Search results for: spiral model
455 Fucoidan: A Potent Seaweed-Derived Polysaccharide with Immunomodulatory and Anti-inflammatory Properties
Authors: Tauseef Ahmad, Muhammad Ishaq, Mathew Eapen, Ahyoung Park, Sam Karpiniec, Vanni Caruso, Rajaraman Eri
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Fucoidans are complex, fucose-rich sulfated polymers discovered in brown seaweeds. Fucoidans are popular around the world, particularly in the nutraceutical and pharmaceutical industries, due to their promising medicinal properties. Fucoidans have been shown to have a variety of biological activities, including anti-inflammatory effects. They are known to inhibit inflammatory processes through a variety of mechanisms, including enzyme inhibition and selectin blockade. Inflammation is a part of the complicated biological response of living systems to damaging stimuli, and it plays a role in the pathogenesis of a variety of disorders, including arthritis, inflammatory bowel disease, cancer, and allergies. In the current investigation, various fucoidan extracts from Undaria pinnatifida, Fucus vesiculosus, Macrocystis pyrifera, Ascophyllum nodosum, and Laminaria japonica were assessed for inhibition of pro-inflammatory cytokine production (TNF-α, IL-1β, and IL-6) in LPS induced human macrophage cell line (THP-1) and human peripheral blood mononuclear cells (PBMCs). Furthermore, we also sought to catalogue these extracts based on their anti-inflammatory effects in the current in-vitro cell model. Materials and Methods: To assess the cytotoxicity of fucoidan extracts, MTT (3-[4,5-dimethylthiazol-2-yl]-2,5, -diphenyltetrazolium bromide) cell viability assay was performed. Furthermore, a dose-response for fucoidan extracts was performed in LPS induced THP-1 cells and PBMCs after pre-treatment for 24 hours, and levels of TNF-α, IL-1β, and IL-6 cytokines were measured using Enzyme-Linked Immunosorbent Assay (ELISA). Results: The MTT cell viability assay demonstrated that fucoidan extracts exhibited no evidence of cytotoxicity in THP-1 cells or PBMCs after 48 hours of incubation. The results of the sandwich ELISA revealed that all fucoidan extracts suppressed cytokine production in LPS-stimulated PBMCs and human THP-1 cells in a dose-dependent manner. Notably, at lower concentrations, the lower molecular fucoidan (5-30 kDa) extract from Macrocystis pyrifera was a highly efficient inhibitor of pro-inflammatory cytokines. Fucoidan extracts from all species including Undaria pinnatifida, Fucus vesiculosus, Macrocystis pyrifera, Ascophyllum nodosum, and Laminaria japonica exhibited significant anti-inflammatory effects. These findings on several fucoidan extracts provide insight into strategies for improving their efficacy against inflammation-related diseases. Conclusion: In the current research, we have successfully catalogued several fucoidan extracts based on their efficiency in LPS-induced macrophages and PBMCs in downregulating the key pro-inflammatory cytokines (TNF-, IL-1 and IL-6), which are prospective targets in human inflammatory illnesses. Further research would provide more information on the mechanism of action, allowing it to be tested for therapeutic purposes as an anti-inflammatory medication.Keywords: fucoidan, PBMCs, THP-1, TNF-α, IL-1β, IL-6, inflammation
Procedia PDF Downloads 59454 Work Related Outcomes of Perceived Authentic Leadership: Moderating Role of Organizational Structures
Authors: Aisha Zubair, Anila Kamal
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Leadership styles and practices greatly influence the organizational effectiveness and productivity. It also plays an important role in employees’ experiences of positive emotions at workplace and creative work behaviors. Authentic leadership as a newly emerging concept has been found as a significant predictor of various desirable work related outcomes. However, leadership practices and its work related outcomes, to a great extent, are determined by the very nature of the organizational structures (tall and flat). Tall organizations are characterized by multiple hierarchical layers with predominant vertical communication patterns, and narrow span of control; while flat organizations are featured by few layers of management employing both horizontal and vertical communication styles, and wide span of control. Therefore, the present study was undertaken to determine the work related outcomes of perceived authentic leadership; that is work related flow and creative work behavior among employees of flat and tall organizations. Moreover, it was also intended to determine the moderating role of organizational structure (flat and tall) in the relationship between perceived authentic leadership with work related flow and creative work behavior. In this regard, two types of companies have been considered; that is, banks as a form of tall organizational structure with multiple hierarchical structures while software companies have been considered as flat organizations with minimal layers of management. Respondents (N = 1180) were full time regular employees of marketing departments of banks (600) and software companies (580) including both men and women with age range of 22-52 years (M = 33.24; SD = 7.81). Confirmatory Factor Analysis yielded factor structures of measures of work related flow and creative work behavior in accordance to the theoretical models. However, model of authentic leadership exhibited variation in terms of two items which were not included in the final measure of the perceived authentic leadership. Results showed that perceived authentic leadership was positively associated with work related flow and creative work behavior. Likewise, work related flow was positively aligned with creative work behavior. Furthermore, type of organizational structure significantly moderated the relationship of perceived authentic leadership with work related flow and creative work behavior. Results of independent sample t-test showed that employees working in flat organization reflected better perceptions of authentic leadership; higher work related flow and elevated levels of creative work behavior as compared to those working in tall organizations. It was also found that employees with extended job experience and more job duration in the same organization displayed better perceptions of authentic leadership, reported more work related flow and augmented levels of creative work behavior. Findings of the present study distinctively highlighted the similarities as well as differences in the interactions of major constructs which function differentially in the context of tall (banks) and flat (software companies) organizations. Implications of the present study for employees and management as well as future recommendations were also discussed.Keywords: creative work behavior, organizational structure, perceived authentic leadership, work related flow
Procedia PDF Downloads 389453 Association of Temperature Factors with Seropositive Results against Selected Pathogens in Dairy Cow Herds from Central and Northern Greece
Authors: Marina Sofia, Alexios Giannakopoulos, Antonia Touloudi, Dimitris C Chatzopoulos, Zoi Athanasakopoulou, Vassiliki Spyrou, Charalambos Billinis
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Fertility of dairy cattle can be affected by heat stress when the ambient temperature increases above 30°C and the relative humidity ranges from 35% to 50%. The present study was conducted on dairy cattle farms during summer months in Greece and aimed to identify the serological profile against pathogens that could affect fertility and to associate the positive serological results at herd level with temperature factors. A total of 323 serum samples were collected from clinically healthy dairy cows of 8 herds, located in Central and Northern Greece. ELISA tests were performed to detect antibodies against selected pathogens that affect fertility, namely Chlamydophila abortus, Coxiella burnetii, Neospora caninum, Toxoplasma gondii and Infectious Bovine Rhinotracheitis Virus (IBRV). Eleven climatic variables were derived from the WorldClim version 1.4. and ArcGIS V.10.1 software was used for analysis of the spatial information. Five different MaxEnt models were applied to associate the temperature variables with the locations of seropositive Chl. abortus, C. burnetii, N. caninum, T. gondii and IBRV herds (one for each pathogen). The logistic outputs were used for the interpretation of the results. ROC analyses were performed to evaluate the goodness of fit of the models’ predictions. Jackknife tests were used to identify the variables with a substantial contribution to each model. The seropositivity rates of pathogens varied among the 8 herds (0.85-4.76% for Chl. abortus, 4.76-62.71% for N. caninum, 3.8-43.47% for C. burnetii, 4.76-39.28% for T. gondii and 47.83-78.57% for IBRV). The variables of annual temperature range, mean diurnal range and maximum temperature of the warmest month gave a contribution to all five models. The regularized training gains, the training AUCs and the unregularized training gains were estimated. The mean diurnal range gave the highest gain when used in isolation and decreased the gain the most when it was omitted in the two models for seropositive Chl.abortus and IBRV herds. The annual temperature range increased the gain when used alone and decreased the gain the most when it was omitted in the models for seropositive C. burnetii, N. caninum and T. gondii herds. In conclusion, antibodies against Chl. abortus, C. burnetii, N. caninum, T. gondii and IBRV were detected in most herds suggesting circulation of pathogens that could cause infertility. The results of the spatial analyses demonstrated that the annual temperature range, mean diurnal range and maximum temperature of the warmest month could affect positively the possible pathogens’ presence. Acknowledgment: This research has been co‐financed by the European Regional Development Fund of the European Union and Greek national funds through the Operational Program Competitiveness, Entrepreneurship and Innovation, under the call RESEARCH–CREATE–INNOVATE (project code: T1EDK-01078).Keywords: dairy cows, seropositivity, spatial analysis, temperature factors
Procedia PDF Downloads 199452 Building Carbon Footprint Comparison between Building Permit, as Built, as Built with Circular Material Usage
Authors: Kadri-Ann Kertsmik, Martin Talvik, Kimmo Lylykangas, Simo Ilomets, Targo Kalamees
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This study compares the building carbon footprint (CF) values for a case study of a private house located in a cold climate, using the Level(s) methodology. It provides a framework for measuring the environmental performance of buildings throughout their life cycle, taking into account various factors. The study presents the results of the three scenarios, comparing their carbon emissions and highlighting the benefits of circular material usage. The construction process was thoroughly documented, and all materials and components (including minuscule mechanical fasteners, each meter of cable, a kilogram of mortar, and the component of HVAC systems, among other things) delivered to the construction site were noted. Transportation distances of each delivery, the fuel consumption of construction machines, and electricity consumption for temporary heating and electrical tools were also monitored. Using the detailed data on material and energy resources, the CF was calculated for two scenarios: one where circular material usage was applied and another where virgin materials were used instead of reused ones. The results were compared with the CF calculated based on the building permit design model using the Level(s) methodology. To study the range of possible results in the early stage of CF assessment, the same building permit design was given to several experts. Results showed that embodied carbon values for a built scenario were significantly lower than the values predicted by the building permit stage as a result of more precise material quantities, as the calculation methodology is designed to overestimate the CF. Moreover, designers made an effort to reduce the building's CF by reusing certain materials such as ceramic tiles, lightweight concrete blocks, and timber during the construction process. However, in a cold climate context where operational energy (B6) continues to dominate, the total building CF value changes between the three scenarios were less significant. The calculation for the building permit project was performed by several experts, and CF results were in the same range. It alludes that, for the first estimation of preliminary building CF, using average values proves to be an appropriate method for the Estonian national carbon footprint estimation phase during building permit application. The study also identified several opportunities for reducing the carbon footprint of the building, such as reusing materials from other construction sites, preferring local material producers, and reducing wastage on site. The findings suggest that using circular materials can significantly reduce the carbon footprint of buildings. Overall, the study highlights the importance of using a comprehensive approach to measure the environmental performance of buildings, taking into account both the project and the actually built house. It also emphasises the need for ongoing monitoring for designing the building and construction site waste. The study also gives some examples of how to enable future circularity of building components and materials, e.g., building in layers, using wood as untreated, etc.Keywords: carbon footprint, circular economy, sustainable construction, level(s) methodology
Procedia PDF Downloads 87451 Shock-Induced Densification in Glass Materials: A Non-Equilibrium Molecular Dynamics Study
Authors: Richard Renou, Laurent Soulard
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Lasers are widely used in glass material processing, from waveguide fabrication to channel drilling. The gradual damage of glass optics under UV lasers is also an important issue to be addressed. Glass materials (including metallic glasses) can undergo a permanent densification under laser-induced shock loading. Despite increased interest on interactions between laser and glass materials, little is known about the structural mechanisms involved under shock loading. For example, the densification process in silica glasses occurs between 8 GPa and 30 GPa. Above 30 GPa, the glass material returns to the original density after relaxation. Investigating these unusual mechanisms in silica glass will provide an overall better understanding in glass behaviour. Non-Equilibrium Molecular Dynamics simulations (NEMD) were carried out in order to gain insight on the silica glass microscopic structure under shock loading. The shock was generated by the use of a piston impacting the glass material at high velocity (from 100m/s up to 2km/s). Periodic boundary conditions were used in the directions perpendicular to the shock propagation to model an infinite system. One-dimensional shock propagations were therefore studied. Simulations were performed with the STAMP code developed by the CEA. A very specific structure is observed in a silica glass. Oxygen atoms around Silicon atoms are organized in tetrahedrons. Those tetrahedrons are linked and tend to form rings inside the structure. A significant amount of empty cavities is also observed in glass materials. In order to understand how a shock loading is impacting the overall structure, the tetrahedrons, the rings and the cavities were thoroughly analysed. An elastic behaviour was observed when the shock pressure is below 8 GPa. This is consistent with the Hugoniot Elastic Limit (HEL) of 8.8 GPa estimated experimentally for silica glasses. Behind the shock front, the ring structure and the cavity distribution are impacted. The ring volume is smaller, and most cavities disappear with increasing shock pressure. However, the tetrahedral structure is not affected. The elasticity of the glass structure is therefore related to a ring shrinking and a cavity closing. Above the HEL, the shock pressure is high enough to impact the tetrahedral structure. An increasing number of hexahedrons and octahedrons are formed with the pressure. The large rings break to form smaller ones. The cavities are however not impacted as most cavities are already closed under an elastic shock. After the material relaxation, a significant amount of hexahedrons and octahedrons is still observed, and most of the cavities remain closed. The overall ring distribution after relaxation is similar to the equilibrium distribution. The densification process is therefore related to two structural mechanisms: a change in the coordination of silicon atoms and a cavity closing. To sum up, non-equilibrium molecular dynamics were carried out to investigate silica behaviour under shock loading. Analysing the structure lead to interesting conclusions upon the elastic and the densification mechanisms in glass materials. This work will be completed with a detailed study of the mechanism occurring above 30 GPa, where no sign of densification is observed after the material relaxation.Keywords: densification, molecular dynamics simulations, shock loading, silica glass
Procedia PDF Downloads 222450 From the Classroom to Digital Learning Environments: An Action Research on Pedagogical Practices in Higher Education
Authors: Marie Alexandre, Jean Bernatchez
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This paper focuses on the complexity of the face-to-face-to-distance learning transition process. Our research action aims to support the process of transition from classroom to distance learning for teachers in higher education with regard to pedagogical practices that can meet the various needs of students using digital learning environments. In Quebec and elsewhere in the world, the advent of digital education is helping to transform teaching, which is significantly changing the role of teachers. While distance education implies a dissociation of teaching and learning to a variable degree in space and time, distance education (DE) is becoming more and increasingly becoming a preferred option for maintaining the delivery of certain programs and providing access to programs and to provide access to quality activities throughout Quebec. Given the impact of teaching practices on educational success, this paper reports on the results of three research objectives: 1) To document teachers' knowledge of teaching in distance education through the design, experimentation and production of a repertoire of the determinants of pedagogical practices in response to students' needs. 2) Explain, according to a gendered logic, the adequacy between the pedagogical practices implemented in distance learning and the response to the profiles and needs expressed by students using digital learning environments; 3) Produce a model of a support approach during the process of transition from classroom to distance learning at the college level. A mixed methodology, i.e., a quantitative component (questionnaire survey) and a qualitative component (explanatory interviews and living lab) was used in cycles that were part of an ongoing validation process. The intervention includes the establishment of a professional collaboration group, webinars training webinars for the participating teachers on the didactic issue of knowledge-teaching in FAD, the didactic use of technologies, and the differentiated socialization models of educational success in college education. All of the tools developed will be used by partners in the target environment as well as by all teacher educators, students in initial teacher training, practicing teachers, and the general public. The results show that access to training leading to qualifications and commitment to educational success reflects the existing links between the people in the educational community. The relational stakes of being present in distance education take on multiple configurations and different dimensions of learning testify to needs and realities that are sometimes distinct depending on the life cycle. This project will be of interest to partners in the targeted field as well as to all teacher trainers, students in initial teacher training, practicing college teachers, and to university professors. The entire educational community will benefit from digital resources in education. The scientific knowledge resulting from this action research will benefit researchers in the fields of pedagogy, didactics, teacher training and pedagogy in higher education in a digital context.Keywords: action research, didactics, digital learning environment, distance learning, higher education, pedagogy technological, pedagogical content knowledge
Procedia PDF Downloads 87449 Evaluation Of A Start Up Business Strategy In Movie Industry: Case Study Of Visinema
Authors: Stacia E. H. Sitohang, S.Mn., Socrates Rudy Sirait
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The first movie theater in Indonesia was established in December 1900. The movie industry started with international movie penetration. After a while, local movie producers started to rise and created local Indonesian movies. The industry is growing through ups and downs in Indonesia. In 2008, Visinema was founded in Jakarta, Indonesia, by AnggaDwimasSasongko, one of the most respected movie director in Indonesia. After getting achievements and recognition, Visinema chose to grow the company horizontally as opposed to only grow vertically and gain another similar achievement. Visinemachose to build the ecosystem that enables them to obtain many more opportunities and generatebusiness sustainability. The company proceed as an agile company. They created several business subsidiaries to support the company’s Intellectual Property (IP) development. This research was done through interview with the key persons in the company and questionnaire to get market insights regarding Visinema. The is able to transform their IP that initially started from movies to different kinds of business model. Interestingly, Angga chose to use the start up approach to create Visinema. In 2019, the company successfully gained Series A funding from Intudo Ventures and got other various investment schemes to support the business. In early 2020, Covid-19 pandemic negatively impacted many industries in Indonesia, especially the entertainment and leisure businesses. Fortunately, Visinema did not face any significant problem regarding survival during the pandemic, there were nolay-offs nor work hour reductions. Instead, they were thinking of much bigger opportunities and problems. While other companies suffer during the pandemic, Visinema created the first focused Transactional Video On Demand (TVOD) in Indonesia named Bioskop Online. The platform was created to keep the company innovating and adapting with the new online market as the result of the Covid-19 pandemic. Other than a digital platform, Visinemainvested heavily in animation to target kids and family business. They believed that penetrating the technology and animation market is going to be the biggest opportunity in Visinema’s road map. Besides huge opportunities, Visinema is also facing problems. The first is company brand positioning. Angga, as the founder, felt the need to detach his name from the brand image of Visinema to create system sustainability and scalability. Second, the company has to create a strategy to refocus in a particular business area to maintain and improve the competitive advantages. The third problem, IP piracy is a huge structural problem in Indonesia, the company considers IP thieves as their biggest competitors as opposed to other production company. As the recommendation, we suggest a set of branding and management strategy to detach the founder’s name from Visinema’s brand and improve the competitive advantages. We also suggest Visinema invest in system building to prevent IP piracy in the entertainment industry, which later can be another business subsidiary of Visinema.Keywords: business ecosystem, agile, sustainability, scalability, start Up, intellectual property, digital platform
Procedia PDF Downloads 137448 University Curriculum Policy Processes in Chile: A Case Study
Authors: Victoria C. Valdebenito
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Located within the context of accelerating globalization in the 21st-century knowledge society, this paper focuses on one selected university in Chile at which radical curriculum policy changes have been taking place, diverging from the traditional curriculum in Chile at the undergraduate level as a section of a larger investigation. Using a ‘policy trajectory’ framework, and guided by the interpretivist approach to research, interview transcripts and institutional documents were analyzed in relation to the meso (university administration) and the micro (academics) level. Inside the case study, participants from the university administration and academic levels were selected both via snow-ball technique and purposive selection, thus they had different levels of seniority, with some participating actively in the curriculum reform processes. Guided by an interpretivist approach to research, documents and interview transcripts were analyzed to reveal major themes emerging from the data. A further ‘bigger picture’ analysis guided by critical theory was then undertaken, involving interrogation of underlying ideologies and how political and economic interests influence the cultural production of policy. The case-study university was selected because it represents a traditional and old case of university setting in the country, undergoing curriculum changes based on international trends such as the competency model and the liberal arts. Also, it is representative of a particular socioeconomic sector of the country. Access to the university was gained through email contact. Qualitative research methods were used, namely interviews and analysis of institutional documents. In all, 18 people were interviewed. The number was defined by when the saturation criterion was met. Semi-structured interview schedules were based on the four research questions about influences, policy texts, policy enactment and longer-term outcomes. Triangulation of information was used for the analysis. While there was no intention to generalize the specific findings of the case study, the results of the research were used as a focus for engagement with broader themes, often evident in global higher education policy developments. The research results were organized around major themes in three of the four contexts of the ‘policy trajectory’. Regarding the context of influences and the context of policy text production, themes relate to hegemony exercised by first world countries’ universities in the higher education field, its associated neoliberal ideology, with accountability and the discourse of continuous improvement, the local responses to those pressures, and the value of interdisciplinarity. Finally, regarding the context of policy practices and effects (enactment), themes emerged around the impacts of the curriculum changes on university staff, students, and resistance amongst academics. The research concluded with a few recommendations that potentially provide ‘food for thought’ beyond the localized settings of this study, as well as possibilities for further research.Keywords: curriculum, global-local dynamics, higher education, policy, sociology of education
Procedia PDF Downloads 78447 Sexual Behaviour and Psychological Well-Being of a Group of African Adolescent Males in Alice, Eastern Cape
Authors: Jabulani Gilford Kheswa, Thembelihle Lobi
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From a cultural perspective, expression of hegemonic masculinity in South Africa continues to escalate among adolescent males who grow up in communities lacking in role models and recreational facilities. However, when the schools are constructive, and peer influence is positive, adolescent male can potentially express character strengths and lead a meaningful life. Drawing from Bronfenbrenner’s Ecological Model and Keyes and Ryff’s six dimensions of psychological well-being and mental health, such youth may exemplify positive self-esteem, problem- focused coping strategies, condom self-efficacy, good leadership skills, enhanced motivation and a positive emotional state, which buffer against risky sexual behaviors. This paper was aimed at investigating the relationships between adolescent males’ sexual behavior and psychological well-being. This study employed a quantitative research to collect data from 54 Xhosa-speaking adolescent males from one school high school in Fort Beaufort, Eastern Cape, South Africa. These learners were from grade nine, ten and eleven with their ages ranging from 14 to 20. Prior the research commenced, the school principal and caregivers of the learners who participated in the study, gave their informed consent. Self- administered closed-ended questionnaire with Section A (that is, biographical information) and Section B with each question rated on the 5–point Likert scale was used. The advantages of questionnaires include a high response rate as they require less time and offer anonymity because participants’ names are not identified. The SPSS version 18 was used for statistical data analysis. The mean age was 16.83 with a standard deviation of 1.611. 44.4% of the participants were from grade 9, 33.3% from grade 10 and 22.2% from grade 11. The Chronbach alpha of 0.79 was yielded, with respect to self- esteem of adolescent males. In this study, 76.9% reported to attend church services whilst 23% indicated not to attend church services. A further 96.2% of adolescent males indicated to have good relations with guardians while only 3.8% had poorer relations. A large proportion of adolescent males (72.9%) indicated to high-quality friendship as opposed to 27.1% who reported being receiving negative guidance from peers. Other findings revealed that 81.1% of the participants’ parents do not drink alcohol, and they cope at school as 79.6% reported protective factors as attributable towards non-engagement to risky sexual practices. As a result, 81.4% of participants reported not to participate in criminal activities although 85% of the participants indicated that in their school there are drugs. It could be speculated from this study that adolescent males whose caregivers are authoritative, find purpose in life and are most likely to be socially and academically competent. This paper leads to further research interest into mental health, coping strategies and sexual decision-making skills of the youth in South Africa.Keywords: church, mental health, school, sexual behaviour
Procedia PDF Downloads 266446 The Effect of Manure Loaded Biochar on Soil Microbial Communities
Authors: T. Weber, D. MacKenzie
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The script in this paper describes the use of advanced simulation environment using electronic systems (microcontroller, operational amplifiers, and FPGA). The simulation was used for non-linear dynamic systems behaviour with required observer structure working with parallel real-time simulation based on state-space representation. The proposed deposited model was used for electrodynamic effects including ionising effects and eddy current distribution also. With the script and proposed method, it is possible to calculate the spatial distribution of the electromagnetic fields in real-time and such systems. For further purpose, the spatial temperature distribution may also be used. With upon system, the uncertainties and disturbances may be determined. This provides the estimation of the more precise system states for the required system and additionally the estimation of the ionising disturbances that arise due to radiation effects in space systems. The results have also shown that a system can be developed specifically with the real-time calculation (estimation) of the radiation effects only. Electronic systems can take damage caused by impacts with charged particle flux in space or radiation environment. TID (Total Ionising Dose) of 1 Gy and Single Effect Transient (SET) free operation up to 50 MeVcm²/mg may assure certain functions. Single-Event Latch-up (SEL) results on the placement of several transistors in the shared substrate of an integrated circuit; ionising radiation can activate an additional parasitic thyristor. This short circuit between semiconductor-elements can destroy the device without protection and measurements. Single-Event Burnout (SEB) on the other hand, increases current between drain and source of a MOSFET and destroys the component in a short time. A Single-Event Gate Rupture (SEGR) can destroy a dielectric of semiconductor also. In order to be able to react to these processes, it must be calculated within a shorter time that ionizing radiation and dose is present. For this purpose, sensors may be used for the realistic evaluation of the diffusion and ionizing effects of the test system. For this purpose, the Peltier element is used for the evaluation of the dynamic temperature increases (dT/dt), from which a measure of the ionization processes and thus radiation will be detected. In addition, the piezo element may be used to record highly dynamic vibrations and oscillations to absorb impacts of charged particle flux. All available sensors shall be used to calibrate the spatial distributions also. By measured value of size and known location of the sensors, the entire distribution in space can be calculated retroactively or more accurately. With the formation, the type of ionisation and the direct effect to the systems and thus possible prevent processes can be activated up to the shutdown. The results show possibilities to perform more qualitative and faster simulations independent of space-systems and radiation environment also. The paper gives additionally an overview of the diffusion effects and their mechanisms.Keywords: cattle, biochar, manure, microbial activity
Procedia PDF Downloads 103445 Inputs and Outputs of Innovation Processes in the Colombian Services Sector
Authors: Álvaro Turriago-Hoyos
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Most research tends to see innovation as an explanatory factor in achieving high levels of competitiveness and productivity. More recent studies have begun to analyze the determinants of innovation in the services sector as opposed to the much-discussed industrial sector of a country’s economy. This research paper focuses on the services sector in Colombia, one of Latin America’s fastest growing and biggest economies. Over the past decade, much of Colombia’s economic expansion has relied on commodity exports (mainly oil and coffee) whilst the industrial sector has performed relatively poorly. Such developments highlight the potential of the innovative role played by the services sector of the Colombian economy and its future growth prospects. This research paper analyzes the relationship between inputs, which at the same time are internal sources of innovation (such as R&D activities), and external sources that are improved by technology acquisition. The outputs are basically the four kinds of innovation that the OECD Oslo Manual recognizes: product, process, marketing and organizational innovations. The instrument used to measure this input-output relationship is based on Knowledge Production Function approaches. We run Probit models in order to identify the existing relationships between the above inputs and outputs, but also to identify spill-overs derived from interactions of the components of the value chain of the services firms analyzed: customers, suppliers, competitors, and complementary firms. Data are obtained from the Colombian National Administrative Department of Statistics for the period 2008 to 2013 published in the II and III Colombian National Innovation Survey. A short summary of the results obtained lead to conclude that firm size and a firm’s level of technological development turn out to be important discriminating factors for the description of the innovative process at the firm level. The model’s outcomes show a positive impact on the probability of introducing any kind of innovation both on R&D and Technology Acquisition investment. Also, cooperation agreements with customers, research institutes, competitors, and the suppliers are significant. Belonging to a particular industrial group is an important determinant but only to product and organizational innovation. It is possible to establish that Health Services, Education, Computer, Wholesale trade, and Financial Intermediation are the ISIC sectors, which report the highest number of frequencies of the considered set of firms. Those five sectors of the sixteen considered, in all cases, explained more than half of the total of all kinds of innovations. Product Innovation, which is followed by Marketing Innovation, gets the highest results. Displaying the same set of firms distinguishing by size, and belonging to high and low tech services sector shows that the larger the firms the larger a number of innovations, but also that always high-tech firms show a better innovation performance.Keywords: Colombia, determinants of innovation, innovation, services sector
Procedia PDF Downloads 267444 Kinematic of Thrusts and Tectonic Vergence in the Paleogene Orogen of Eastern Iran, Sechangi Area
Authors: Shahriyar Keshtgar, Mahmoud Reza Heyhat, Sasan Bagheri, Ebrahim Gholami, Seyed Naser Raiisosadat
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The eastern Iranian range is a Z-shaped sigmoidal outcrop appearing with a NS-trending general strike on the satellite images, has already been known as the Sistan suture zone, recently identified as the product of an orogenic event introduced either by the Paleogene or Sistan orogen names. The flysch sedimentary basin of eastern Iran was filled by a huge volume of fine-grained Eocene turbiditic sediments, smaller amounts of pelagic deposits and Cretaceous ophiolitic slices, which are entirely remnants of older accretionary prisms appeared in a fold-thrust belt developed onto a subduction zone under the Lut/Afghan block, portions of the Cimmerian superterrane. In these ranges, there are Triassic sedimentary and carbonate sequences (equivalent to Nayband and Shotori Formations) along with scattered outcrops of Permian limestones (equivalent to Jamal limestone) and greenschist-facies metamorphic rocks, probably belonging to the basement of the Lut block, which have tectonic contacts with younger rocks. Moreover, the younger Eocene detrital-volcanic rocks were also thrusted onto the Cretaceous or younger turbiditic deposits. The first generation folds (parallel folds) and thrusts with slaty cleavage appeared parallel to the NE edge of the Lut block. Structural analysis shows that the most vergence of thrusts is toward the southeast so that the Permo-Triassic units in Lut have been thrusted on the younger rocks, including older (probably Jurassic) granites. Additional structural studies show that the regional transport direction in this deformation event is from northwest to the southeast where, from the outside to the inside of the orogen in the Sechengi area. Younger thrusts of the second deformation event were either directly formed as a result of the second deformation event, or they were older thrusts that reactivated and folded so that often, two sets or more slickenlines can be recognized on the thrust planes. The recent thrusts have been redistributed in directions nearly perpendicular to the edge of the Lut block and parallel to the axial surfaces of the northwest second generation large-scale folds (radial folds). Some of these younger thrusts follow the out-of-the-syncline thrust system. The both axial planes of these folds and associated penetrative shear cleavage extended towards northwest appeared with both northeast and southwest dips parallel to the younger thrusts. The large-scale buckling with the layer-parallel stress field has created this deformation event. Such consecutive deformation events perpendicular to each other cannot be basically explained by the simple linear orogen models presented for eastern Iran so far and are more consistent with the oroclinal buckling model.Keywords: thrust, tectonic vergence, orocline buckling, sechangi, eastern iranian ranges
Procedia PDF Downloads 79443 Examining Gender Bias in the Sport Concussion Assessment Tool 3 (SCAT3): A Differential Item Functioning Analysis in NCAA Sports
Authors: Rachel M. Edelstein, John D. Van Horn, Karen M. Schmidt, Sydney N. Cushing
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As a consequence of sports-related concussions, female athletes have been documented as reporting more symptoms than their male counterparts, in addition to incurring longer periods of recovery. However, the role of sex and its potential influence on symptom reporting and recovery outcomes in concussion management has not been completely explored. The present aims to investigate the relationship between female concussion symptom severity and the presence of assessment bias. The Sport Concussion Assessment Tool 3 (SCAT3), collected by the NCAA and DoD CARE Consortium, was quantified at five different time points post-concussion. N= 1,258 NCAA athletes, n= 473 female (soccer, rugby, lacrosse, ice hockey) and n=785 male athletes (football, rugby, lacrosse, ice hockey). A polytomous Item Response Theory (IRT) Graded Response Model (GRM) was used to assess the relationship between sex and symptom reporting. Differential Item Functioning (DIF) and Differential Group Functioning (DGF) were used to examine potential group-level bias. Interactions for DIF were utilized to explore the impact of sex on symptom reporting among NCAA male and female athletes throughout and after their concussion recovery. DIF was significantly detected after B-H corrections displayed in limited items; however, one symptom, “Pressure in Head” (-0.29, p=0.04 vs -0.20, p =0.04), was statistically significant at both < 6 hours and 24-48 hours. Thus, implies that at < 6 hours, males were 29% less likely to indicate “Pressure in the Head” compared to female athletes and 20% less likely at 24-48 hours. Overall, the DGF suggested significant group differences, suggesting that male athletes might be at a higher risk for returning to play prematurely (logits = -0.38, p < 0.001). However, after analyzing the SCAT 3, a clinically relevant trend was discovered. Twelve out of the twenty-two symptoms suggest higher difficulty in female athletes within three or more of the five-time points. These symptoms include Balance Problems, Blurry Vision, Confusion, Dizziness, Don’t Feel Right, Feel in Fog, Feel Slow Down, Low Energy, Neck Pain, Sensitivity to Light, Sensitivity to Noise, Trouble Falling Asleep. Despite a lack of statistical significance, this tendency is contrary to current literature stating that males may be unclear on symptoms, but females may be more honest in reporting symptoms. Further research, which includes possible modifying socioecological factors, is needed to determine whether females may consistently experience more symptoms and require longer recovery times or if, parsimoniously, males tend to present their symptoms and readiness for play differently than females. Such research will help to improve the validity of current assumptions concerning male as compared to female head injuries and optimize individualized treatments for sports-related head injuries.Keywords: female athlete, sports-related concussion, item response theory, concussion assessment
Procedia PDF Downloads 77442 The South African Polycentric Water Resource Governance-Management Nexus: Parlaying an Institutional Agent and Structured Social Engagement
Authors: J. H. Boonzaaier, A. C. Brent
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South Africa, a water scarce country, experiences the phenomenon that its life supporting natural water resources is seriously threatened by the users that are totally dependent on it. South Africa is globally applauded to have of the best and most progressive water laws and policies. There are however growing concerns regarding natural water resource quality deterioration and a critical void in the management of natural resources and compliance to policies due to increasing institutional uncertainties and failures. These are in accordance with concerns of many South African researchers and practitioners that call for a change in paradigm from talk to practice and a more constructive, practical approach to governance challenges in the management of water resources. A qualitative theory-building case study through longitudinal action research was conducted from 2014 to 2017. The research assessed whether a strategic positioned institutional agent can be parlayed to facilitate and execute WRM on catchment level by engaging multiple stakeholders in a polycentric setting. Through a critical realist approach a distinction was made between ex ante self-deterministic human behaviour in the realist realm, and ex post governance-management in the constructivist realm. A congruence analysis, including Toulmin’s method of argumentation analysis, was utilised. The study evaluated the unique case of a self-steering local water management institution, the Impala Water Users Association (WUA) in the Pongola River catchment in the northern part of the KwaZulu-Natal Province of South Africa. Exploiting prevailing water resource threats, it expanded its ancillary functions from 20,000 to 300,000 ha. Embarking on WRM activities, it addressed natural water system quality assessments, social awareness, knowledge support, and threats, such as: soil erosion, waste and effluent into water systems, coal mining, and water security dimensions; through structured engagement with 21 different catchment stakeholders. By implementing a proposed polycentric governance-management model on a catchment scale, the WUA achieved to fill the void. It developed a foundation and capacity to protect the resilience of the natural environment that is critical for freshwater resources to ensure long-term water security of the Pongola River basin. Further work is recommended on appropriate statutory delegations, mechanisms of sustainable funding, sufficient penetration of knowledge to local levels to catalyse behaviour change, incentivised support from professionals, back-to-back expansion of WUAs to alleviate scale and cost burdens, and the creation of catchment data monitoring and compilation centres.Keywords: institutional agent, water governance, polycentric water resource management, water resource management
Procedia PDF Downloads 138441 Influence of Surface Fault Rupture on Dynamic Behavior of Cantilever Retaining Wall: A Numerical Study
Authors: Partha Sarathi Nayek, Abhiparna Dasgupta, Maheshreddy Gade
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Earth retaining structure plays a vital role in stabilizing unstable road cuts and slopes in the mountainous region. The retaining structures located in seismically active regions like the Himalayas may experience moderate to severe earthquakes. An earthquake produces two kinds of ground motion: permanent quasi-static displacement (fault rapture) on the fault rupture plane and transient vibration, traveling a long distance. There has been extensive research work to understand the dynamic behavior of retaining structures subjected to transient ground motions. However, understanding the effect caused by fault rapture phenomena on retaining structures is limited. The presence of shallow crustal active faults and natural slopes in the Himalayan region further highlights the need to study the response of retaining structures subjected to fault rupture phenomena. In this paper, an attempt has been made to understand the dynamic response of the cantilever retaining wall subjected to surface fault rupture. For this purpose, a 2D finite element model consists of a retaining wall, backfill and foundation have been developed using Abaqus 6.14 software. The backfill and foundation material are modeled as per the Mohr-Coulomb failure criterion, and the wall is modeled as linear elastic. In this present study, the interaction between backfill and wall is modeled as ‘surface-surface contact.’ The entire simulation process is divided into three steps, i.e., the initial step, gravity load step, fault rupture step. The interaction property between wall and soil and fixed boundary condition to all the boundary elements are applied in the initial step. In the next step, gravity load is applied, and the boundary elements are allowed to move in the vertical direction to incorporate the settlement of soil due to the gravity load. In the final step, surface fault rupture has been applied to the wall-backfill system. For this purpose, the foundation is divided into two blocks, namely, the hanging wall block and the footwall block. A finite fault rupture displacement is applied to the hanging wall part while the footwall bottom boundary is kept as fixed. Initially, a numerical analysis is performed considering the reverse fault mechanism with a dip angle of 45°. The simulated result is presented in terms of contour maps of permanent displacements of the wall-backfill system. These maps highlighted that surface fault rupture can induce permanent displacement in both horizontal and vertical directions, which can significantly influence the dynamic behavior of the wall-backfill system. Further, the influence of fault mechanism, dip angle, and surface fault rupture position is also investigated in this work.Keywords: surface fault rupture, retaining wall, dynamic response, finite element analysis
Procedia PDF Downloads 106440 Regulating the Ottomans on Turkish Television and the Making of Good Citizens
Authors: Chien Yang Erdem
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This paper takes up the proliferating historical dramas and children’s programs featuring the Ottoman-Islamic legacy on Turkish television as a locus where the processes of subjectification take place. A critical analysis of this emergent cultural phenomenon reveals an alliance of neoliberal and neoconservative political rationalities based on which the Turkish media is restructured to transform society. The existing debates have focused on how the Ottoman historical dramas manifest the Justice and Development Party’s (Adalet ve Kalkınma Partisi) neo-Ottomanist ideology and foreign policy. However, this approach tends to overlook the more complex relationship between the media, government, and society. Employing Michel Foucault’s notion of 'technologies of the self,' this paper aims to examine the governing practices that are deployed to regulate the media and to transform individual citizens into governable subjects in contemporary Turkey. First, through a brief discussion of recent development of the Turkish media towards an authoritarian model, the paper suggests that the relation between the Ottoman television drama and the political subject in question cannot be adequately examined without taking into account the force of the market. Second, by focusing on the managerial restructuring of the Turkish Television and Radio Corporation (Türkiye Radyo ve Televizyon Kurumu), the paper aims to illustrate the rationale and process through which the Turkish media sector is transformed into an integral part of the free market where the government becomes a key actor. The paper contends that this new sphere of free market is organized in a way that enables direct interference of the government and divides media practitioners and consumers into opposing categories through their own participation in the media market. On the one hand, a 'free subject' is constituted based on the premise that the market is a sphere where individuals are obliged to exercise their right to freedom (of choice, lifestyle, and expression). On the other hand, this 'free subject' is increasingly subjugated to such disciplinary practices as censorship for being on the wrong side of the government. Finally, the paper examines the relation between the restructured Turkish media market and the proliferation of Ottoman television drama in the 2010s. The study maintains that the reorganization of the media market has produced a condition where private sector is encouraged to take an active role in reviving Turkey’s Ottoman-Islamic cultural heritage and promulgating moral-religious values. Paying specific attention to the controversial case of Magnificent Century (Muhteşem Yüzyıl) in contrast with TRT’s Ottoman historical drama and children’s programs, the paper aims to identify the ways in which individual citizens are directed to conduct themselves as a virtuous citizenry. It is through the double movement between the governing practices associated with the media market and those concerning the making of a 'conservative generation' that a subject of citizenry of new Turkey is constituted.Keywords: neoconservatism, neoliberalism, ottoman historical drama, technologies of the self, Turkish television
Procedia PDF Downloads 141439 Case Report: Opioid Sparing Anaesthesia with Dexmedetomidine in General Surgery
Authors: Shang Yee Chong
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Perioperative pain is a complex mechanism activated by various nociceptive, neuropathic, and inflammatory pathways. Opioids have long been a mainstay for analgesia in this period, even as we are continuously moving towards a multimodal model to improve pain control while minimising side effects. Dexmedetomidine, a potent alpha-2 agonist, is a useful sedative and hypnotic agent. Its use in the intensive care unit has been well described, and it is increasingly an adjunct intraoperatively for its opioid sparing effects and to decrease pain scores. We describe a case of a general surgical patient in whom minimal opioids was required with dexmedetomidine use. The patient was a 61-year-old Indian gentleman with a history of hyperlipidaemia and type 2 diabetes mellitus, presenting with rectal adenocarcinoma detected on colonoscopy. He was scheduled for a robotic ultra-low anterior resection. The patient was induced with intravenous fentanyl 75mcg, propofol 160mg and atracurium 40mg. He was intubated conventionally and mechanically ventilated. Anaesthesia was maintained with inhalational desflurane and anaesthetic depth was measured with the Masimo EEG Sedline brain function monitor. An initial intravenous dexmedetomidine dose (bolus) of 1ug/kg for 10 minutes was given prior to anaesthetic induction and thereafter, an infusion of 0.2-0.4ug/kg/hr to the end of surgery. In addition, a bolus dose of intravenous lignocaine 1.5mg/kg followed by an infusion at 1mg/kg/hr throughout the surgery was administered. A total of 10mmol of magnesium sulphate and intravenous paracetamol 1000mg were also given for analgesia. There were no significant episodes of bradycardia or hypotension. A total of intravenous phenylephrine 650mcg was given throughout to maintain the patient’s mean arterial pressure within 10-15mmHg of baseline. The surgical time lasted for 5 hours and 40minutes. Postoperatively the patient was reversed and extubated successfully. He was alert and comfortable and pain scores were minimal in the immediate post op period in the postoperative recovery unit. Time to first analgesia was 4 hours postoperatively – with paracetamol 1g administered. This was given at 6 hourly intervals strictly for 5 days post surgery, along with celecoxib 200mg BD as prescribed by the surgeon regardless of pain scores. Oral oxycodone was prescribed as a rescue analgesic for pain scores > 3/10, but the patient did not require any dose. Neither was there nausea or vomiting. The patient was discharged on postoperative day 5. This case has reinforced the use of dexmedetomidine as an adjunct in general surgery cases, highlighting its excellent opioid-sparing effects. In the entire patient’s hospital stay, the only dose of opioid he received was 75mcg of fentanyl at the time of anaesthetic induction. The patient suffered no opioid adverse effects such as nausea, vomiting or postoperative ileus, and pain scores varied from 0-2/10. However, intravenous lignocaine infusion was also used in this instance, which would have helped improve pain scores. Paracetamol, lignocaine, and dexmedetomidine is thus an effective, opioid-sparing combination of multi-modal analgesia for major abdominal surgery cases.Keywords: analgesia, dexmedetomidine, general surgery, opioid sparing
Procedia PDF Downloads 135438 Single Cell Rna Sequencing Operating from Benchside to Bedside: An Interesting Entry into Translational Genomics
Authors: Leo Nnamdi Ozurumba-Dwight
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Single-cell genomic analytical systems have proved to be a platform to isolate bulk cells into selected single cells for genomic, proteomic, and related metabolomic studies. This is enabling systematic investigations of the level of heterogeneity in a diverse and wide pool of cell populations. Single cell technologies, embracing techniques such as high parameter flow cytometry, single-cell sequencing, and high-resolution images are playing vital roles in these investigations on messenger ribonucleic acid (mRNA) molecules and related gene expressions in tracking the nature and course of disease conditions. This entails targeted molecular investigations on unit cells that help us understand cell behavoiur and expressions, which can be examined for their health implications on the health state of patients. One of the vital good sides of single-cell RNA sequencing (scRNA seq) is its probing capacity to detect deranged or abnormal cell populations present within homogenously perceived pooled cells, which would have evaded cursory screening on the pooled cell populations of biological samples obtained as part of diagnostic procedures. Despite conduction of just single-cell transcriptome analysis, scRNAseq now permits comparison of the transcriptome of the individual cells, which can be evaluated for gene expressional patterns that depict areas of heterogeneity with pharmaceutical drug discovery and clinical treatment applications. It is vital to strictly work through the tools of investigations from wet lab to bioinformatics and computational tooled analyses. In the precise steps for scRNAseq, it is critical to do thorough and effective isolation of viable single cells from the tissues of interest using dependable techniques (such as FACS) before proceeding to lysis, as this enhances the appropriate picking of quality mRNA molecules for subsequent sequencing (such as by the use of Polymerase Chain Reaction machine). Interestingly, scRNAseq can be deployed to analyze various types of biological samples such as embryos, nervous systems, tumour cells, stem cells, lymphocytes, and haematopoietic cells. In haematopoietic cells, it can be used to stratify acute myeloid leukemia patterns in patients, sorting them out into cohorts that enable re-modeling of treatment regimens based on stratified presentations. In immunotherapy, it can furnish specialist clinician-immunologist with tools to re-model treatment for each patient, an attribute of precision medicine. Finally, the good predictive attribute of scRNAseq can help reduce the cost of treatment for patients, thus attracting more patients who would have otherwise been discouraged from seeking quality clinical consultation help due to perceived high cost. This is a positive paradigm shift for patients’ attitudes primed towards seeking treatment.Keywords: immunotherapy, transcriptome, re-modeling, mRNA, scRNA-seq
Procedia PDF Downloads 176437 The Influence of the State on the Internal Governance of Universities: A Comparative Study of Quebec (Canada) and Western Systems
Authors: Alexandre Beaupré-Lavallée, Pier-André Bouchard St-Amant, Nathalie Beaulac
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The question of internal governance of universities is a political and scientific debate in the province of Quebec (Canada). Governments have called or set up inquiries on the subject on three separate occasions since the complete overhaul of the educational system in the 1960s: the Parent Commission (1967), the Angers Commission (1979) and the Summit on Higher Education (2013). All three produced reports that highlight the constant tug-of-war for authority and legitimacy within universities. Past and current research that cover Quebec universities have studied several aspects regarding internal governance: the structure as a whole or only some parts of it, the importance of certain key aspects such as collegiality or strategic planning, or of stakeholders, such as students or administrators. External governance has also been studied, though, as with internal governance, research so far as only covered well delineated topics like financing policies or overall impacts from wider societal changes such as New Public Management. The latter, NPM, is often brought up as a factor that influenced overall State policies like “steering-at-a-distance” or internal shifts towards “managerialism”. Yet, to the authors’ knowledge, there is not study that specifically maps how the Quebec State formally influences internal governance. In addition, most studies about the Quebec university system are not comparative in nature. This paper presents a portion of the results produced by a 2022- 2023 study that aims at filling these last two gaps in knowledge. Building on existing governmental, institutional, and scientific papers, we documented the legal and regulatory framework of the Quebec university system and of twenty-one other university systems in North America and Europe (2 in Canada, 2 in the USA, 16 in Europe, with the addition of the European Union as a distinct case). This allowed us to map the presence (or absence) of mandatory structures of governance enforced by States, as well as their composition. Then, using Clark’s “triangle of coordination”, we analyzed each system to assess the relative influences of the market, the State and the collegium upon the governance model put in place. Finally, we compared all 21 non-Quebec systems to characterize the province’s policies in an internal perspective. Preliminary findings are twofold. First, when all systems are placed on a continuum ranging from “no State interference in internal governance” to “State-run universities”, Quebec comes in the middle of the pack, albeit with a slight lean towards institutional freedom. When it comes to overall governance (like Boards and Senates), the dual nature of the Quebec system, with its public university and its coopted yet historically private (or ecclesiastic) institutions, in fact mimics the duality of all university systems. Second, however, is the sheer abundance of legal and regulatory mandates from the State that, while not expressly addressing internal governance, seems to require de facto modification of internal governance structure and dynamics to ensure institutional conformity with said mandates. This study is only a fraction of the research that is needed to better understand State-universities interactions regarding governance. We hope it will set the stage for future studies.Keywords: internal governance, legislation, Quebec, universities
Procedia PDF Downloads 84436 Interplay of Material and Cycle Design in a Vacuum-Temperature Swing Adsorption Process for Biogas Upgrading
Authors: Federico Capra, Emanuele Martelli, Matteo Gazzani, Marco Mazzotti, Maurizio Notaro
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Natural gas is a major energy source in the current global economy, contributing to roughly 21% of the total primary energy consumption. Production of natural gas starting from renewable energy sources is key to limit the related CO2 emissions, especially for those sectors that heavily rely on natural gas use. In this context, biomethane produced via biogas upgrading represents a good candidate for partial substitution of fossil natural gas. The upgrading process of biogas to biomethane consists in (i) the removal of pollutants and impurities (e.g. H2S, siloxanes, ammonia, water), and (ii) the separation of carbon dioxide from methane. Focusing on the CO2 removal process, several technologies can be considered: chemical or physical absorption with solvents (e.g. water, amines), membranes, adsorption-based systems (PSA). However, none emerged as the leading technology, because of (i) the heterogeneity in plant size, ii) the heterogeneity in biogas composition, which is strongly related to the feedstock type (animal manure, sewage treatment, landfill products), (iii) the case-sensitive optimal tradeoff between purity and recovery of biomethane, and iv) the destination of the produced biomethane (grid injection, CHP applications, transportation sector). With this contribution, we explore the use of a technology for biogas upgrading and we compare the resulting performance with benchmark technologies. The proposed technology makes use of a chemical sorbent, which is engineered by RSE and consists of Di-Ethanol-Amine deposited on a solid support made of γ-Alumina, to chemically adsorb the CO2 contained in the gas. The material is packed into fixed beds that cyclically undergo adsorption and regeneration steps. CO2 is adsorbed at low temperature and ambient pressure (or slightly above) while the regeneration is carried out by pulling vacuum and increasing the temperature of the bed (vacuum-temperature swing adsorption - VTSA). Dynamic adsorption tests were performed by RSE and were used to tune the mathematical model of the process, including material and transport parameters (i.e. Langmuir isotherms data and heat and mass transport). Based on this set of data, an optimal VTSA cycle was designed. The results enabled a better understanding of the interplay between material and cycle tuning. As exemplary application, the upgrading of biogas for grid injection, produced by an anaerobic digester (60-70% CO2, 30-40% CH4), for an equivalent size of 1 MWel was selected. A plant configuration is proposed to maximize heat recovery and minimize the energy consumption of the process. The resulting performances are very promising compared to benchmark solutions, which make the VTSA configuration a valuable alternative for biomethane production starting from biogas.Keywords: biogas upgrading, biogas upgrading energetic cost, CO2 adsorption, VTSA process modelling
Procedia PDF Downloads 277435 Attitudes of Gratitude: An Analysis of 30 Cancer Patient Narratives Published by Leading U.S. Cancer Care Centers
Authors: Maria L. McLeod
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This study examines the ways in which cancer patient narratives are portrayed and framed on the websites of three leading U.S. cancer care centers –The University of Texas MD Anderson Cancer Center in Houston, Memorial Sloan Kettering Cancer Center in New York, and Seattle Cancer Care Alliance. Thirty patient stories, ten from each cancer center website blog, were analyzed using qualitative and quantitative textual analysis of unstructured data, documenting repeated use of specific metaphors and tropes while charting common themes and other elements of story structure and content. Patient narratives were coded using grounded theory as the basis for conducting emergent qualitative research. As part of a systematic, inductive approach to collecting and analyzing data, recurrent and unique themes were examined and compared in terms of positive and negative framing, patient agency, and institutional praise. All three of these cancer care centers are teaching hospitals with university affiliations, that emphasizes an evidence-based scientific approach to treatment that utilizes the latest research and cutting-edge techniques and technology. Thus, the use of anecdotal evidence presented in patient narratives could be perceived as being in conflict with this evidence-based model, as the patient stories are not an accurate representation of scientific outcomes related to developing cancer, cancer reoccurrence, or cancer outcomes. The representative patient narratives tend to exclude or downplay adverse responses to treatment, survival rates, integrative and/or complementary cancer treatments, cancer prevention and causes, and barriers to treatment, such as the limitation of insurance plans, costs of treatment, and/or other issues related to access, potentially contributing to false narratives and inaccurate notions of cancer prevention, cancer care treatment and the potential for a cure. Both quantitative and qualitative findings demonstrate that cancer patient stories featured on the blogsites of the nation’s top cancer care centers deemphasize patient agency and, instead, emphasize deference and gratitude toward the institutions where the featured patients received treatment. Along these lines, language choices reflect positive framing of the cancer experience. Accompanying portrait photos of healthy appearing subjects as well as positive-framed headlines, subheads, and pull quotes function similarly, reflecting hopeful, transformative experiences and outcomes over hardship and suffering. Although patient narratives include real, factual scientific details and descriptions of actual events, the stories lack references to more negative realities of cancer diagnosis and treatment. Instead, they emphasize the triumph of survival by which the cancer care center, in the savior/hero role, enables the patient’s success, represented as a cathartic medical journey.Keywords: cancer framing, cancer stories, medical gaze, patient narratives
Procedia PDF Downloads 160434 Ruta graveolens Fingerprints Obtained with Reversed-Phase Gradient Thin-Layer Chromatography with Controlled Solvent Velocity
Authors: Adrian Szczyrba, Aneta Halka-Grysinska, Tomasz Baj, Tadeusz H. Dzido
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Since prehistory, plants were constituted as an essential source of biologically active substances in folk medicine. One of the examples of medicinal plants is Ruta graveolens L. For a long time, Ruta g. herb has been famous for its spasmolytic, diuretic, or anti-inflammatory therapeutic effects. The wide spectrum of secondary metabolites produced by Ruta g. includes flavonoids (eg. rutin, quercetin), coumarins (eg. bergapten, umbelliferone) phenolic acids (eg. rosmarinic acid, chlorogenic acid), and limonoids. Unfortunately, the presence of produced substances is highly dependent on environmental factors like temperature, humidity, or soil acidity; therefore standardization is necessary. There were many attempts of characterization of various phytochemical groups (eg. coumarins) of Ruta graveolens using the normal – phase thin-layer chromatography (TLC). However, due to the so-called general elution problem, usually, some components remained unseparated near the start or finish line. Therefore Ruta graveolens is a very good model plant. Methanol and petroleum ether extract from its aerial parts were used to demonstrate the capabilities of the new device for gradient thin-layer chromatogram development. The development of gradient thin-layer chromatograms in the reversed-phase system in conventional horizontal chambers can be disrupted by problems associated with an excessive flux of the mobile phase to the surface of the adsorbent layer. This phenomenon is most likely caused by significant differences between the surface tension of the subsequent fractions of the mobile phase. An excessive flux of the mobile phase onto the surface of the adsorbent layer distorts the flow of the mobile phase. The described effect produces unreliable, and unrepeatable results, causing blurring and deformation of the substance zones. In the prototype device, the mobile phase solution is delivered onto the surface of the adsorbent layer with controlled velocity (by moving pipette driven by 3D machine). The delivery of the solvent to the adsorbent layer is equal to or lower than that of conventional development. Therefore chromatograms can be developed with optimal linear mobile phase velocity. Furthermore, under such conditions, there is no excess of eluent solution on the surface of the adsorbent layer so the higher performance of the chromatographic system can be obtained. Directly feeding the adsorbent layer with eluent also enables to perform convenient continuous gradient elution practically without the so-called gradient delay. In the study, unique fingerprints of methanol and petroleum ether extracts of Ruta graveolens aerial parts were obtained with stepwise gradient reversed-phase thin-layer chromatography. Obtained fingerprints under different chromatographic conditions will be compared. The advantages and disadvantages of the proposed approach to chromatogram development with controlled solvent velocity will be discussed.Keywords: fingerprints, gradient thin-layer chromatography, reversed-phase TLC, Ruta graveolens
Procedia PDF Downloads 288433 Parametric Study for Obtaining the Structural Response of Segmental Tunnels in Soft Soil by Using No-Linear Numerical Models
Authors: Arturo Galván, Jatziri Y. Moreno-Martínez, Israel Enrique Herrera Díaz, José Ramón Gasca Tirado
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In recent years, one of the methods most used for the construction of tunnels in soft soil is the shield-driven tunneling. The advantage of this construction technique is that it allows excavating the tunnel while at the same time a primary lining is placed, which consists of precast segments. There are joints between segments, also called longitudinal joints, and joints between rings (called as circumferential joints). This is the reason because of this type of constructions cannot be considered as a continuous structure. The effect of these joints influences in the rigidity of the segmental lining and therefore in its structural response. A parametric study was performed to take into account the effect of different parameters in the structural response of typical segmental tunnels built in soft soil by using non-linear numerical models based on Finite Element Method by means of the software package ANSYS v. 11.0. In the first part of this study, two types of numerical models were performed. In the first one, the segments were modeled by using beam elements based on Timoshenko beam theory whilst the segment joints were modeled by using inelastic rotational springs considering the constitutive moment-rotation relation proposed by Gladwell. In this way, the mechanical behavior of longitudinal joints was simulated. On the other hand for simulating the mechanical behavior of circumferential joints elastic springs were considered. As well as, the stability given by the soil was modeled by means of elastic-linear springs. In the second type of models, the segments were modeled by means of three-dimensional solid elements and the joints with contact elements. In these models, the zone of the joints is modeled as a discontinuous (increasing the computational effort) therefore a discrete model is obtained. With these contact elements the mechanical behavior of joints is simulated considering that when the joint is closed, there is transmission of compressive and shear stresses but not of tensile stresses and when the joint is opened, there is no transmission of stresses. This type of models can detect changes in the geometry because of the relative movement of the elements that form the joints. A comparison between the numerical results with two types of models was carried out. In this way, the hypothesis considered in the simplified models were validated. In addition, the numerical models were calibrated with (Lab-based) experimental results obtained from the literature of a typical tunnel built in Europe. In the second part of this work, a parametric study was performed by using the simplified models due to less used computational effort compared to complex models. In the parametric study, the effect of material properties, the geometry of the tunnel, the arrangement of the longitudinal joints and the coupling of the rings were studied. Finally, it was concluded that the mechanical behavior of segment and ring joints and the arrangement of the segment joints affect the global behavior of the lining. As well as, the effect of the coupling between rings modifies the structural capacity of the lining.Keywords: numerical models, parametric study, segmental tunnels, structural response
Procedia PDF Downloads 229432 Developing Digital Competencies in Aboriginal Students through University-College Partnerships
Authors: W. S. Barber, S. L. King
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This paper reports on a pilot project to develop a collaborative partnership between a community college in rural northern Ontario, Canada, and an urban university in the greater Toronto area in Oshawa, Canada. Partner institutions will collaborate to address learning needs of university applicants whose goals are to attain an undergraduate university BA in Educational Studies and Digital Technology degree, but who may not live in a geographical location that would facilitate this pathways process. The UOIT BA degree is attained through a 2+2 program, where students with a 2 year college diploma or equivalent can attain a four year undergraduate degree. The goals reported on the project are as: 1. Our aim is to expand the BA program to include an additional stream which includes serious educational games, simulations and virtual environments, 2. Develop fully (using both synchronous and asynchronous technologies) online learning modules for use by university applicants who otherwise are not geographically located close to a physical university site, 3. Assess the digital competencies of all students, including members of local, distance and Indigenous communities using a validated tool developed and tested by UOIT across numerous populations. This tool, the General Technical Competency Use and Scale (GTCU) will provide the collaborating institutions with data that will allow for analyzing how well students are prepared to succeed in fully online learning communities. Philosophically, the UOIT BA program is based on a fully online learning communities model (FOLC) that can be accessed from anywhere in the world through digital learning environments via audio video conferencing tools such as Adobe Connect. It also follows models of adult learning and mobile learning, and makes a university degree accessible to the increasing demographic of adult learners who may use mobile devices to learn anywhere anytime. The program is based on key principles of Problem Based Learning, allowing students to build their own understandings through the co-design of the learning environment in collaboration with the instructors and their peers. In this way, this degree allows students to personalize and individualize the learning based on their own culture, background and professional/personal experiences. Using modified flipped classroom strategies, students are able to interrogate video modules on their own time in preparation for one hour discussions occurring in video conferencing sessions. As a consequence of the program flexibility, students may continue to work full or part time. All of the partner institutions will co-develop four new modules, administer the GTCU and share data, while creating a new stream of the UOIT BA degree. This will increase accessibility for students to bridge from community colleges to university through a fully digital environment. We aim to work collaboratively with Indigenous elders, community members and distance education instructors to increase opportunities for more students to attain a university education.Keywords: aboriginal, college, competencies, digital, universities
Procedia PDF Downloads 215431 Case-Based Reasoning for Modelling Random Variables in the Reliability Assessment of Existing Structures
Authors: Francesca Marsili
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The reliability assessment of existing structures with probabilistic methods is becoming an increasingly important and frequent engineering task. However probabilistic reliability methods are based on an exhaustive knowledge of the stochastic modeling of the variables involved in the assessment; at the moment standards for the modeling of variables are absent, representing an obstacle to the dissemination of probabilistic methods. The framework according to probability distribution functions (PDFs) are established is represented by the Bayesian statistics, which uses Bayes Theorem: a prior PDF for the considered parameter is established based on information derived from the design stage and qualitative judgments based on the engineer past experience; then, the prior model is updated with the results of investigation carried out on the considered structure, such as material testing, determination of action and structural properties. The application of Bayesian statistics arises two different kind of problems: 1. The results of the updating depend on the engineer previous experience; 2. The updating of the prior PDF can be performed only if the structure has been tested, and quantitative data that can be statistically manipulated have been collected; performing tests is always an expensive and time consuming operation; furthermore, if the considered structure is an ancient building, destructive tests could compromise its cultural value and therefore should be avoided. In order to solve those problems, an interesting research path is represented by investigating Artificial Intelligence (AI) techniques that can be useful for the automation of the modeling of variables and for the updating of material parameters without performing destructive tests. Among the others, one that raises particular attention in relation to the object of this study is constituted by Case-Based Reasoning (CBR). In this application, cases will be represented by existing buildings where material tests have already been carried out and an updated PDFs for the material mechanical parameters has been computed through a Bayesian analysis. Then each case will be composed by a qualitative description of the material under assessment and the posterior PDFs that describe its material properties. The problem that will be solved is the definition of PDFs for material parameters involved in the reliability assessment of the considered structure. A CBR system represent a good candi¬date in automating the modelling of variables because: 1. Engineers already draw an estimation of the material properties based on the experience collected during the assessment of similar structures, or based on similar cases collected in literature or in data-bases; 2. Material tests carried out on structure can be easily collected from laboratory database or from literature; 3. The system will provide the user of a reliable probabilistic description of the variables involved in the assessment that will also serve as a tool in support of the engineer’s qualitative judgments. Automated modeling of variables can help in spreading probabilistic reliability assessment of existing buildings in the common engineering practice, and target at the best intervention and further tests on the structure; CBR represents a technique which may help to achieve this.Keywords: reliability assessment of existing buildings, Bayesian analysis, case-based reasoning, historical structures
Procedia PDF Downloads 337430 State, Public Policies, and Rights: Public Expenditure and Social and Welfare Policies in America, as Opposed to Argentina
Authors: Mauro Cristeche
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This paper approaches the intervention of the American State in the social arena and the modeling of the rights system from the Argentinian experience, by observing the characteristics of its federal budgetary system, the evolution of social public spending and welfare programs in recent years, labor and poverty statistics, and the changes on the labor market structure. The analysis seeks to combine different methodologies and sources: in-depth interviews with specialists, analysis of theoretical and mass-media material, and statistical sources. Among the results, it could be mentioned that the tendency to state interventionism (what has been called ‘nationalization of social life’) is quite evident in the United States, and manifests itself in multiple forms. The bibliography consulted, and the experts interviewed pointed out this increase of the state presence in historical terms (beyond short-term setbacks) in terms of increase of public spending, fiscal pressure, public employment, protective and control mechanisms, the extension of welfare policies to the poor sectors, etc. In fact, despite the significant differences between both countries, the United States and Argentina have common patterns of behavior in terms of the aforementioned phenomena. On the other hand, dissimilarities are also important. Some of them are determined by each country's own political history. The influence of political parties on the economic model seems more decisive in the United States than in Argentina, where the tendency to state interventionism is more stable. The centrality of health spending is evident in America, while in Argentina that discussion is more concentrated in the social security system and public education. The biggest problem of the labor market in the United States is the disqualification as a consequence of the technological development while in Argentina it is a result of its weakness. Another big difference is the huge American public spending on Defense. Then, the more federal character of the American State is also a factor of differential analysis against a centralized Argentine state. American public employment (around 10%) is comparatively quite lower than the Argentinian (around 18%). The social statistics show differences, but inequality and poverty have been growing as a trend in the last decades in both countries. According to public rates, poverty represents 14% in The United States and 33% in Argentina. American public spending is important (welfare spending and total public spending represent around 12% and 34% of GDP, respectively), but a bit lower than Latin-American or European average). In both cases, the tendency to underemployment and disqualification unemployment does not assume a serious gravity. Probably one of the most important aspects of the analysis is that private initiative and public intervention are much more intertwined in the United States, which makes state intervention more ‘fuzzy’, while in Argentina the difference is clearer. Finally, the power of its accumulation of capital and, more specifically, of the industrial and services sectors in the United States, which continues to be the engine of the economy, express great differences with Argentina, supported by its agro-industrial power and its public sector.Keywords: state intervention, welfare policies, labor market, system of rights, United States of America
Procedia PDF Downloads 131429 Production and Characterization of Biochars from Torrefaction of Biomass
Authors: Serdar Yaman, Hanzade Haykiri-Acma
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Biomass is a CO₂-neutral fuel that is renewable and sustainable along with having very huge global potential. Efficient use of biomass in power generation and production of biomass-based biofuels can mitigate the greenhouse gasses (GHG) and reduce dependency on fossil fuels. There are also other beneficial effects of biomass energy use such as employment creation and pollutant reduction. However, most of the biomass materials are not capable of competing with fossil fuels in terms of energy content. High moisture content and high volatile matter yields of biomass make it low calorific fuel, and it is very significant concern over fossil fuels. Besides, the density of biomass is generally low, and it brings difficulty in transportation and storage. These negative aspects of biomass can be overcome by thermal pretreatments that upgrade the fuel property of biomass. That is, torrefaction is such a thermal process in which biomass is heated up to 300ºC under non-oxidizing conditions to avoid burning of the material. The treated biomass is called as biochar that has considerably lower contents of moisture, volatile matter, and oxygen compared to the parent biomass. Accordingly, carbon content and the calorific value of biochar increase to the level which is comparable with that of coal. Moreover, hydrophilic nature of untreated biomass that leads decay in the structure is mostly eliminated, and the surface properties of biochar turn into hydrophobic character upon torrefaction. In order to investigate the effectiveness of torrefaction process on biomass properties, several biomass species such as olive milling residue (OMR), Rhododendron (small shrubby tree with bell-shaped flowers), and ash tree (timber tree) were chosen. The fuel properties of these biomasses were analyzed through proximate and ultimate analyses as well as higher heating value (HHV) determination. For this, samples were first chopped and ground to a particle size lower than 250 µm. Then, samples were subjected to torrefaction in a horizontal tube furnace by heating from ambient up to temperatures of 200, 250, and 300ºC at a heating rate of 10ºC/min. The biochars obtained from this process were also tested by the methods applied to the parent biomass species. Improvement in the fuel properties was interpreted. That is, increasing torrefaction temperature led to regular increases in the HHV in OMR, and the highest HHV (6065 kcal/kg) was gained at 300ºC. Whereas, torrefaction at 250ºC was seen optimum for Rhododendron and ash tree since torrefaction at 300ºC had a detrimental effect on HHV. On the other hand, the increase in carbon contents and reduction in oxygen contents were determined. Burning characteristics of the biochars were also studied using thermal analysis technique. For this purpose, TA Instruments SDT Q600 model thermal analyzer was used and the thermogravimetric analysis (TGA), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), and differential thermal analysis (DTA) curves were compared and interpreted. It was concluded that torrefaction is an efficient method to upgrade the fuel properties of biomass and the biochars from which have superior characteristics compared to the parent biomasses.Keywords: biochar, biomass, fuel upgrade, torrefaction
Procedia PDF Downloads 373428 Waveguiding in an InAs Quantum Dots Nanomaterial for Scintillation Applications
Authors: Katherine Dropiewski, Michael Yakimov, Vadim Tokranov, Allan Minns, Pavel Murat, Serge Oktyabrsky
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InAs Quantum Dots (QDs) in a GaAs matrix is a well-documented luminescent material with high light yield, as well as thermal and ionizing radiation tolerance due to quantum confinement. These benefits can be leveraged for high-efficiency, room temperature scintillation detectors. The proposed scintillator is composed of InAs QDs acting as luminescence centers in a GaAs stopping medium, which also acts as a waveguide. This system has appealing potential properties, including high light yield (~240,000 photons/MeV) and fast capture of photoelectrons (2-5ps), orders of magnitude better than currently used inorganic scintillators, such as LYSO or BaF2. The high refractive index of the GaAs matrix (n=3.4) ensures light emitted by the QDs is waveguided, which can be collected by an integrated photodiode (PD). Scintillation structures were grown using Molecular Beam Epitaxy (MBE) and consist of thick GaAs waveguiding layers with embedded sheets of modulation p-type doped InAs QDs. An AlAs sacrificial layer is grown between the waveguide and the GaAs substrate for epitaxial lift-off to separate the scintillator film and transfer it to a low-index substrate for waveguiding measurements. One consideration when using a low-density material like GaAs (~5.32 g/cm³) as a stopping medium is the matrix thickness in the dimension of radiation collection. Therefore, luminescence properties of very thick (4-20 microns) waveguides with up to 100 QD layers were studied. The optimization of the medium included QD shape, density, doping, and AlGaAs barriers at the waveguide surfaces to prevent non-radiative recombination. To characterize the efficiency of QD luminescence, low temperature photoluminescence (PL) (77-450 K) was measured and fitted using a kinetic model. The PL intensity degrades by only 40% at RT, with an activation energy for electron escape from QDs to the barrier of ~60 meV. Attenuation within the waveguide (WG) is a limiting factor for the lateral size of a scintillation detector, so PL spectroscopy in the waveguiding configuration was studied. Spectra were measured while the laser (630 nm) excitation point was scanned away from the collecting fiber coupled to the edge of the WG. The QD ground state PL peak at 1.04 eV (1190 nm) was inhomogeneously broadened with FWHM of 28 meV (33 nm) and showed a distinct red-shift due to self-absorption in the QDs. Attenuation stabilized after traveling over 1 mm through the WG, at about 3 cm⁻¹. Finally, a scintillator sample was used to test detection and evaluate timing characteristics using 5.5 MeV alpha particles. With a 2D waveguide and a small area of integrated PD, the collected charge averaged 8.4 x10⁴ electrons, corresponding to a collection efficiency of about 7%. The scintillation response had 80 ps noise-limited time resolution and a QD decay time of 0.6 ns. The data confirms unique properties of this scintillation detector which can be potentially much faster than any currently used inorganic scintillator.Keywords: GaAs, InAs, molecular beam epitaxy, quantum dots, III-V semiconductor
Procedia PDF Downloads 256427 Correlation between Defect Suppression and Biosensing Capability of Hydrothermally Grown ZnO Nanorods
Authors: Mayoorika Shukla, Pramila Jakhar, Tejendra Dixit, I. A. Palani, Vipul Singh
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Biosensors are analytical devices with wide range of applications in biological, chemical, environmental and clinical analysis. It comprises of bio-recognition layer which has biomolecules (enzymes, antibodies, DNA, etc.) immobilized over it for detection of analyte and transducer which converts the biological signal into the electrical signal. The performance of biosensor primarily the depends on the bio-recognition layer and therefore it has to be chosen wisely. In this regard, nanostructures of metal oxides such as ZnO, SnO2, V2O5, and TiO2, etc. have been explored extensively as bio-recognition layer. Recently, ZnO has the attracted attention of researchers due to its unique properties like high iso-electric point, biocompatibility, stability, high electron mobility and high electron binding energy, etc. Although there have been many reports on usage of ZnO as bio-recognition layer but to the authors’ knowledge, none has ever observed correlation between optical properties like defect suppression and biosensing capability of the sensor. Here, ZnO nanorods (ZNR) have been synthesized by a low cost, simple and low-temperature hydrothermal growth process, over Platinum (Pt) coated glass substrate. The ZNR have been synthesized in two steps viz. initially a seed layer was coated over substrate (Pt coated glass) followed by immersion of it into nutrient solution of Zinc nitrate and Hexamethylenetetramine (HMTA) with in situ addition of KMnO4. The addition of KMnO4 was observed to have a profound effect over the growth rate anisotropy of ZnO nanostructures. Clustered and powdery growth of ZnO was observed without addition of KMnO4, although by addition of it during the growth, uniform and crystalline ZNR were found to be grown over the substrate. Moreover, the same has resulted in suppression of defects as observed by Normalized Photoluminescence (PL) spectra since KMnO4 is a strong oxidizing agent which provides an oxygen rich growth environment. Further, to explore the correlation between defect suppression and biosensing capability of the ZNR Glucose oxidase (Gox) was immobilized over it, using physical adsorption technique followed by drop casting of nafion. Here the main objective of the work was to analyze effect of defect suppression over biosensing capability, and therefore Gox has been chosen as model enzyme, and electrochemical amperometric glucose detection was performed. The incorporation of KMnO4 during growth has resulted in variation of optical and charge transfer properties of ZNR which in turn were observed to have deep impact on biosensor figure of merits. The sensitivity of biosensor was found to increase by 12-18 times, due to variations introduced by addition of KMnO4 during growth. The amperometric detection of glucose in continuously stirred buffer solution was performed. Interestingly, defect suppression has been observed to contribute towards the improvement of biosensor performance. The detailed mechanism of growth of ZNR along with the overall influence of defect suppression on the sensing capabilities of the resulting enzymatic electrochemical biosensor and different figure of merits of the biosensor (Glass/Pt/ZNR/Gox/Nafion) will be discussed during the conference.Keywords: biosensors, defects, KMnO4, ZnO nanorods
Procedia PDF Downloads 282426 Intriguing Modulations in the Excited State Intramolecular Proton Transfer Process of Chrysazine Governed by Host-Guest Interactions with Macrocyclic Molecules
Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury
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Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies
Procedia PDF Downloads 121