Search results for: input state stability (ISS)

Authors: R. M. Kashim

Abstract:

The study investigated primary school teachers’ conceptual and procedural knowledge of rational numbers and its effects on pupil’s achievement in rational numbers. Specifically, primary school teachers’ level of conceptual knowledge about rational numbers, primary school teachers’ level of procedural knowledge about rational numbers, and the effects of teachers conceptual and procedural knowledge on their pupils understanding of rational numbers in primary schools is investigated. The study was carried out in Bauchi metropolis in the Bauchi state of Nigeria. The design of the study was a multi-stage design. The first stage was a descriptive design. The second stage involves a pre-test, post-test only quasi-experimental design. Two instruments were used for the data collection in the study. These were Conceptual and Procedural knowledge test (CPKT) and Rational number achievement test (RAT), the population of the study comprises of three (3) mathematics teachers’ holders of Nigerian Certificate in Education (NCE) teaching primary six and 210 pupils in their intact classes were used for the study. The data collected were analyzed using mean, standard deviation, analysis of variance, analysis of covariance and t- test. The findings indicated that the pupils taught rational number by a teacher that has high conceptual and procedural knowledge understand and perform better than the pupil taught by a teacher who has low conceptual and procedural knowledge of rational number. It is, therefore, recommended that teachers in primary schools should be encouraged to enrich their conceptual knowledge of rational numbers. Also, the superiority performance of teachers in procedural knowledge in rational number should not become an obstruction of understanding. Teachers Conceptual and procedural knowledge of rational numbers should be balanced so that primary school pupils will have a view of better teaching and learning of rational number in our contemporary schools.

Keywords: conceptual, procedural knowledge, rational number, pupils

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Authors: Tuba Sari

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One of the major transformations caused by the industrial revolution, technological developments and globalization is undoubtedly acceleration of urbanization process. Globalization, in particular, is one of the major factors that trigger this transformation. In this context, as a result of the global metropolitan city system, multifunctional rising structure forms are becoming undeniable fact of the world’s leading metropolises as the manifestation of prestige and power with different life choices, easy accessibility to services related to the era of technology. The scope of research deals with five different urban centers in İstanbul where high-rise housing is increasing dramatically after 2000’s. Therefore, the research regards multi-centered urban residential pattern being created by high-rise housing structures in the city. The methodology of the research is based on two main issue, one of them is related to sampling method of high-rise housing projects in İstanbul, while the other method of the research is based on the model of Semantics. In the framework of research hypothesis, it is aimed to prove that the character of vertical intensive structuring in Istanbul is based on seeking of different forms and images in the expressive quality, considering the production of existing high-rise buildings in residential areas in recent years. In respect to rising discourse of 'World City' in the globalizing world, it is very important to state the place of Istanbul in other developing world metropolises. In the perspective of 'World City' discourse, Istanbul has different projects concerning with globalization, international finance companies, cultural activities, mega projects, etc. In brief, the aim of this research is examining transformation forms of high-rise housing development in Istanbul within the frame of developing world cities, searching and analyzing discourse and image related to these projects.

Keywords: globalization, high-rise, housing, image

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Authors: Muhammad Arsalan

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The efficiency of a financial intermediation system is assessed by its ability to achieve allocative efficiency, asset transformation, and the subsequent economic development. Islamic Banking and Finance (IBF) was conceived to serve as an alternate financial intermediation system adherent to the injunctions of Islam. A critical appraisal of the state of contemporary IBF reveals that it neither fulfills the aspirations of Islamic rhetoric nor is efficient in terms of asset transformation and economic development. This paper is an intuitive pursuit to explore the economic rationale of established principles of IBF, and the reasons of the persistent divergence of IBF being accused of ruses and sophistry. Disentangling the varying viewpoints, the underdevelopment of IBF has been attributed to misinterpretation of Riba, which has been explicated through a narrow fiqhi and legally deterministic approach. It presents a critical account of how incorrect conceptualization of the key injunction on Riba, steered flawed institutionalization of an Islamic Financial intermediation system. It also emphasizes on the wrong interpretation of the ontological and epistemological sources of Islamic Law (primarily Riba), that explains the perennial economic underdevelopment of the Muslim world. Deeming ‘a collaborative and dynamic Ijtihad’ as the elixir, this paper insists on the exigency of redefining Riba, i.e., a definition that incorporates the modern modes of economic cooperation and the contemporary financial intermediation ecosystem. Finally, Riba has been articulated in an agency theoretic framework to eschew expropriation of wealth, and assure protection of property rights, aimed at realizing the twin goals of a) Shari’ah adherence in true spirit, b) financial and economic development of the Muslim world.

Keywords: agency theory, financial intermediation, Islamic banking and finance, ijtihad, economic development, Riba, information asymmetry

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Authors: A. Zecchin, E. Vallicella, I. Alberi, A. Dalle Carbonare, A. Festi, F. Galeone, S. Garzon, R. Raffaelli, P. Pomini, M. Franchi

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Introduction: Severe endometriosis is a multiorgan disease, that involves bowel in 31% of cases. Disabling symptoms and deep infiltration can lead to bowel obstruction: surgical bowel treatment may be needed. In these cases, colorectal segment resection is usually performed by inferior mesenteric artery ligature, as radically as for oncological surgery. This study was made on surgery based on intestinal vascular axis’ preservation. It was assessed postoperative complications risks (mainly rate of dehiscence of intestinal anastomoses), and results were compared with the ones found in literature about classical colorectal resection. Materials and methods: This was a retrospective study based on 62 patients with deep infiltrating endometriosis of the bowel, which undergo segmental resection with intestinal vascular axis preservation, between 2013 and 2016. It was assessed complications related to the intervention both during hospitalization and 30-60 days after resection. Particular attention was paid to the presence of anastomotic dehiscence. 52 patients were finally telephonically interviewed in order to investigate the presence or absence of intestinal constipation. Results and Conclusion: Segmental intestinal resection performed in this study ensured a more conservative vascular approach, with lower rate of anastomotic dehiscence (1.6%) compared to classical literature data (10.0% to 11.4% ). No complications were observed regarding spontaneous recovery of intestinal motility and bladder emptying. Constipation in some patients, even after years of intervention, is not assessable in the absence of a preoperative constipation state assessment.

Keywords: anastomotic dehiscence, deep infiltrating endometriosis, colorectal resection, vascular axis preservation

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Authors: Tom Ryan

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This paper investigates the rural mobility and accessibility challenges of a specific target group - Seniors. The target group is those over 66 years of age who are entitled to use the Public Transport (PT) Free Travel Scheme in rural Ireland. The paper explores at a high level some of the projected rural PT challenges and requirements over the next 10-15 years, noting that statistical predictions show that there will be a significant population demographic shift within the Senior's age profile. Using the PESTEL framework, the literature review explored existing research concerning mobility, accessibility challenges, and the opportunities Seniors face. Twenty-seven qualitative in-depth interviews with stakeholders within the ecosystem were undertaken. The stakeholders included: rural PT customers, Local-Link managers, NTA senior management, a Minister of State, and a European parliament policymaker. Tier 1 interviewee feedback spotlights that the PT network system does not exist for rural patients to access hospital facilities. There was no evidence from the Tier 2 research findings to show that health policymakers and transport planners are working to deliver a national solution to support patients getting access to hospital appointments. Several research interviewees discussed the theme of isolation and the perceived stigma of senior males utilising PT. The findings indicated that MaaS is potentially revolutionary in the PT arena. Finally, this paper suggests several short-, medium- and long-term recommendations based on the research findings. These recommendations are a potential springboard to ensure that rural PT is suitable for future Irish generations.

Keywords: accessibility, active ageing, car dependence, isolation, seniors health issues, behavioural changes, environmental challenges, internet of things, demand responsive, mobility as a service

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Authors: Tamar Lazariashvili

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Introduction: The agro-insurance has great importance for agricultural development in the country. In the article, the insurance market of the Georgian agricultural sector has been studied, the level of interest of farmers with insurance products and the trend of demand for those products are revealed; also, the importance of insurance is substantiated. Methodology: The following research methods are applied in the presented paper: statistical (selection, grouping, observation, trend) and qualitative research (in-depth interview with farmers). They claim that the main reason for aggravation is the low level of trust, less awareness about the conditions of the insurance contract. In order to eradicate distrust towards agro-insurance, it is recommended to increase awareness of insured farmers in terms of an insurance agreement. In the case of disputable issues between insurance companies and the customers (farmers), it is advisable to enact the Mediation Service, which will be able to protect the rights of insured farmers. Main Findings: Insurance companies prefer to deal with large farmers, the number of them is very small in Georgia as the credit market. The government interference in this sector is also a very cautious topic. However, the government can strengthen the awareness of farmers about the characteristics and advantages of the insurance system in order to increase the number of insured and reduce insurance premiums for farmers. Conclusion: Enactment of agro-insurance will increase the interest and confidence of financial institutions in the farming sector, financial resources will be accessible to the farmers that will facilitate the stable development of the sector in the country. The size of the agro-insurance market in the country should be increased, and the new territories should be covered. The State must have an obligation to ensure the risk of farmers and subsidize insurance companies. Based on the analysis of the insurance market, the conclusions on agro-insurance issues and the relevant recommendations are proposed.

Keywords: Agro-insurance, agricultural product, Agro-market, farming

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Authors: Adane Kassa Shikur

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Today’s supply chains (SC) have become vulnerable to unexpected and ever-intensifying disruptions from myriad sources. Consequently, the concept of supply chain resilience (SCRes) has become crucial to complement the conventional risk management paradigm, which has failed to cope with unexpected SC disruptions, resulting in severe consequences affecting SC performances and making business continuity questionable. Advancements in cutting-edge technologies like artificial intelligence (AI) and their potential to enhance SCRes by improving critical antecedents in the different phases have attracted the attention of scholars and practitioners. The research from academia and the practical interest of the industry have yielded significant publications at the nexus of AI and SCRes during the last two decades. However, the applications and examinations have been primarily conducted independently, and the extant literature is dispersed into research streams despite the complex nature of SCRes. To close this research gap, this study conducts a systematic literature review of 106 peer-reviewed articles by curating, synthesizing, and consolidating up-to-date literature and presents the state-of-the-art development from 2010 to 2022. Bayesian networks are the most topical ones among the 13 AI techniques evaluated. Concerning the critical antecedents, visibility is the first ranking to be realized by the techniques. The study revealed that AI techniques support only the first 3 phases of SCRes (readiness, response, and recovery), and readiness is the most popular one, while no evidence has been found for the growth phase. The study proposed an AI-SCRes framework to inform research and practice to approach SCRes holistically. It also provided implications for practice, policy, and theory as well as gaps for impactful future research.

Keywords: ANNs, risk, Bauesian networks, vulnerability, resilience

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Authors: Hanlei Yang

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As a kind of popular culture in modern China, advice book on intimate relationship is turning into an important and controversial site with conflicts among neoliberalism, authoritative socialism, market-oriented principles, the science of successful sex and relationship, cosmopolitan notions of nuclear families, and the revitalization of Confucian conservatism and patriarchy. Accelerated modernization and marketization has contributed to great changes in China’s culture and social relations, which accordingly reconceptualizes and reconstructs family structures and moral ethics, particularly urban middle-class nuclear families. To comprehend the meaning of advice book fad in moral and social order, this research proposes to (i) understand the implication of Ayawawa through discourse analysis and how she mobilizes rhetorical devices and cultural resources to present a persuasive and scientific method of managing intimate relationship, (ii) examine the critical role of neoliberalism, post-feminism, and Confucian patriarchy assumed by Ayawawa in her books, (iii) explore how Ayawawa and her fans engage in establishing a model of intimate relationship and sexual subjectivity ordered by neoliberalism, class identity and authoritative socialism. Finally, this research argues that such new fad of a cultural phenomenon is gradually completed in the process of cooperation and negotiation of the state, commercial institutions, and intellectual elite agents. It helps to further learn about (i) the routine life under the influence of neoliberalism and modern hegemony, (ii) the perplexing relationship between China's indigenous cultural forms, global socio-economic and cultural influences in the late modern era.

Keywords: cultural study, intimate relationship, culture sociology, gender study

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Authors: Rian O. Miranda, Lidia V. de Sa, Julio C. Suita

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The Brazilian Nuclear Energy Commission (CNEN) is the main manufacturer of radiopharmaceuticals in Brazil. The Nuclear Engineering Institute (IEN), located at Rio de Janeiro, is one of its main centers of research and production, attending public and private hospitals in the state. This radiopharmaceutical production is used in diagnostic and therapy procedures and allows one and a half million nuclear medicine procedures annually. Despite this, the country is not self-sufficient to meet national demand, creating the need for importation and consequent dependence on other countries. However, IEN facilities were designed in the 60's, and today its structure is inadequate in relation to the good manufacturing practices established by sanitary regulator (ANVISA) and radiological protection leading to the need for a new project. In order to adapt and increase production in the country, a new plant will be built and integrated to the existing facilities with a new 30 MeV Cyclotron that is actually in project detailing process. Thus, it is proposed to survey current CNEN and ANVISA standards for radiopharmaceutical production facilities, as well as the radiological protection analysis of each area of the plant, following good manufacturing practices recommendations adopted nationally besides licensing exigencies for radioactive facilities. In this way, the main requirements for proper operation, equipment location, building materials, area classification, and maintenance program have been implemented. The access controls, interlocks, segregation zones and pass-through boxes integrated into the project were also analyzed. As a result, IEN will in future have the flexibility to produce all necessary radioisotopes for nuclear medicine application, more efficiently by simultaneously bombarding two targets, allowing the simultaneous production of two different radioisotopes, minimizing radiation exposure and saving operating costs.

Keywords: cyclotron, legislation, norms, production, radiopharmaceuticals

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Authors: Wael Mohamed, Per-Erik Austrell, Ola Dahlblom

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Wind farms repowering is a significant topic nowadays. Wind farms repowering means the complete dismantling of the existing turbine, tower and foundation at an existing site and replacing these units with taller and larger units. Modern wind turbines are designed to withstand approximately for 20~25 years. However, a very long design life of 100 years or more can be expected for high-quality concrete foundations. Based on that there are significant economic and environmental benefits of replacing the out-of-date wind turbine with a new turbine of better power generation capacity and reuse the foundation. The big difference in lifetime shows a potential for new foundation solution to allow wind farms to be updated with taller and larger units in order to increase the energy production. This also means a significant change in the design loads on the foundations. Therefore, the new foundation solution should be able to handle the additional overturning loads. A raft surrounded by an active stabilisation system is proposed in this study. The concept of an active stabilisation system is a novel idea using a movable load to stabilise against the overturning moment. The active stabilisation system consists of a water tank being divided into eight compartments. The system uses the water as a movable load by pumping it into two compartments to stabilise against the overturning moment. The position of the water will rely on the wind direction and a water movement system depending on a number of electric motors and pipes with electric valves is used. One of the advantages of this active foundation solution is that some cost-efficient adjustment could be done to make this foundation able to support larger and taller units. After the end of the first turbine lifetime, an option is presented here to reuse this foundation and make it able to support taller and larger units. This option is considered using extra water volume to fill four compartments instead of two compartments. This extra water volume will increase the stability moment by 41% compared to using water in two compartments. The geotechnical performance of the new foundation solution is investigated using two existing weak soil profiles in Egypt and Sweden. A comparative study of the new solution and a piled raft with long friction piles is performed using finite element simulations. The results show that using a raft surrounded by an active stabilisation system decreases the tilting compared to a piled raft with friction piles. Moreover, it is found that using a raft surrounded by an active stabilisation system decreases the foundation costs compared to a piled raft with friction piles. In term of the environmental impact, it is found that the new foundation has a beneficial impact on the CO2 emissions. It saves roughly from 296.1 tonnes-CO2 to 518.21 tonnes-CO2 from the manufacture of concrete if the new foundation solution is used for another turbine-lifetime.

Keywords: active stabilisation system, CO2 emissions, FE analysis, reusable, weak soils

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Authors: Chukwudi S. Osondu

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Currently, the two most economically viable states in Nigeria, Lagos State and Rivers, are challenging the National Government over the legality of the latter’s continued collection and disbursement of the Value Added Tax (VAT) in their respective states. These states recently enacted laws empowering their respective states agencies to collect and administer the Value Added Tax (VAT) in their states. Before now, it was the Federal Inland Revenue Service (FIRS) that is mandated by the National Government to collect VAT throughout the Federation, and have same administered by the Federal Revenue Mobilization Allocation and Fiscal Commission, another Federal agency. Most states in the South-South and South-West geopolitical zones and a handful of states in the South-East are supportive of the actions taken by Lagos and Rivers states and are ready to follow suit. This action is seen as the beginning of resistance by the states over the continued strangulating over-centralized systems operating in the country. The Nigeria Federation has over the years operated a unitary system with grave consequences for development and possible implosion of the polity. The Quota System, the Federal Character policy, the control of the natural resources, and the security infrastructure by the National Government have been in place for decades with the attendant misgivings by some sections in the Nigeria Project. This paper evaluates the impact of the over-centralization power on the National Government with reference to fiscal policies, security, resource exploitation, infrastructural development, and national cohesion. It concludes that “unitary federalism” scuttles national development, inflames disunity, and stokes dissatisfaction among states in the federation. The paper concludes by suggesting a federation where power is devolved to the states, with the states as the federating units allowed to, each develop at its own pace.

Keywords: peace, conflict, insecurity, corporate existence, sustainable development, peaceful coexistence

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Authors: Gordon James Knowles

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Historically the Chinatown district in Sandwich Islands has been plagued with the traditional vice crimes of illegal drugs, gambling, and prostitution since the early 1800s. However, a new form of psychologically addictive arcade style table gambling machines has become the dominant form of illegal revenue made in Honolulu, Hawaii. This study attempts to document the drive, desire, or will to play and wager with arcade style video gaming and understand the role of illegal game rooms in facilitating pathological gambling addiction. Indicators of police corruption by Chinese organized crime syndicates related to protection rackets, bribery, and pay-offs were revealed. Information fusion from a police science and sociological intelligence perspective indicates insurgent warfare is being waged on the streets of Honolulu by the People’s Republic of China. This state-sponsored communist terrorism in the Hawaiian Islands used “contactless” irregular warfare entailing: (1) the deployment of psychologically addictive gambling machines, (2) the distribution of the physically addictive fentanyl drug as a lethal chemical weapon, and (3) psychological warfare by circulating pro-China anti-American propaganda newspapers targeted at the small island populace.

Keywords: Chinese and Polynesian organized crime, china daily newspaper, electronic arcade style table games, gaming technology addiction, illegal compulsive gambling, and police intelligence

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Authors: Samuel E. Okere, Anthony E. Ataga

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Introduction: The microbial ecology of Pleurotus osteratus and Pleurotus tuber–regium spent mushroom substrate (SMS) were characterized to determine other ways of its utilization. Materials and Methods: The microbiological properties of the spent mushroom substrate were determined using standard methods. This study was carried out at the Microbiology Laboratory University of Port Harcourt, Rivers State, Nigeria. Results: Quantitative microbiological analysis revealed that Pleurotus osteratus spent mushroom substrate (POSMS) contained 7.9x10⁵ and 1.2 x10³ cfu/g of total heterotrophic bacteria and total fungi count respectively while Pleurotus tuber-regium spent mushroom substrate (PTSMS) contained 1.38x10⁶ and 9.0 x10² cfu/g of total heterotrophic bacteria count and total fungi count respectively. The fungi species encountered from Pleurotus tuber-regium spent mushroom substrate (PTSMS) include Aspergillus and Cladosporum species, while Aspergillus and Penicillium species were encountered from Pleurotus osteratus spent mushroom substrate (POSMS). However, the bacteria species encountered from Pleurotus tuber-regium spent mushroom substrate include Bacillus, Acinetobacter, Alcaligenes, Actinobacter, and Pseudomonas species while Bacillus, Actinobacteria, Aeromonas, Lactobacillus and Aerococcus species were encountered from Pleurotus osteratus spent mushroom substrate (POSMS). Conclusion: Therefore based on the findings from this study, it can be concluded that spent mushroom substrate contain microorganisms that can be utilized both in bioremediation of oil-polluted soils as they contain important hydrocarbon utilizing microorganisms such as Penicillium, Aspergillus and Bacillus species and also as sources of plant growth-promoting rhizobacteria (PGPR) such as Pseudomonas and Bacillus species which can induce resistance on plants. However, further studies are recommended, especially to molecularly characterize these microorganisms.

Keywords: characterization, microorganisms, mushroom, spent substrate

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Authors: Janos Juhasz, Sandor Pongor, Balazs Ligeti

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Next-generation sequencing, especially whole genome shotgun sequencing, is becoming a common approach to gain insight into the microbiomes in a culture-independent way, even in clinical practice. It does not only give us information about the species composition of an environmental sample but opens the possibility to detect antimicrobial resistance and novel, or currently unknown, pathogens. Accurately and reliably detecting the microbial strains is a challenging task. Here we present a sensitive approach for detecting pathogens in metagenomics samples with special regard to detecting novel variants of known pathogens. We have developed a pipeline that uses fast, short read aligner programs (i.e., Bowtie2/BWA) and comprehensive nucleotide databases. Taxonomic binning is based on the lowest common ancestor (LCA) principle; each read is assigned to a taxon, covering the most significantly hit taxa. This approach helps in balancing between sensitivity and running time. The program was tested both on experimental and synthetic data. The results implicate that our method performs as good as the state-of-the-art BLAST-based ones, furthermore, in some cases, it even proves to be better, while running two orders magnitude faster. It is sensitive and capable of identifying taxa being present only in small abundance. Moreover, it needs two orders of magnitude less reads to complete the identification than MetaPhLan2 does. We analyzed an experimental anthrax dataset (B. anthracis strain BA104). The majority of the reads (96.50%) was classified as Bacillus anthracis, a small portion, 1.2%, was classified as other species from the Bacillus genus. We demonstrate that the evaluation of high-throughput sequencing data is feasible in a reasonable time with good classification accuracy.

Keywords: metagenomics, taxonomy binning, pathogens, microbiome, B. anthracis

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Authors: Lie-Fen Lin, Tzu-Hsuan Lin, Ching-Heng Lin

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Hospice care for terminally ill patients provides not only a better quality of life but also cost-saving benefits. However, the utilization of home-based hospice care (HBH care) remains low even for countries covered by National Health Insurance (NHI) programs in Taiwan. In the current commercial insurance policy, only hospital-based hospice benefits were covered. It may have an influence on the insureds chosen to receive end-of-life care in a hospitalized manner. Thus, how to propose a feasible method to advocate HBH care utilization rate of public health policies is an important issue. A total of 130,219 cancer decedents in the year 2011-2013 from the National Health Insurance Research Database (NHIRD) in Taiwan were included in this study. By adding a day volume pays benefits of HBH care as a commercial insurance rider, will provide alternative benefits for the insureds. A multiple-state Markov chain model was incorporated to estimate the transition intensities of patients in different states at the end of their lives (Non-hospice, HBH, hospital-based hospice), and the premiums were estimated. HBH care insurance benefits provide financial support and reduce the burden of care for patients. The rate-making of this product is very sensitive while the utilization rate is rising, especially for high ages. The proposed HBH care insurance is a feasible way to reduce the financial burden, enhance the care quality and family satisfaction of insureds. Meanwhile, insurance companies can participate in advocating a good medical policy to enhance the social image. In addition, the medical costs of NHI can reduce effectively.

Keywords: home-based hospice care, commercial insurance, Markov chain model, the day volume pays

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Authors: Rakesh Kumar Soni

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Under free living conditions, human biological clocks show a periodicity of 24 hour for numerous physiological, behavioral and biochemical variables. However, this period is not the original period; rather it merely exhibits synchronization with the solar clock. It is, therefore, most important to investigate characteristics of human circadian clock, essentially in shift workers, who normally confront with contrasting social clocks. Aim of the present study was to investigate rest-activity rhythm and to vouch for the best technique for the computation of periods in this rhythm in subjects randomly selected from different groups of shift workers. The rest-activity rhythm was studied in forty-eight shift workers from three different organizations, namely Newspaper Printing Press (NPP), Chhattisgarh State Electricity Board (CSEB) and Raipur Alloys (RA). Shift workers of NPP (N = 20) were working on a permanent night shift schedule (NS; 20:00-04:00). However, in CSEB (N = 14) and RA (N = 14), shift workers were working in a 3-shift system comprising of rotations from night (NS; 22:00-06:00) to afternoon (AS; 14:00-22:00) and to morning shift (MS; 06:00-14:00). Each subject wore an Actiwatch (AW64, Mini Mitter Co. Inc., USA) for 7 and/or 21 consecutive days, only after furnishing a certificate of consent. One-minute epoch length was chosen for the collection of wrist activity data. Period was determined by using Actiware sleep software (Periodogram), Lomb-Scargle Periodogram (LSP) and Spectral analysis software (Spectre). Other statistical techniques, such as ANOVA and Duncan’s multiple-range test were also used whenever required. A statistically significant circadian rhythm in rest-activity, gauged by cosinor, was documented in all shift workers, irrespective of shift work. Results indicate that the efficiency of the technique to determine the period (τ) depended upon the clipping limits of the τs. It appears that the technique of spectre is more reliable.

Keywords: biological clock, rest activity rhythm, spectre, periodogram

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Authors: Maria Del Mar Maira Vidal, Alvaro Briales

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In this paper, we will conduct an analysis of the results of the I+D+i research project “New types of socio-existential vulnerability, support and care in Spain” (VULSOCU) (2016-20). This project had the objective to analyze the new types of vulnerability that are the result of the combination of several factors as the economic crisis, the unemployment, the transformations of the Welfare State, the individualization, etc. We have, therefore, analyzed the way that Spanish long-term unemployed over 45 years experience vulnerability and its consequences on their lives. We have focused on long-term unemployed over 45 that had previously developed stable career paths and have been looking for a job for two years or more. In order to carry out this analysis, we will try to break the dichotomy between the social and the individual, between the socio-historical and the subjectivity, to overcome some of the limits of the research on unemployment. The fieldwork consisted of more than ten focus groups and fifty in-depth interviews. The work and life ethics completely changed at the turn of the nineteenth and twentieth centuries. In the nineteenth century, companies had trouble maintaining their staff, but in the 21st century, unemployed workers feel that they are useless people. Workers value themselves if they have a job. This unveils that labor is a comprehensive social relationship in capitalist societies. In general, unemployed workers are not able to analyze their unemployment as a social problem. They analyze their unemployment as an individual problem. They blame themselves for their unemployment; instead of taking into account that there are millions of unemployed, they talk about themselves as if they were on their own. And the problems caused by unemployment are explained as psychological problems and are medicalized. Anyway, it is important to highlight that this is the result of an ideology and a social relationship that is part of our historical time.

Keywords: life ethics, work ethics, unemployment, unemployed over 45 years old

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Authors: Cezary Kulesza, Katarzyna Lapinska

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Regarding the nature of the notion of fair trial, one must see the source of the fair trial principle in the following acts of international law: art. 6 of the ECHR of 1950 and art.14 the International Covenant on Civil and Political Rights of 1966, as well as in art. 45 of the Polish Constitution. However, the problem is that the above-mentioned acts essentially apply the principle of a fair trial to the main hearing and not to appeal proceedings. Therefore, the main thesis of the work is to answer the question whether the Polish model of appeal proceedings is fair. The paper presents the problem of fair appeal proceedings in Poland in comparative perspective. Thus, the authors discuss the basic features of English, German and Russian appeal systems. The matter is also analysed in the context of the last reforms of Polish criminal procedure, because since 2013 Polish parliament has significantly changed criminal procedure almost three times: by the Act of 27th September, 2013, the Act of 20th February, 2015 which came into effect on 1st July, 2015 and the Act of 11th March, 2016. The most astonishing is that these three amendments have been varying from each other – changing Polish criminal procedure to more adversarial one and then rejecting all measures just involved in previous acts. Additional intent of the Polish legislator was amending the forms of plea bargaining: conviction of the defendant without trial or voluntary submission to a penalty, which were supposed to become tools allowing accelerating the criminal process and, at the same time, implementing the principle of speedy procedure. The next part of the paper will discuss the matter, how the changes of plea bargaining and the main trial influenced the appellate procedure in Poland. The authors deal with the right to appeal against judgments issued in negotiated case-ending settlements in the light of Art. 2 of Protocol No. 7 to the ECHR and the Polish Constitution. The last part of the presentation will focus on the basic changes in the appeals against judgments issued after the main trial. This part of the paper also presents the results of examination of court files held in the Polish Appeal Courts in Białystok, Łódź and Warsaw. From these considerations it is concluded that the Polish CCP of 1997 in ordinary proceedings basically meets both standards: the standard adopted in Protocol No. 7 of the Convention and the Polish constitutional standard. But the examination of case files shows in particular the following phenomena: low effectiveness of appeals and growing stability of the challenged judgments of district courts, extensive duration of appeal proceedings and narrow scope of evidence proceedings before the appellate courts. On the other hand, limitations of the right to appeal against the judgments issued in consensual modes of criminal proceedings justify the fear that such final judgments may violate the principle of criminal accurate response or the principle of material truth.

Keywords: adversarial trial, appeal, ECHR, England, evidence, fair trial, Germany, Polish criminal procedure, reform, Russia

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Authors: A. Sathish, N. N. Lingaraju, K. N. Geetha, C. A. Srinivasamurthy, S. Bhaskar

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Under dryland conditions, it is observed that the soil organic matter is low due to low organic carbon content due to poor management with less use of inputs. On the other hand, disposal of sugar industry waste, i.e., spentwash is a major concern with limited space for land based treatment and disposal which causes environmental pollution. Spentwash is also a resource that can be applied for productive uses since it contains nutrients that have the potential for use in agriculture. The disposal of spent wash may lead to environmental pollution. Hence as an alternative mechanism, it was applied once to dry lands, and the experiments were conducted from 2012-13 to 2016-17 in kharif season in Maddur Taluk, Mandya District, Karnataka State, India. The study conducted was in 93 different farmers field (maize-11, finger millet-80 & horsegram-14). Spentwash was applied at the rate of 100 m³ ha⁻¹ before sowing of the crops. The results showed that yield of dryland crops like finger millet, horse gram and maize was recorded 14.75 q ha⁻¹, 6 q ha⁻¹ and 31.00 q ha⁻¹, respectively and the yield increase to an extent of 10-25 per cent with one time application of spentwash to dry lands compared to farmers practice, i.e., chemical fertilizer application. The higher yield may be attributed to slow and steady release of nutrients by spentwash throughout the crop growth period. In addition, the growth promoting and other beneficial substances present in spentwash might have also helped in better plant growth and yield. The soil sample analysis after harvest of the crops indicate acidic to neutral pH, EC of 0.11 dSm⁻¹ and Na of 0.20 C mol (P⁺) kg⁻¹ in the normal range which are not harmful. Hence, it can be applied to drylands at least once in 3 years which enhances yield as well as reduces environmental pollution.

Keywords: dryland crops, pollution, sugar industry waste, spentwash

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Authors: Biruk Abate

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Evaporative cooling occurs when air with high temperature and reduced humidity passes over a wet porous surface and a higher degree of cooling process is achieved for storage of fruits and vegetables due to greater rate of evaporation. The main objective of this reviewed study is to understand the effect of evaporative surface pad thickness and geometric configuration on the saturation efficiency of evaporative cooler and to state some related factors affecting the performance of the system. From this overview, selection of pad thickness and geometrical shape with suitable characteristics of heat and mass transfer and water holding capacity of the pads was reviewed as these parameters are important for saturation efficiency of evaporative cooling. Increasing the cooling pad thickness through increasing the face velocity increases the effectiveness of wet-bulb saturation. Increasing ambient temperature, inlet air speed and ambient air humidity decreases the wet bulb effectiveness and it increases with increasing length of the pad. Increasing the ambient temperature and inlet air velocity decreases the humidity ratio, but increases with increasing ambient air humidity and lengths of the pad. Increasing the temperature-humidity index is possible with increasing ambient temperature, inlet air velocity, ambient air humidity and pad length. Generally, all materials having a higher wetted surface area per unit volume give higher efficiency. Materials with higher thickness increase the wetted surface area for better mix-up of air and water to give higher efficiency for the same shape and this in turn helps to store fruits and vegetables.

Keywords: Degree of cooling, heat and mass transfer, evaporative cooling, porous surface

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Authors: Rai Mansoor Imtiaz

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Guardians in hybrid regimes fragment opposition parties and ban their political leaders, and disenfranchise their voters' political participation. When guardians in hybrid regimes are so powerful that they remain decisive on electoral politics of states, and have powers to ban political parties and their leadership, then "why do political parties backed by those powerful guardians lose elections" and "how do anti-establishment parties make electoral inroads at the local and national levels." These two questions are interrelated with the key research question of my research "why do people vote for political parties rejected by powerful guardians in establishmentarian democracies." Furthermore, this research question is important to be explored for two reasons. First, existing literature only reflects the electoral victories of opposition parties or defeats of military-sponsored parties (see Thailand and Turkey) but remains silent on political change that led the anti-military parties to win the elections. Second, why is it a case that people belonging to the countries where militaries remain popular among the public (see Turkey and Pakistan) have started putting their trust in anti-establishment politicians who criticise the military against their intervention in politics? For instance, in Pakistan, where commenting against the military is meant to comment against the state –– an anti-military narrative is getting popular support. The conceptual framework of hybrid states in this research relies on the concept of a 'reserved domain/tutelary body' (guardians of hybrid states). However, this research makes a case that hybrid states are not consolidated separate political entities but rather vacillated states that fluctuate between democratic and authoritarian practices. This paper, therefore, uses the term establishmentarian democracy as a subtype of the hybrid regime, which is more consolidated than a hybrid democracy.

Keywords: Guardians, Hybrid Regimes, Voters, Elections, Democracy, South Asia

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Authors: Jocelyn D. Perreault

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An exploratory study has been launched in 2013-2014 in the province of Quebec, the state of Vermont (USA) and the region of Zaer in Morocco. We have realized three first case studies in order to better understand the marketing strategies of starting up vineries, which are defined as having a maximum of five years of operations. The methodology used consisted of visiting the vineyards; conducting semi-directed interviews with owner-managers; visiting points-of-sale of the wines and analysing the web sites using an assessment grid. The results indicate many differences between the three firms in their use of their web sites. More precisely, we have noticed that: -The Quebec vineyard uses its web site in collaboration with the touristic actors of its region and the association of the wine makers of the province of Quebec.Positioning is as a touristic attraction. -In comparison,the Moroccan firm limits the content of the web site to itself and its activities and somehow to the wine industry.Positioning is as a wine specialist. -The american firm associated its web site more to farm markets actors and activities of the region.Positioning is as an agricultural actor. -The positionings of the three vineyards are very different from each others and will be discussed more thoroughly during the presentation to better understand the use of web sites, thus contributing to the «brand image». -Improvements to the three web sites have been identified and suggested by more than a hundred of persons using the same grid and comprising students of bachelor and MBA degrees from our university. In general, the web sites have been considered satisfying but requiring several improvements at different levels. Changes or updates have been observed for the Quebec winery web site but practically no changes have been made to the others in the last months. The assessment grid will be presented in more details as well as the global and the partial scores given by the respondents. In conclusion, we have noticed that only one winery is considered as a «heavy and strategic user» of its web site and of Facebook and Twitter.

Keywords: web site, wineries, marketing, positioning, starting up strategies

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Authors: Domenico Chizzoniti, Monica Moscatelli, Letizia Cattani, Piero Favino, Luca Preis

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A settlement strategy is to anticipate and respond the needs of existing and future communities through the provision of primary health care facilities in marginalized areas. Access to a health care network is important to improving healthcare coverage, often lacking, in developing countries. The study explores that a good sanitary system strategy of rural contexts brings advantages to an existing settlement: improving transport, communication, water and social facilities. The objective of this paper is to define a possible methodology to implement primary health care facilities in disadvantaged areas of emerging countries. In this research, we analyze the case study of Lauro de Freitas, a municipality in the Brazilian state of Bahia, part of the Metropolitan Region of Salvador, with an area of 57,662 km² and 194.641 inhabitants. The health localization system in Lauro de Freitas is an integrated process that involves not only geographical aspects, but also a set of factors: population density, epidemiological data, allocation of services, road networks, and more. Data were collected also using semi-structured interviews and questionnaires to the local population. Synthesized data suggest that moving away from the coast where there is the greatest concentration of population and services, a network of primary health care facilities is able to improve the living conditions of small-dispersed communities. Based on the health service needs of populations, we have developed a methodological approach that is particularly useful in rural and remote contexts in emerging countries.

Keywords: healthcare, settlement strategy, urban health, rural

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Authors: Anna Drabczyk, Sonia Kudlacik-Kramarczyk, Dagmara Malina, Bozena Tyliszczak, Agnieszka Sobczak-Kupiec

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Nowadays, nano-size materials are very popular group of materials among scientists. What is more, these materials find an application in a wide range of various areas. Therefore constantly increasing demand for nanomaterials including metallic nanoparticles such as silver of gold ones is observed. Therefore, new routes of their preparation are sought. Considering potential application of nanoparticles, it is important to select an adequate methodology of their preparation because it determines their size and shape. Among the most commonly applied methods of preparation of nanoparticles chemical and electrochemical techniques are leading. However, currently growing attention is directed into the biological or biochemical aspects of syntheses of metallic nanoparticles. This is associated with a trend of developing of new routes of preparation of given compounds according to the principles of green chemistry. These principles involve e.g. the reduction of the use of toxic compounds in the synthesis as well as the reduction of the energy demand or minimization of the generated waste. As a result, a growing popularity of the use of such components as natural plant extracts, infusions or essential oils is observed. Such natural substances may be used both as a reducing agent of metal ions and as a stabilizing agent of formed nanoparticles therefore they can replace synthetic compounds previously used for the reduction of metal ions or for the stabilization of obtained nanoparticles suspension. Methods that proceed in the presence of previously mentioned natural compounds are environmentally friendly and proceed without the application of any toxic reagents. Methodology: Presented research involves preparation of silver nanoparticles using selected plant extracts, e.g. artichoke extract. Extracts of natural origin were used as reducing and stabilizing agents at the same time. Furthermore, syntheses were carried out in the presence of additional polymeric stabilizing agent. Next, such features of obtained suspensions of nanoparticles as total antioxidant activity as well as content of phenolic compounds have been characterized. First of the mentioned studies involved the reaction with DPPH (2,2-Diphenyl-1-picrylhydrazyl) radical. The content of phenolic compounds was determined using Folin-Ciocalteu technique. Furthermore, an essential issue was also the determining of the stability of formed suspensions of nanoparticles. Conclusions: In the research it was demonstrated that metallic nanoparticles may be obtained using plant extracts or infusions as stabilizing or reducing agent. The methodology applied, i.e. a type of plant extract used during the synthesis, had an impact on the content of phenolic compounds as well as on the size and polydispersity of obtained nanoparticles. What is more, it is possible to prepare nano-size particles that will be characterized by properties desirable from the viewpoint of their potential application and such an effect may be achieved with the use of non-toxic reagents of natural origin. Furthermore, proposed methodology stays in line with the principles of green chemistry.

Keywords: green chemistry principles, metallic nanoparticles, plant extracts, stabilization of nanoparticles

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Authors: Sharon Sibanda, Benny Motileng

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The World Health Organisation (WHO) identified the Sars-Cov-2 (COVID-19) as a pandemic on the 12ᵗʰ of March 2020, with South Africa recording its first case on the 5ᵗʰ of March 2020. The rapidly spreading virus led the South African government to implement one of the strictest nationwide lockdowns globally, resulting in the closing down of all institutions of higher learning effective March 18ᵗʰ 2020. Thus, this qualitative study primarily aimed to explore whether post-graduate psychology students were in a state of a depleted or cohesive self, post the psychological isolation of COVID-19 risk-adjusted level 5 lockdown. Semi-structured interviews from a qualitative interpretive approach comprising N=6 psychology post-graduate students facilitated a rich understanding of their intra-psychic experiences of the self. Thematic analysis of data gathered from the interviews illuminated how students were forced into the self by the emotional isolation of hard lockdown, with the emergence of core psychic conflict often defended against through external self-object experiences. The findings also suggest that lockdown stripped off this sample of psychology post-graduate students’ defensive escape from the inner self through external self-object distractions. The external self was stripped to the core of the internal self by the isolation of hard lockdown, thereby uncovering the psychic function of roles and defenses amalgamated throughout modern cultural consciousness that dictates self-functioning. The study suggests modelling reflexivity skills in the integration of internal and external self-experience dynamics as part of a training model for continued personal and professional development for psychology students.

Keywords: COVID-19, fragmentation, self-object experience, true/false self

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Authors: Natalia V. Beloglazova, Pieterjan Lenain, Martin Hedstrom, Dietmar Knopp, Sarah De Saeger

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In recent years polycyclic aromatic hydrocarbons (PAHs), which represent a hazard to humans and entire ecosystem, have been receiving an increased interest due to their mutagenic, carcinogenic and endocrine disrupting properties. They are formed in all incomplete combustion processes of organic matter and, as a consequence, ubiquitous in the environment. Benzo(a)pyrene (BaP) is on the priority list published by the Environmental Agency (US EPA) as the first PAH to be identified as a carcinogen and has often been used as a marker for PAHs contamination in general. It can be found in different types of water samples, therefore, the European Commission set up a limit value of 10 ng L–1 (10 ppt) for BAP in water intended for human consumption. Generally, different chromatographic techniques are used for PAHs determination, but these assays require pre-concentration of analyte, create large amounts of solvent waste, and are relatively time consuming and difficult to perform on-site. An alternative robust, stand-alone, and preferably cheap solution is needed. For example, a sensing unit which can be submerged in a river to monitor and continuously sample BaP. An affinity sensor based on capacitive transduction was developed. Natural antibodies or their synthetic analogues can be used as ligands. Ideally the sensor should operate independently over a longer period of time, e.g. several weeks or months, therefore the use of molecularly imprinted polymers (MIPs) was discussed. MIPs are synthetic antibodies which are selective for a chosen target molecule. Their robustness allows application in environments for which biological recognition elements are unsuitable or denature. They can be reused multiple times, which is essential to meet the stand-alone requirement. BaP is a highly lipophilic compound and does not contain any functional groups in its structure, thus excluding non-covalent imprinting methods based on ionic interactions. Instead, the MIPs syntheses were based on non-covalent hydrophobic and π-π interactions. Different polymerization strategies were compared and the best results were demonstrated by the MIPs produced using electropolymerization. 4-vinylpyridin (VP) and divinylbenzene (DVB) were used as monomer and cross-linker in the polymerization reaction. The selectivity and recovery of the MIP were compared to a non-imprinted polymer (NIP). Electrodes were functionalized with natural receptor (monoclonal anti-BaP antibody) and with MIPs selective towards BaP. Different sets of electrodes were evaluated and their properties such as sensitivity, selectivity and linear range were determined and compared. It was found that both receptor can reach the cut-off level comparable to the established ML, and despite the fact that the antibody showed the better cross-reactivity and affinity, MIPs were more convenient receptor due to their ability to regenerate and stability in river till 7 days.

Keywords: antibody, benzo(a)pyrene, capacitive sensor, MIPs, river water

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Authors: Ahlad Neti, Elisa Arch, Martha Hall

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Studies have shown that individuals who use Ankle-Foot-Orthoses (AFOs) have a high level of dissatisfaction regarding their current AFOs. Studies point to the focus on technical design with little attention given to the user perspective as a source of AFO designs that leave users dissatisfied. To design a new AFO that satisfies users and thereby improves their quality of life, the reasons for their dissatisfaction and their wants and needs for an improved AFO design must be identified. There has been little research into the user perspective on AFO use and desired improvements, so the relationship between AFO design and satisfaction in daily use must be assessed to develop appropriate metrics and constraints prior to designing a novel AFO. To assess the user perspective on AFO design, structured interviews were conducted with 7 individuals (average age of 64.29±8.81 years) who use AFOs. All interviews were transcribed and coded to identify common themes using Grounded Theory Method in NVivo 12. Qualitative analysis of these results identified sources of user dissatisfaction such as heaviness, bulk, and uncomfortable material and overall needs and wants for an AFO. Beyond the user perspective, certain objective factors must be considered in the construction of metrics and constraints to ensure that the AFO fulfills its medical purpose. These more objective metrics are rooted in a common medical device market and technical standards. Given the large body of research concerning these standards, these objective metrics and constraints were derived through a literature review. Through these two methods, a comprehensive list of metrics and constraints accounting for both the user perspective on AFO design and the AFO’s medical purpose was compiled. These metrics and constraints will establish the framework for designing a new AFO that carries out its medical purpose while also improving the user experience. The metrics can be categorized into several overarching areas for AFO improvement. Categories of user perspective related metrics include comfort, discreteness, aesthetics, ease of use, and compatibility with clothing. Categories of medical purpose related metrics include biomechanical functionality, durability, and affordability. These metrics were used to guide an iterative prototyping process. Six concepts were ideated and compared using system-level analysis. From these six concepts, two concepts – the piano wire model and the segmented model – were selected to move forward into prototyping. Evaluation of non-functional prototypes of the piano wire and segmented models determined that the piano wire model better fulfilled the metrics by offering increased stability, longer durability, fewer points for failure, and a strong enough core component to allow a sock to cover over the AFO while maintaining the overall structure. As such, the piano wire AFO has moved forward into the functional prototyping phase, and healthy subject testing is being designed and recruited to conduct design validation and verification.

Keywords: ankle-foot orthotic, assistive technology, human centered design, medical devices

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Authors: Majid Mardaniyan Ghahfarokhi, Abdolhamid Habibi, Majid Mohammad Shahi

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The combination of exercise and diet as the most important strategy to reduce weight and control obesity-related factors, including Irisin, Insulin, and Glucose was raised. The aim of this study was to investigate the effect of aerobic exercise combined with four different diets on serum levels of Irisin, Insulin, and Glucose in overweight men. Methods: In this quasi-experimental study, 8 overweight men (BMI 29.23±0.47) with average age of (23±1.6) voluntarily participated in 4 sessions by one-week interval. The study was done in exercise physiology lab. In each session, subjects performed a 30 minutes treadmill test with 60-70% of maximum heart rate, after consuming a high carbohydrate, high-fat, high-protein and normal diet. For biochemical measurement, three blood samples were taken in fasting state, two hours after meals and after exercise Results: Statistical analysis of data showed that the serum levels of Irisin after consumption all four diets had been reduced which this reduce as a result of high-fat diet that were significantly (p ≤ 0/038). Serum concentration of Insulin and Glucose increased after consuming four diets. However, increase in serum Insulin and Glucose was significant only after consuming high-carbohydrate diet (Respectively p ≤ 0/001, p ≤ 0/042). In addition, during exercise after consuming all four regular diet, high carbohydrate, high-protein and high-fat, Irisin significant increased significantly (Respectively p ≤ 0/021, p ≤ 0/049, p ≤ 0/001, P ≤ 0/003), Insulin decreased significantly (Respectively p ≤ 0/002, p ≤ 0/001, p ≤ 0/001, p ≤ 0/002) and Glucose were significantly reduced (Respectively p ≤ 0/001, p ≤ 0/001, P ≤ 0/001, p ≤ 0/002). After aerobic activity following the consumption of a high protein diet the highest increase in irisin levels, and after aerobic exercise following consumption of high carbohydrate diet the greatest decrease in insulin and glucose levels were observed. Conclusion: It seems that diet alone and exercises following different consumption diets can have a significant effect on Irisin, Insulin, and Glucose serum levels in overweight young men.

Keywords: acute aerobic exercise, diet, irisin, overweight

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Authors: Pradeep Kumar

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The present work is based on application of cement mortar with natural sand and discontinuous steel fiber through which bending behavior of skinny beam was evaluated. This research is to study the effects of combining reinforcing steel meshes (continuous steel reinforcement) with discontinuous fibers as reinforcement in skinny walled Portland cement based cement mortar with crushed stone dust as a fine aggregate. The term ‘skinny’ means thickness of the beams is less than 25 mm. The main idea behind this combination is to satisfy the ultimate strength limit state through the steel mesh reinforcement (as a main reinforcement) and to control the cracking under service loads through fiber (Recron 3s) reinforcement (as secondary reinforcement). The main object of this study is to carry out the bending behavior of mortar reinforced thin beam with only one layer of steel mesh (with various transfer wire spacing) and with a recron 3s (Reliance) fifers. The wide experimental program with bending tests is undertaken. The following variables are investigated: (a) the reference mesh size - 25.4 x 25.4 mm and 50.8 x 50.8 mm; (b) the transverse wire spacing - 25.4 mm, 50.8 mm, and no transverse wires; (c) the type of fibers – Reliance (Recron 3s, 6mm length); and (d) the fiber volume fraction – 0.1% and 0.25%. Some of the main conclusions are: (a) the use of recron 3s fibers leads to a little better overall performance than that with no fiber; (b) an increase in equivalent stress is observed when 0.1% RF,0.25% R Fibers are used; (c) when 25.4 x 50.8 size steel mesh is used, no noticeable change in behavior is observed in comparison to specimens without fibers; and (d) for no fibers 0.1% and o.1% RF the transverse wire spacing has some little effect on the equivalent stress for RF fibers, the transverse wire has no influence but the equivalent stress are increased.

Keywords: cement mortar, crushed stone dust, fibre, steel mesh

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Authors: C. Rajalakshmi, Vibin Ipe Thomas

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Sonogashira coupling reactions are widely employed in the synthesis of molecules of biological and pharmaceutical importance. Copper catalyzed Sonogashira coupling reactions are gaining importance owing to the low cost and less toxicity of copper as compared to the palladium catalyst. In the present work, a detailed computational study has been carried out on the Sonogashira coupling reaction between aryl halides and terminal alkynes catalyzed by Copper (I) species with trans-1, 2 Diaminocyclohexane as ligand. All calculations are performed at Density Functional Theory (DFT) level, using the hybrid Becke3LYP functional. Cu and I atoms are described using an effective core potential (LANL2DZ) for the inner electrons and its associated double-ζ basis set for the outer electrons. For all other atoms, 6-311G+* basis set is used. We have identified that the active catalyst species is a neutral 3-coordinate trans-1,2 diaminocyclohexane ligated Cu (I) alkyne complex and found that the oxidative addition and reductive elimination occurs in a single step proceeding through one transition state. This is owing to the ease of reductive elimination involving coupling of Csp2-Csp carbon atoms and the less stable Cu (III) intermediate. This shows the mechanism of copper catalyzed Sonogashira coupling reactions are quite different from those catalyzed by palladium. To gain further insights into the mechanism, substrates containing various functional groups are considered in our study to traverse their effect on the feasibility of the reaction. We have also explored the effect of ligand on the catalytic cycle of the coupling reaction. The theoretical results obtained are in good agreement with the experimental observation. This shows the relevance of a combined theoretical and experimental approach for rationally improving the cross-coupling reaction mechanisms.

Keywords: copper catalysed, density functional theory, reaction mechanism, Sonogashira coupling

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