demographics and medical histories during the first 24 hours of admission, and the information was contrasted with the doctors' orders. The doctor then discovered medication inconsistencies between the two lists and double-checked them to separate the intentional from the accidental anomalies. Finally, using SPSS software version 22, it was determined how common medical discrepancies are and how different sorts of discrepancies relate to various variables. Results: The average age of the participants in this study was 57.6915.84 years, with 57.7% of men and 42.3% of women. 95.9% of the patients among these people encountered at least one medication discrepancy, and 58.9% of them suffered at least one unintentional drug cessation. Out of the 659 medications registered in the study, 399 cases (60.54%) had inconsistencies, of which 161 cases (40.35%) involved the intentional stopping of a medication, 123 cases (30.82%) involved the stopping of a medication unintentionally, and 115 cases (28.82%) involved the continued use of a medication by adjusting the dose. Additionally, the category of cardiovascular pharmaceuticals and the category of gastrointestinal medications were found to have the highest medical inconsistencies in the current study. Furthermore, there was no correlation between the frequency of medical discrepancies and the following variables: age, ward, date of visit, type, and number of underlying diseases (P=0.13), P=0.61, P=0.72, P=0.82, P=0.44, and so forth. On the other hand, there was a statistically significant correlation between the number of medications taken at home (P=0.037) and the prevalence of medical discrepancies with gender (P=0.029). The results of this study revealed that 96% of patients admitted to the cardiovascular unit at Imam Reza Hospital had at least one medication error, which was typically an intentional drug discontinuance. According to the study's findings, patients admitted to Imam Reza Hospital's cardiovascular ward have a great potential for identifying and correcting various medication discrepancies as well as for avoiding prescription errors when the medication reconciliation method is used. As a result, it is essential to carry out a precise assessment to achieve the best treatment outcomes and avoid unintended medication discontinuation, unwanted drug-related events, and drug interactions between the patient's home medications and those prescribed in the hospital.

Keywords: drug combination, drug side effects, drug incompatibility, cardiovascular department

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1102 Killing for the Great Peace: An Internal Perspective on the Anti-Manchu Theme in the Taiping Movement

Authors: Zihao He

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The majority of existing studies on the Taiping Movement (1851-1864) viewed their anti-Manchu attitudes as nationalist agendas: Taiping was aimed at revolting against the Manchu government and establishing a new political regime. To explain these aggressive and violent attitudes towards Manchu, these studies mainly found socio-economic factors and stressed the status of “being deprived”. Even the ‘demon-slaying’ narrative of the Taiping to dehumanize the Manchu tends to be viewed as a “religious tool” to achieve their political, nationalist aim. This paper argues that these studies on Taiping’s anti-Manchu attitudes and behaviors are analyzed from an external angle and have two major problems. Firstly, they distinguished “religion” from “nationalist” or “political”, focusing on the “political” nature of the movement. “Religion” and the religious experience within Taiping were largely ignored. This paper argues that there was no separable and independent “religion” in the Taiping Movement, as opposed to secular, nationalist politics. Secondly, these analyses held an external perspective on Taiping’s anti-Manchu agenda. Demonizing and killing Manchu were viewed as purely political actions. On the contrary, this paper focuses on the internal perspective of anti-Manchu narratives in the Taiping Movement. The method of this paper is mainly textual analysis, focusing on the official documents, edicts, and proclamations of the Taiping movement. It views the writing of the Taiping as a coherent narrative and rhetoric, which was attractive and convincing for its followers. In terms of the main findings, firstly, internal and external perspectives on anti-Manchu violence are different. Externally, violence was viewed as a tool and necessary process to achieve the political goal. However, internally speaking, in Taiping’s writing, violence was a result of Godlessness, which would be solved as far as the faith in God is restored in China. Having a framework of universal love among human beings as sons and daughters of the Heavenly Father and killing was forbidden, the Taiping excluded Manchus from the family of human beings and demonized them. “Demon-slaying” was not violence. It was constructed as a necessary process to achieve the Great Peace. Moreover, Taiping’s anti-Manchu violence was not merely “political.” Rather, the category “religion” and its binary opposition, “secular,” is not suitable for Taiping. A key point related to this argument is the revolutionary violence against the Manchu government, which inherited the traditional “Heavenly Mandate” model. From an internal, theological perspective, anti-Manchu was ordained and commanded by the Heavenly Father. Manchu, as a regime, was standing as a hindrance in the path toward God. Besides, Manchu was not only viewed as a regime, but they were also “demons.” Therefore, the paper examines how Manchus were dehumanized in Taiping’s writings and were situated outside of the consideration of nonviolent and love. Manchu as a regime and Manchu as demons are in a dynamic relationship. As a regime, the Manchu government was preventing Chinese people from worshipping the Heavenly Father, so they were demonized. As they were demons, killing Manchus during the revolt was justified and not viewed as being contradicted the universal love among human beings.

Keywords: anti-manchu, demon-slaying, heavenly mandate, religion and violence, the taiping movement.

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1101 Monitoring of Vector Mosquitors of Diseases in Areas of Energy Employment Influence in the Amazon (Amapa State), Brazil

Authors: Ribeiro Tiago Magalhães

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Objective: The objective of this study was to evaluate the influence of a hydroelectric power plant in the state of Amapá, and to present the results obtained by dimensioning the diversity of the main mosquito vectors involved in the transmission of pathogens that cause diseases such as malaria, dengue and leishmaniasis. Methodology: The present study was conducted on the banks of the Araguari River, in the municipalities of Porto Grande and Ferreira Gomes in the southern region of Amapá State. Nine monitoring campaigns were conducted, the first in April 2014 and the last in March 2016. The selection of the catch sites was done in order to prioritize areas with possible occurrence of the species considered of greater importance for public health and areas of contact between the wild environment and humans. Sampling efforts aimed to identify the local vector fauna and to relate it to the transmission of diseases. In this way, three phases of collection were established, covering the schedules of greater hematophageal activity. Sampling was carried out using Shannon Shack and CDC types of light traps and by means of specimen collection with the hold method. This procedure was carried out during the morning (between 08:00 and 11:00), afternoon-twilight (between 15:30 and 18:30) and night (between 18:30 and 22:00). In the specific methodology of capture with the use of the CDC equipment, the delimited times were from 18:00 until 06:00 the following day. Results: A total of 32 species of mosquitoes was identified, and a total of 2,962 specimens was taxonomically subdivided into three genera (Culicidae, Psychodidae and Simuliidae) Psorophora, Sabethes, Simulium, Uranotaenia and Wyeomyia), besides those represented by the family Psychodidae that due to the morphological complexities, allows the safe identification (without the method of diaphanization and assembly of slides for microscopy), only at the taxonomic level of subfamily (Phlebotominae). Conclusion: The nine monitoring campaigns carried out provided the basis for the design of the possible epidemiological structure in the areas of influence of the Cachoeira Caldeirão HPP, in order to point out among the points established for sampling, which would represent greater possibilities, according to the group of identified mosquitoes, of disease acquisition. However, what should be mainly considered, are the future events arising from reservoir filling. This argument is based on the fact that the reproductive success of Culicidae is intrinsically related to the aquatic environment for the development of its larvae until adulthood. From the moment that the water mirror is expanded in new environments for the formation of the reservoir, a modification in the process of development and hatching of the eggs deposited in the substrate can occur, causing a sudden explosion in the abundance of some genera, in special Anopheles, which holds preferences for denser forest environments, close to the water portions.

Keywords: Amazon, hydroelectric, power, plants

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1100 Patterns of Libido, Sexual Activity and Sexual Performance in Female Migraineurs

Authors: John Farr Rothrock

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Although migraine traditionally has been assumed to convey a relative decrease in libido, sexual activity and sexual performance, recent data have suggested that the female migraine population is far from homogenous in this regard. We sought to determine the levels of libido, sexual activity and sexual performance in the female migraine patient population both generally and according to clinical phenotype. In this single-blind study, a consecutive series of sexually active new female patients ages 25-55 initially presenting to a university-based headache clinic and having a >1 year history of migraine were asked to complete anonymously a survey assessing their sexual histories generally and as they related to their headache disorder and the 19-item Female Sexual Function Index (FSFI). To serve as 2 separate control groups, 100 sexually active females with no history of migraine and 100 female migraineurs from the general (non-clinic) population but matched for age, marital status, educational background and socioeconomic status completed a similar survey. Over a period of 3 months, 188 consecutive migraine patients were invited to participate. Twenty declined, and 28 of the remaining 160 potential subjects failed to meet the inclusion criterion utilized for “sexually active” (ie, heterosexual intercourse at a frequency of > once per month in each of the preceding 6 months). In all groups younger age (p<.005), higher educational level attained (p<.05) and higher socioeconomic status (p<.025) correlated with a higher monthly frequency of intercourse and a higher likelihood of intercourse resulting in orgasm. Relative to the 100 control subjects with no history of migraine, the two migraine groups (total n=232) reported a lower monthly frequency of intercourse and recorded a lower FSFI score (both p<.025), but the contribution to this difference came primarily from the chronic migraine (CM) subgroup (n=92). Patients with low frequency episodic migraine (LFEM) and mid frequency episodic migraine (MFEM) reported a higher FSFI score, higher monthly frequency of intercourse, higher likelihood of intercourse resulting in orgasm and higher likelihood of multiple active sex partners than controls. All migraine subgroups reported a decreased likelihood of engaging in intercourse during an active migraine attack, but relative to the CM subgroup (8/92=9%), a higher proportion of patients in the LFEM (12/49=25%), MFEM (14/67=21%) and high frequency episodic migraine (HFEM: 6/14=43%) subgroups reported utilizing intercourse - and orgasm specifically - as a means of potentially terminating a migraine attack. In the clinic vs no-clinic groups there were no significant differences in the dependent variables assessed. Research subjects with LFEM and MFEM may report a level of libido, frequency of intercourse and likelihood of orgasm-associated intercourse that exceeds what is reported by age-matched controls free of migraine. Many patients with LFEM, MFEM and HFEM appear to utilize intercourse/orgasm as a means to potentially terminate an acute migraine attack.

Keywords: migraine, female, libido, sexual activity, phenotype

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1099 Improvement of the Traditional Techniques of Artistic Casting through the Development of Open Source 3D Printing Technologies Based on Digital Ultraviolet Light Processing

Authors: Drago Diaz Aleman, Jose Luis Saorin Perez, Cecile Meier, Itahisa Perez Conesa, Jorge De La Torre Cantero

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Traditional manufacturing techniques used in artistic contexts compete with highly productive and efficient industrial procedures. The craft techniques and associated business models tend to disappear under the pressure of the appearance of mass-produced products that compete in all niche markets, including those traditionally reserved for the work of art. The surplus value derived from the prestige of the author, the exclusivity of the product or the mastery of the artist, do not seem to be sufficient reasons to preserve this productive model. In the last years, the adoption of open source digital manufacturing technologies in small art workshops can favor their permanence by assuming great advantages such as easy accessibility, low cost, and free modification, adapting to specific needs of each workshop. It is possible to use pieces modeled by computer and made with FDM (Fused Deposition Modeling) 3D printers that use PLA (polylactic acid) in the procedures of artistic casting. Models printed by PLA are limited to approximate minimum sizes of 3 cm, and optimal layer height resolution is 0.1 mm. Due to these limitations, it is not the most suitable technology for artistic casting processes of smaller pieces. An alternative to solve size limitation, are printers from the type (SLS) "selective sintering by laser". And other possibility is a laser hardens, by layers, metal powder and called DMLS (Direct Metal Laser Sintering). However, due to its high cost, it is a technology that is difficult to introduce in small artistic foundries. The low-cost DLP (Digital Light Processing) type printers can offer high resolutions for a reasonable cost (around 0.02 mm on the Z axis and 0.04 mm on the X and Y axes), and can print models with castable resins that allow the subsequent direct artistic casting in precious metals or their adaptation to processes such as electroforming. In this work, the design of a DLP 3D printer is detailed, using backlit LCD screens with ultraviolet light. Its development is totally "open source" and is proposed as a kit made up of electronic components, based on Arduino and easy to access mechanical components in the market. The CAD files of its components can be manufactured in low-cost FDM 3D printers. The result is less than 500 Euros, high resolution and open-design with free access that allows not only its manufacture but also its improvement. In future works, we intend to carry out different comparative analyzes, which allow us to accurately estimate the print quality, as well as the real cost of the artistic works made with it.

Keywords: traditional artistic techniques, DLP 3D printer, artistic casting, electroforming

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1098 Implications of Internationalization for Management and Practice in Higher Education

Authors: Naziema Begum Jappie

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The internationalization of higher education has become a focal point for academic institutions worldwide, including those in South Africa. This paper explores the multifaceted implications of internationalization on management and practice within the South African higher education landscape. Universities all over the world are increasingly recognizing the challenges of globalization and the pressures towards internationalization. Internationalization in higher education encompasses a range of activities, including academic exchange programs, research collaborations, joint degree programs, and the recruitment of international students and faculty. In South Africa, this process is driven by various factors, including the quest for global competitiveness, the pursuit of academic excellence, and the promotion of cultural diversity. However, while internationalization presents numerous opportunities, it also brings forth significant challenges that require careful consideration by management and practitioners in higher education institutions. Furthermore, the internationalization of higher education in South Africa has significant implications for teaching and learning practices. With an increasingly diverse student body, educators must employ innovative pedagogical approaches that cater to the needs and preferences of a multicultural cohort. This may involve the integration of global perspectives into the curriculum, the use of technology-enhanced learning platforms, and the promotion of intercultural competence among students and faculty. Additionally, the exchange of knowledge and ideas with international partners can enrich research activities and contribute to the advancement of knowledge in various fields. The internationalization of higher education in South Africa has profound implications for management and practice within academic institutions. While it offers opportunities for enhancing academic quality, promoting cultural exchange, and advancing research agendas, it also presents challenges that require strategic planning, resource allocation, and stakeholder engagement. By addressing these challenges proactively and leveraging the opportunities presented by internationalization, South African universities can position themselves as global leaders in higher education while contributing to the socio-economic development of the country and the continent at large. This paper draws together the international experience in South Africa to explore the emerging patterns of strategy and practice in internationalizing Higher Education and will highlight some critical notions of how the concepts of internationalization and globalization in the context of higher education are understood by those who lead universities and what new challenges are being created as universities seek to become more international. Institutions cannot simply have bullet points in the strategic plan for the recruitment of international students; there has to be a complete commitment to a national strategy of inclusivity. This paper will further examine the leadership styles that ensure transformation together with the goals set out for internationalization. Discussions around adding the international relations dimension to the curriculum. Addressing the issues relevant to cross-border delivery of higher education.

Keywords: challenges, higher education, internationalization, strategic focus

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1097 Privacy Rights of Children in the Social Media Sphere: The Benefits and Challenges Under the EU and US Legislative Framework

Authors: Anna Citterbergova

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This study explores the safeguards and guarantees to children’s personal data protection under the current EU and US legislative framework, namely the GDPR (2018) and COPPA (2000). Considering that children are online for the majority of their free time, one cannot overlook the negative side effects that may be associated with online participation, which may put children’s wellbeing and their fundamental rights at risk. The question of whether the current relevant legislative framework in relation to the responsibilities of the internet service providers (ISPs) are adequate safeguards and guarantees to children’s personal data protection has been an evolving debate both in the US and in the EU. From a children’s rights perspective, processors of personal data have certain obligations that must meet the international human rights principles (e. g. the CRC, ECHR), which require taking into account the best interest of the child. Accordingly, the need to protect children’s privacy online remains strong and relevant with the expansion of the number and importance of social media platforms to human life. At the same time, the landscape of the internet is rapidly evolving, and commercial interests are taking a more targeted approach in seeking children’s data. Therefore, it is essential to constantly evaluate the ongoing and evolving newly adopted market policies of ISPs that may misuse the gap in the current letter of the law. Previous studies in the field have already pointed out that both GDPR and COPPA may theoretically not be sufficient in protecting children’s personal data. With the focus on social media platforms, this study uses the doctrinal-descriptive method to identifiy the mechanisms enshrined in the GDPR and COPPA designed to protect children’s personal data. In its second part, the study includes a data gathering phase by the national data protection authorities responsible for monitoring and supervision of the GDPR in relation to children’s personal data protection who monitor the enforcement of the data protection rules throughout the European Union an contribute to their consistent application. These gathered primary source of data will later be used to outline the series of benefits and challenges to children’s persona lata protection faced by these institutes and the analysis that aims to suggest if and/or how to hold ISPs accountable while striking a fair balance between the commercial rights and the right to protection of the personal data of children. The preliminary results can be divided into two categories. First, conclusions in the doctrinal-descriptive part of the study. Second, specific cases and situations from the practice of national data protection authorities. While for the first part, concrete conclusions can already be presented, the second part is currently still in the data gathering phase. The result of this research is a comprehensive analysis on the safeguards and guarantees to children’s personal data protection under the current EU and US legislative framework, based on doctrinal-descriptive approach and original empirical data.

Keywords: personal data of children, personal data protection, GDPR, COPPA, ISPs, social media

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1096 Robotics Education Continuity from Diaper Age to Doctorate

Authors: Vesa Salminen, Esa Santakallio, Heikki Ruohomaa

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Introduction: The city of Riihimäki has decided robotics on well-being, service and industry as the main focus area on their ecosystem strategy. Robotics is going to be an important part of the everyday life of citizens and present in the working day of the average citizen and employee in the future. For that reason, also education system and education programs on all levels of education from diaper age to doctorate have been directed to fulfill this ecosystem strategy. Goal: The objective of this activity has been to develop education continuity from diaper age to doctorate. The main target of the development activity is to create a unique robotics study entity that enables ongoing robotics studies from preprimary education to university. The aim is also to attract students internationally and supply a skilled workforce to the private sector, capable of the challenges of the future. Methodology: Education instances (high school, second grade, Universities on all levels) in a large area of Tavastia Province have gradually directed their education programs to support this goal. On the other hand, applied research projects have been created to make proof of concept- phases on areal real environment field labs to test technology opportunities and digitalization to change business processes by applying robotic solutions. Customer-oriented applied research projects offer for students in robotics education learning environments to learn new knowledge and content. That is also a learning environment for education programs to adapt and co-evolution. New content and problem-based learning are used in future education modules. Major findings: Joint robotics education entity is being developed in cooperation with the city of Riihimäki (primary education), Syria Education (secondary education) and HAMK (bachelor and master education). The education modules have been developed to enable smooth transitioning from one institute to another. This article is introduced a case study of the change of education of wellbeing education because of digitalization and robotics. Riihimäki's Elderly citizen's service house, Riihikoti, has been working as a field lab for proof-of-concept phases on testing technology opportunities. According to successful case studies also education programs on various levels of education have been changing. Riihikoti has been developed as a physical learning environment for home care and robotics, investigating and developing a variety of digital devices and service opportunities and experimenting and learn the use of equipment. The environment enables the co-development of digital service capabilities in the authentic environment for all interested groups in transdisciplinary cooperation.

Keywords: ecosystem strategy, digitalization and robotics, education continuity, learning environment, transdisciplinary co-operation

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1095 Numerical Investigation of Combustion Chamber Geometry on Combustion Performance and Pollutant Emissions in an Ammonia-Diesel Common Rail Dual-Fuel Engine

Authors: Youcef Sehili, Khaled Loubar, Lyes Tarabet, Mahfoudh Cerdoun, Clement Lacroix

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As emissions regulations grow more stringent and traditional fuel sources become increasingly scarce, incorporating carbon-free fuels in the transportation sector emerges as a key strategy for mitigating the impact of greenhouse gas emissions. While the utilization of hydrogen (H2) presents significant technological challenges, as evident in the engine limitation known as knocking, ammonia (NH3) provides a viable alternative that overcomes this obstacle and offers convenient transportation, storage, and distribution. Moreover, the implementation of a dual-fuel engine using ammonia as the primary gas is promising, delivering both ecological and economic benefits. However, when employing this combustion mode, the substitution of ammonia at high rates adversely affects combustion performance and leads to elevated emissions of unburnt NH3, especially under high loads, which requires special treatment of this mode of combustion. This study aims to simulate combustion in a common rail direct injection (CRDI) dual-fuel engine, considering the fundamental geometry of the combustion chamber as well as fifteen (15) alternative proposed geometries to determine the configuration that exhibits superior engine performance during high-load conditions. The research presented here focuses on improving the understanding of the equations and mechanisms involved in the combustion of finely atomized jets of liquid fuel and on mastering the CONVERGETM code, which facilitates the simulation of this combustion process. By analyzing the effect of piston bowl shape on the performance and emissions of a diesel engine operating in dual fuel mode, this work combines knowledge of combustion phenomena with proficiency in the calculation code. To select the optimal geometry, an evaluation of the Swirl, Tumble, and Squish flow patterns was conducted for the fifteen (15) studied geometries. Variations in-cylinder pressure, heat release rate, turbulence kinetic energy, turbulence dissipation rate, and emission rates were observed, while thermal efficiency and specific fuel consumption were estimated as functions of crankshaft angle. To maximize thermal efficiency, a synergistic approach involving the enrichment of intake air with oxygen (O2) and the enrichment of primary fuel with hydrogen (H2) was implemented. Based on the results obtained, it is worth noting that the proposed geometry (T8_b8_d0.6/SW_8.0) outperformed the others in terms of flow quality, reduction of pollutants emitted with a reduction of more than 90% in unburnt NH3, and an impressive improvement in engine efficiency of more than 11%.

Keywords: ammonia, hydrogen, combustion, dual-fuel engine, emissions

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1094 Impact of Displacements Durations and Monetary Costs on the Labour Market within a City Consisting on Four Areas a Theoretical Approach

Authors: Aboulkacem El Mehdi

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We develop a theoretical model at the crossroads of labour and urban economics, used for explaining the mechanism through which the duration of home-workplace trips and their monetary costs impact the labour demand and supply in a spatially scattered labour market and how they are impacted by a change in passenger transport infrastructures and services. The spatial disconnection between home and job opportunities is referred to as the spatial mismatch hypothesis (SMH). Its harmful impact on employment has been subject to numerous theoretical propositions. However, all the theoretical models proposed so far are patterned around the American context, which is particular as it is marked by racial discrimination against blacks in the housing and the labour markets. Therefore, it is only natural that most of these models are developed in order to reproduce a steady state characterized by agents carrying out their economic activities in a mono-centric city in which most unskilled jobs being created in the suburbs, far from the Blacks who dwell in the city-centre, generating a high unemployment rates for blacks, while the White population resides in the suburbs and has a low unemployment rate. Our model doesn't rely on any racial discrimination and doesn't aim at reproducing a steady state in which these stylized facts are replicated; it takes the main principle of the SMH -the spatial disconnection between homes and workplaces- as a starting point. One of the innovative aspects of the model consists in dealing with a SMH related issue at an aggregate level. We link the parameters of the passengers transport system to employment in the whole area of a city. We consider here a city that consists of four areas: two of them are residential areas with unemployed workers, the other two host firms looking for labour force. The workers compare the indirect utility of working in each area with the utility of unemployment and choose between submitting an application for the job that generate the highest indirect utility or not submitting. This arbitration takes account of the monetary and the time expenditures generated by the trips between the residency areas and the working areas. Each of these expenditures is clearly and explicitly formulated so that the impact of each of them can be studied separately than the impact of the other. The first findings show that the unemployed workers living in an area benefiting from good transport infrastructures and services have a better chance to prefer activity to unemployment and are more likely to supply a higher 'quantity' of labour than those who live in an area where the transport infrastructures and services are poorer. We also show that the firms located in the most accessible area receive much more applications and are more likely to hire the workers who provide the highest quantity of labour than the firms located in the less accessible area. Currently, we are working on the matching process between firms and job seekers and on how the equilibrium between the labour demand and supply occurs.

Keywords: labour market, passenger transport infrastructure, spatial mismatch hypothesis, urban economics

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1093 Regularizing Software for Aerosol Particles

Authors: Christine Böckmann, Julia Rosemann

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We present an inversion algorithm that is used in the European Aerosol Lidar Network for the inversion of data collected with multi-wavelength Raman lidar. These instruments measure backscatter coefficients at 355, 532, and 1064 nm, and extinction coefficients at 355 and 532 nm. The algorithm is based on manually controlled inversion of optical data which allows for detailed sensitivity studies and thus provides us with comparably high quality of the derived data products. The algorithm allows us to derive particle effective radius, volume, surface-area concentration with comparably high confidence. The retrieval of the real and imaginary parts of the complex refractive index still is a challenge in view of the accuracy required for these parameters in climate change studies in which light-absorption needs to be known with high accuracy. Single-scattering albedo (SSA) can be computed from the retrieve microphysical parameters and allows us to categorize aerosols into high and low absorbing aerosols. From mathematical point of view the algorithm is based on the concept of using truncated singular value decomposition as regularization method. This method was adapted to work for the retrieval of the particle size distribution function (PSD) and is called hybrid regularization technique since it is using a triple of regularization parameters. The inversion of an ill-posed problem, such as the retrieval of the PSD, is always a challenging task because very small measurement errors will be amplified most often hugely during the solution process unless an appropriate regularization method is used. Even using a regularization method is difficult since appropriate regularization parameters have to be determined. Therefore, in a next stage of our work we decided to use two regularization techniques in parallel for comparison purpose. The second method is an iterative regularization method based on Pade iteration. Here, the number of iteration steps serves as the regularization parameter. We successfully developed a semi-automated software for spherical particles which is able to run even on a parallel processor machine. From a mathematical point of view, it is also very important (as selection criteria for an appropriate regularization method) to investigate the degree of ill-posedness of the problem which we found is a moderate ill-posedness. We computed the optical data from mono-modal logarithmic PSD and investigated particles of spherical shape in our simulations. We considered particle radii as large as 6 nm which does not only cover the size range of particles in the fine-mode fraction of naturally occurring PSD but also covers a part of the coarse-mode fraction of PSD. We considered errors of 15% in the simulation studies. For the SSA, 100% of all cases achieve relative errors below 12%. In more detail, 87% of all cases for 355 nm and 88% of all cases for 532 nm are well below 6%. With respect to the absolute error for non- and weak-absorbing particles with real parts 1.5 and 1.6 in all modes the accuracy limit +/- 0.03 is achieved. In sum, 70% of all cases stay below +/-0.03 which is sufficient for climate change studies.

Keywords: aerosol particles, inverse problem, microphysical particle properties, regularization

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1092 Inhibition of the Activity of Polyphenol Oxidase Enzyme Present in Annona muricata and Musa acuminata by the Experimentally Identified Natural Anti-Browning Agents

Authors: Michelle Belinda S. Weerawardana, Gobika Thiripuranathar, Priyani A. Paranagama

Abstract:

Most of fresh vegetables and fruits available in the retail markets undergo a physiological disorder in its appearance and coloration, which indeed discourages consumer purchase. A loss of millions of dollars yearly to the food industry had been due to this pronounced color reaction called Enzymatic Browning which is driven due to the catalytic activity by an oxidoreductase enzyme, polyphenol oxidase (PPO). The enzyme oxidizes the phenolic compounds which are abundantly available in fruits and vegetables as substrates into quinones, which could react with proteins in its surrounding to generate black pigments, called melanins, which are highly UV-active compounds. Annona muricata (Katu anoda) and Musa acuminata (Ash plantains) is a fruit and a vegetable consumed by Sri Lankans widely due to their high nutritional values, medicinal properties and economical importance. The objective of the present study was to evaluate and determine the effective natural anti-browning inhibitors that could prevent PPO activity in the selected fruit and vegetable. Enzyme extracts from Annona muricata (Katu anoda) and Musa acuminata (Ash plantains), were prepared by homogenizing with analytical grade acetone, and pH of each enzyme extract was maintained at 7.0 using a phosphate buffer. The extracts of inhibitors were prepared using powdered ginger rhizomes and essential oil from the bark of Cinnamomum zeylanicum. Water extracts of ginger were prepared and the essential oil from Ceylon cinnamon bark was extracted using steam distillation method. Since the essential oil is not soluble in water, 0.1µl of cinnamon bark oil was mixed with 0.1µl of Triton X-100 emulsifier and 5.00 ml of water. The effect of each inhibitor on the PPO activity was investigated using catechol (0.1 mol dm-3) as the substrate and two samples of enzyme extracts prepared. The dosages of the prepared Cinnamon bark oil, and ginger (2 samples) which were used to measure the activity were 0.0035 g/ml, 0.091 g/ml and 0.087 g/ml respectively. The measurements of the inhibitory activity were obtained at a wavelength of 525 nm using the UV-visible spectrophotometer. The results evaluated thus revealed that % inhibition observed with cinnamon bark oil, and ginger for Annona muricata was 51.97%, and 60.90% respectively. The effects of cinnamon bark oil, and ginger extract on PPO activity of Musa acuminata were 49.51%, and 48.10%. The experimental findings thus revealed that Cinnamomum zeylanicum bark oil was a more effective inhibitor for PPO enzyme present in Musa acuminata and ginger was effective for PPO enzyme present in Annona muricata. Overall both the inhibitors were proven to be more effective towards the activities of PPO enzyme present in both samples. These inhibitors can thus be corroborated as effective, natural, non-toxic, anti-browning extracts, which when added to the above fruit and vegetable will increase the shelf life and also the acceptance of the product by the consumers.

Keywords: anti-browning agent, enzymatic browning, inhibitory activity, polyphenol oxidase

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1091 “Uninformed” Religious Orientation Can Lead to Violence in Any Given Community: The Case of African Independence Churches in South Africa

Authors: Ngwako Daniel Sebola

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Introductory Statement: Religions are necessary as they offer and teach something to their adherence. People in one religion may not have a complete understanding of the Supreme Being (Deity) in a certain religion other than their own. South Africa, like other countries in the world, consists of various religions, including Christianity. Almost 80% of South African population adheres to the Christian faith, though in different denominations and sects. Each church fulfils spiritual needs that perhaps others cannot fill. African Independent Churches is one of the denominations in the country. These churches arose as a protest to the Western forms and expressions of Christianity. Their major concern was to develop an indigenous expression of Christianity. The relevance of African Independent Churches includes addressing the needs of the people holistically. Controlling diseases was an important aspect of change in different historical periods. Through healing services, leaders of African churches are able to attract many followers. The healing power associated with the founders of many African Initiated Churches leads to people following and respecting them as true leaders within many African communities. Despite its strong points, African Independent Churches, like many others, face a variety of challenges, especially conflicts. Ironically, destructive conflicts resulted in violence.. Such violence demonstrates a lack of informed religious orientation among those concerned. This paper investigates and analyses the causes of conflict and violence in the African Independent Church. The researcher used the Shembe and International Pentecostal Holiness Churches, in South Africa, as a point of departure. As a solution to curb violence, the researcher suggests useful strategies in handling conflicts. Methodology: Comparative and qualitative approaches have been used as methods of collecting data in this research. The intention is to analyse the similarities and differences of violence among members of the Shembe and International Pentecostal Holiness Churches. Equally important, the researcher aims to obtain data through interviews, questionnaires, focus groups, among others. The researcher aims to interview fifteen individuals from both churches. Finding: Leadership squabbles and power struggle appear to be the main contributing factors of violence in many Independent Churches. Ironically, violence resulted in the loss of life and destruction of properties, like in the case of the Shembe and International Pentecostal Holiness Churches. Violence is an indication that congregations and some leaders have not been properly equipped to deal with conflict. Concluding Statement: Conflict is a common part of every human existence in any given community. The concern is when such conflict becomes contagious; it leads to violence. There is a need to understand consciously and objectively towards devising the appropriate measures to handle the conflict. Conflict management calls for emotional maturity, self-control, empathy, patience, tolerance and informed religious orientation.

Keywords: African, church, religion, violence

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1090 Recycling the Lanthanides from Permanent Magnets by Electrochemistry in Ionic Liquid

Authors: Celine Bonnaud, Isabelle Billard, Nicolas Papaiconomou, Eric Chainet

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Thanks to their high magnetization and low mass, permanent magnets (NdFeB and SmCo) have quickly became essential for new energies (wind turbines, electrical vehicles…). They contain large quantities of neodymium, samarium and dysprosium, that have been recently classified as critical elements and that therefore need to be recycled. Electrochemical processes including electrodissolution followed by electrodeposition are an elegant and environmentally friendly solution for the recycling of such lanthanides contained in permanent magnets. However, electrochemistry of the lanthanides is a real challenge as their standard potentials are highly negative (around -2.5V vs ENH). Consequently, non-aqueous solvents are required. Ionic liquids (IL) are novel electrolytes exhibiting physico-chemical properties that fulfill many requirements of the sustainable chemistry principles, such as extremely low volatility and non-flammability. Furthermore, their chemical and electrochemical properties (solvation of metallic ions, large electrochemical windows, etc.) render them very attractive media to implement alternative and sustainable processes in view of integrated processes. All experiments that will be presented were carried out using butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. Linear sweep, cyclic voltammetry and potentiostatic electrochemical techniques were used. The reliability of electrochemical experiments, performed without glove box, for the classic three electrodes cell used in this study has been assessed. Deposits were obtained by chronoamperometry and were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The IL cathodic behavior under different constraints (argon, nitrogen, oxygen atmosphere or water content) and using several electrode materials (Pt, Au, GC) shows that with argon gas flow and gold as a working electrode, the cathodic potential can reach the maximum value of -3V vs Fc+/Fc; thus allowing a possible reduction of lanthanides. On a gold working electrode, the reduction potential of samarium and neodymium was found to be -1.8V vs Fc+/Fc while that of dysprosium was -2.1V vs Fc+/Fc. The individual deposits obtained were found to be porous and presented some significant amounts of C, N, F, S and O atoms. Selective deposition of neodymium in presence of dysprosium was also studied and will be discussed. Next, metallic Sm, Nd and Dy electrodes were used in replacement of Au, which induced changes in the reduction potential values and the deposit structures of lanthanides. The individual corrosion potentials were also measured in order to determine the parameters influencing the electrodissolution of these metals. Finally, a full recycling process was investigated. Electrodissolution of a real permanent magnet sample was monitored kinetically. Then, the sequential electrodeposition of all lanthanides contained in the IL was investigated. Yields, quality of the deposits and consumption of chemicals will be discussed in depth, in view of the industrial feasibility of this process for real permanent magnets recycling.

Keywords: electrodeposition, electrodissolution, ionic liquids, lanthanides, rcycling

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1089 Theoretical Study on the Visible-Light-Induced Radical Coupling Reactions Mediated by Charge Transfer Complex

Authors: Lishuang Ma

Abstract:

Charge transfer (CT) complex, also known as Electron donor-acceptor (EDA) complex, has received attentions increasingly in the field of synthetic chemistry community, due to the CT complex can absorb the visible light through the intermolecular charge transfer excited states, various of catalyst-free photochemical transformations under mild visible-light conditions. However, a number of fundamental questions are still ambiguous, such as the origin of visible light absorption, the photochemical and photophysical properties of the CT complex, as well as the detailed mechanism of the radical coupling pathways mediated by CT complex. Since these are critical factors for target-specific design and synthesis of more new-type CT complexes. To this end, theoretical investigations were performed in our group to answer these questions based on multiconfigurational perturbation theory. The photo-induced fluoroalkylation reactions are mediated by CT complexes, which are formed by the association of an acceptor of perfluoroalkyl halides RF−X (X = Br, I) and a suitable donor molecule such as β-naphtholate anion, were chosen as a paradigm example in this work. First, spectrum simulations were carried out by both CASPT2//CASSCF/PCM and TD-DFT/PCM methods. The computational results showed that the broadening spectra in visible light range (360-550nm) of the CT complexes originate from the 1(σπ*) excitation, accompanied by an intermolecular electron transfer, which was also found closely related to the aggregate states of the donor and acceptor. Moreover, from charge translocation analysis, the CT complex that showed larger charge transfer in the round state would exhibit smaller charge transfer in excited stated of 1(σπ*), causing blue shift relatively. Then, the excited-state potential energy surface (PES) was calculated at CASPT2//CASSCF(12,10)/ PCM level of theory to explore the photophysical properties of the CT complexes. The photo-induced C-X (X=I, Br) bond cleavage was found to occur in the triplet state, which is accessible through a fast intersystem crossing (ISC) process that is controlled by the strong spin-orbit coupling resulting from the heavy iodine and bromine atoms. Importantly, this rapid fragmentation process can compete and suppress the backward electron transfer (BET) event, facilitating the subsequent effective photochemical transformations. Finally, the reaction pathways of the radical coupling were also inspected, which showed that the radical chain propagation pathway could easy to accomplish with a small energy barrier no more than 3.0 kcal/mol, which is the key factor that promote the efficiency of the photochemical reactions induced by CT complexes. In conclusion, theoretical investigations were performed to explore the photophysical and photochemical properties of the CT complexes, as well as the mechanism of radical coupling reactions mediated by CT complex. The computational results and findings in this work can provide some critical insights into mechanism-based design for more new-type EDA complexes

Keywords: charge transfer complex, electron transfer, multiconfigurational perturbation theory, radical coupling

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