Search results for: velocity and trajectory control
2500 Generalized Additive Model for Estimating Propensity Score
Authors: Tahmidul Islam
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Propensity Score Matching (PSM) technique has been widely used for estimating causal effect of treatment in observational studies. One major step of implementing PSM is estimating the propensity score (PS). Logistic regression model with additive linear terms of covariates is most used technique in many studies. Logistics regression model is also used with cubic splines for retaining flexibility in the model. However, choosing the functional form of the logistic regression model has been a question since the effectiveness of PSM depends on how accurately the PS been estimated. In many situations, the linearity assumption of linear logistic regression may not hold and non-linear relation between the logit and the covariates may be appropriate. One can estimate PS using machine learning techniques such as random forest, neural network etc for more accuracy in non-linear situation. In this study, an attempt has been made to compare the efficacy of Generalized Additive Model (GAM) in various linear and non-linear settings and compare its performance with usual logistic regression. GAM is a non-parametric technique where functional form of the covariates can be unspecified and a flexible regression model can be fitted. In this study various simple and complex models have been considered for treatment under several situations (small/large sample, low/high number of treatment units) and examined which method leads to more covariate balance in the matched dataset. It is found that logistic regression model is impressively robust against inclusion quadratic and interaction terms and reduces mean difference in treatment and control set equally efficiently as GAM does. GAM provided no significantly better covariate balance than logistic regression in both simple and complex models. The analysis also suggests that larger proportion of controls than treatment units leads to better balance for both of the methods.Keywords: accuracy, covariate balances, generalized additive model, logistic regression, non-linearity, propensity score matching
Procedia PDF Downloads 3672499 Effect of Austenitizing Temperature, Soaking Time and Grain Size on Charpy Impact Toughness of Quenched and Tempered Steel
Authors: S. Gupta, R. Sarkar, S. Pathak, D. H. Kela, A. Pramanick, P. Talukdar
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Low alloy quenched and tempered steels are typically used in cast railway components such as knuckles, yokes, and couplers. Since these components experience extensive impact loading during their service life, adequate impact toughness of these grades need to be ensured to avoid catastrophic failure of parts in service. Because of the general availability of Charpy V Test equipment, Charpy test is the most common and economical means to evaluate the impact toughness of materials and is generally used in quality control applications. With this backdrop, an experiment was designed to evaluate the effect of austenitizing temperature, soaking time and resultant grain size on the Charpy impact toughness and the related fracture mechanisms in a quenched and tempered low alloy steel, with the aim of optimizing the heat treatment parameters (i.e. austenitizing temperature and soaking time) with respect to impact toughness. In the first phase, samples were austenitized at different temperatures viz. 760, 800, 840, 880, 920 and 960°C, followed by quenching and tempering at 600°C for 4 hours. In the next phase, samples were subjected to different soaking times (0, 2, 4 and 6 hours) at a fixed austenitizing temperature (980°C), followed by quenching and tempering at 600°C for 4 hours. The samples corresponding to different test conditions were then subjected to instrumented Charpy tests at -40°C and energy absorbed were recorded. Subsequently, microstructure and fracture surface of samples corresponding to different test conditions were observed under scanning electron microscope, and the corresponding grain sizes were measured. In the final stage, austenitizing temperature, soaking time and measured grain sizes were correlated with impact toughness and the fracture morphology and mechanism.Keywords: heat treatment, grain size, microstructure, retained austenite and impact toughness
Procedia PDF Downloads 3382498 Experimental Research on Neck Thinning Dynamics of Droplets in Cross Junction Microchannels
Authors: Yilin Ma, Zhaomiao Liu, Xiang Wang, Yan Pang
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Microscale droplets play an increasingly important role in various applications, including medical diagnostics, material synthesis, chemical engineering, and cell research due to features of high surface-to-volume ratio and tiny scale, which can significantly improve reaction rates, enhance heat transfer efficiency, enable high-throughput parallel studies as well as reduce reagent usage. As a mature technique to manipulate small amounts of liquids, droplet microfluidics could achieve the precise control of droplet parameters such as size, uniformity, structure, and thus has been widely adopted in the engineering and scientific research of multiple fields. Necking processes of the droplet in the cross junction microchannels are experimentally and theoretically investigated and dynamic mechanisms of the neck thinning in two different regimes are revealed. According to evolutions of the minimum neck width and the thinning rate, the necking process is further divided into different stages and the main driving force during each stage is confirmed. Effects of the flow rates and the cross-sectional aspect ratio on the necking process as well as the neck profile at different stages are provided in detail. The distinct features of the two regimes in the squeezing stage are well captured by the theoretical estimations of the effective flow rate and the variations of the actual flow rates in different channels are reasonably reflected by the channel width ratio. In the collapsing stage, the quantitative relation between the minimum neck width and the remaining time is constructed to identify the physical mechanism.Keywords: cross junction, neck thinning, force analysis, inertial mechanism
Procedia PDF Downloads 1102497 Polystyrene Paste as a Substitute for a Portland Cement: A Solution to the Nigerian Dilemma
Authors: Lanre Oluwafemi Akinyemi
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The reduction of limestone to cement in Nigeria is expensive and requires huge amounts of energy. This significantly affects the cost of cement. Concrete is heavy: a cubic foot of it weighs about 150 lbs. and a cubic yard is about 4000 lbs. Thus a ready-mix truck with 9 cubic yards is carrying 36,000 lbs excluding the weight of the truck itself, thereby accumulating cost for also manufacturers. Therein lies the need to find a substitute for cement by using the polystyrene paste that benefits both the manufactures and the consumers. Polystyrene Paste Constructional Cement (PPCC), a patented material obtained by dissolving Waste EPS in volatile organic solvent, has recently been identified as a suitable binder/cement for construction and building material production. This paper illustrates the procedures of a test experiment undertaken to determine the splitting tensile strength of PPCC mortar compared to that of OPC (Ordinary Portland Cement). Expanded polystyrene was dissolved in gasoline to form a paste referred to as Polystyrene Paste Constructional Cement (PPCC). Mortars of mix ratios 1:4, 1:5, 1:6, 1:7 (PPCC: fine aggregate) batched by volume were used to produce 50mm x 100mm cylindrical PPCC mortar splitting tensile strength specimens. The control experiment was done by creating another series of cylindrical OPC mortar splitting tensile strength specimens following the same mix ratio used earlier. The PPCC cylindrical splitting tensile strength specimens were left to air-set, and the ones made with Ordinary Portland Cement (OPC) were demoded after 24 hours and cured in water. The cylindrical PPCC splitting tensile strength specimens were tested at 28 days and compared with those of the Ordinary Portland cement splitting tensile strength specimens. The result shows that hence for this two mixes, PPCC exhibits a better binding property than the OPC. With this my new invention I recommend the use of PPCC as a substitute for a Portland cement.Keywords: polystyrene paste, Portland cement, construction, mortar
Procedia PDF Downloads 1572496 The Effect of Acute Aerobic Exercise after Consumption of Four Different Diets on Serum Levels Irisin, Insulin and Glucose in Overweight Men
Authors: Majid Mardaniyan Ghahfarokhi, Abdolhamid Habibi, Majid Mohammad Shahi
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The combination of exercise and diet as the most important strategy to reduce weight and control obesity-related factors, including Irisin, Insulin, and Glucose was raised. The aim of this study was to investigate the effect of aerobic exercise combined with four different diets on serum levels of Irisin, Insulin, and Glucose in overweight men. Methods: In this quasi-experimental study, 8 overweight men (BMI 29.23±0.47) with average age of (23±1.6) voluntarily participated in 4 sessions by one-week interval. The study was done in exercise physiology lab. In each session, subjects performed a 30 minutes treadmill test with 60-70% of maximum heart rate, after consuming a high carbohydrate, high-fat, high-protein and normal diet. For biochemical measurement, three blood samples were taken in fasting state, two hours after meals and after exercise Results: Statistical analysis of data showed that the serum levels of Irisin after consumption all four diets had been reduced which this reduce as a result of high-fat diet that were significantly (p ≤ 0/038). Serum concentration of Insulin and Glucose increased after consuming four diets. However, increase in serum Insulin and Glucose was significant only after consuming high-carbohydrate diet (Respectively p ≤ 0/001, p ≤ 0/042). In addition, during exercise after consuming all four regular diet, high carbohydrate, high-protein and high-fat, Irisin significant increased significantly (Respectively p ≤ 0/021, p ≤ 0/049, p ≤ 0/001, P ≤ 0/003), Insulin decreased significantly (Respectively p ≤ 0/002, p ≤ 0/001, p ≤ 0/001, p ≤ 0/002) and Glucose were significantly reduced (Respectively p ≤ 0/001, p ≤ 0/001, P ≤ 0/001, p ≤ 0/002). After aerobic activity following the consumption of a high protein diet the highest increase in irisin levels, and after aerobic exercise following consumption of high carbohydrate diet the greatest decrease in insulin and glucose levels were observed. Conclusion: It seems that diet alone and exercises following different consumption diets can have a significant effect on Irisin, Insulin, and Glucose serum levels in overweight young men.Keywords: acute aerobic exercise, diet, irisin, overweight
Procedia PDF Downloads 2592495 Performance Evaluation of Cement Mortar with Crushed Stone Dust as Fine Aggregates
Authors: Pradeep Kumar
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The present work is based on application of cement mortar with natural sand and discontinuous steel fiber through which bending behavior of skinny beam was evaluated. This research is to study the effects of combining reinforcing steel meshes (continuous steel reinforcement) with discontinuous fibers as reinforcement in skinny walled Portland cement based cement mortar with crushed stone dust as a fine aggregate. The term ‘skinny’ means thickness of the beams is less than 25 mm. The main idea behind this combination is to satisfy the ultimate strength limit state through the steel mesh reinforcement (as a main reinforcement) and to control the cracking under service loads through fiber (Recron 3s) reinforcement (as secondary reinforcement). The main object of this study is to carry out the bending behavior of mortar reinforced thin beam with only one layer of steel mesh (with various transfer wire spacing) and with a recron 3s (Reliance) fifers. The wide experimental program with bending tests is undertaken. The following variables are investigated: (a) the reference mesh size - 25.4 x 25.4 mm and 50.8 x 50.8 mm; (b) the transverse wire spacing - 25.4 mm, 50.8 mm, and no transverse wires; (c) the type of fibers – Reliance (Recron 3s, 6mm length); and (d) the fiber volume fraction – 0.1% and 0.25%. Some of the main conclusions are: (a) the use of recron 3s fibers leads to a little better overall performance than that with no fiber; (b) an increase in equivalent stress is observed when 0.1% RF,0.25% R Fibers are used; (c) when 25.4 x 50.8 size steel mesh is used, no noticeable change in behavior is observed in comparison to specimens without fibers; and (d) for no fibers 0.1% and o.1% RF the transverse wire spacing has some little effect on the equivalent stress for RF fibers, the transverse wire has no influence but the equivalent stress are increased.Keywords: cement mortar, crushed stone dust, fibre, steel mesh
Procedia PDF Downloads 3122494 Nation Branding as Reframing: From the Perspective of Translation Studies
Authors: Ye Tian
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Soft power has replaced hard power and become one of the most attractive ways nations pursue to expand their international influence. One of the ways to improve a nation’s soft power is to commercialise the country and brand or rebrand it to the international audience, and thus attract interests or foreign investments. In this process, translation has often been regarded as merely a tool, and researches in it are either in translating literature as culture export or in how (in)accuracy of translation influences the branding campaign. This paper proposes to analyse nation branding campaign with framing theory, and thus gives an entry for translation studies to come to a central stage in today’s soft power research. To frame information or elements of a text, an event, or, as in this paper, a nation is to put them in a mental structure. This structure can be built by outsiders or by those who create the text, the event, or by citizens of the nation. To frame information like this can be regarded as a process of translation, as what translation does in its traditional meaning of ‘translating a text’ is to put a framework on the text to, deliberately or not, highlight some of the elements while hiding the others. In the discourse of nations, then, people unavoidably simplify a national image and put the nation into their imaginary framework. In this way, problems like stereotype and prejudice come into being. Meanwhile, if nations seek ways to frame or reframe themselves, they make efforts to have in control what and who they are in the eyes of international audiences, and thus make profits, economically or politically, from it. The paper takes African nations, which are usually perceived as a whole, and the United Kingdom as examples to justify passive and active framing process, and assesses both positive and negative influence framing has on nations. In conclusion, translation as framing causes problems like prejudice, and the image of a nation is not always in the hands of nation branders, but reframing the nation in a positive way has the potential to turn the tide.Keywords: framing, nation branding, stereotype, translation
Procedia PDF Downloads 1552493 The Role of Community Museum in Ethnic Identity: A Case of Tharu Cultural Museum and Research Center in Chitwan Nepal
Authors: Birendra Mahato, Shiva Narayan Chaudhary
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Tharus are indigenous inhabitants of the Tarai, the narrow strip of flat and fertile land that lies at the foothills of the Himalayas. They have unique rituals, festivals, and music, while their clothes and ornaments are similar to some ethnic groups of India. After the control of malaria in the Terai between 1955 to 1965, (with the help of the U.S. Government, the WHO and the government of Nepal) the rate of in-migration skyrocketed, particularly of Nepal’s hill people, whose culture, along with the use of the Western education system, was gradually adopted by the Tharus. Among the many challenges, the Tharus face is their assimilation into the dominant Nepali culture. .The Tharus are thus under threat of slowly losing their ethnic identity and cultural values. In order to preserve the indigenous Tharu Culture, Tharu Cultural Museum, and Research Center. It is a community based non-governmental and non-profitable museum established in 2005 by Tharu intellectuals, traditional leaders and youths. The main goal of the museum is to preserve Tharu culture through different activities with direct and indirect involvement of community people. It aims to preserve arts, culture, handicrafts, and artifacts related to Indigenous Tharu People. Similarly, the museum displays an exhibition about the Tharu histories, lives, culture, and their indigenous knowledge and skills. The paper aims to demonstrate that community museums can be one of the key hubs for the preservation of culture with the collection and promotion of cultural objects, artifacts, and intangible cultural heritages. The preservation of culture not only has contributed to establishing their ethnic identity but also has contributed to establishing their recognition of their political space in the mainstream politics - the constitution of Nepal has recognized Tharus to provide reservation for the political space.Keywords: community museum, tharu, , identity, culture
Procedia PDF Downloads 1332492 Anti-inflammatory and Hemostatic Activities of Methanolic Extract from Atriplex Halimus. Leaves
Authors: Yahia Massinissa, Benhouda Afaf, Benbia Souhila, Meddour Noura, Takellalet Karima, Zeroual Amina
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Introduction: chenopodiaceae family species are known for their important biological activity, in which Atriplex halimus belongs . However, the inflammatory effect of this plant leaves has not been studied. This work aimed at assessing the anti- inflammatory and hemostatic activities of the methanolic extract AHMeOH of Atriplex halimus’s leaves. Methods: The extract was obtained using sonication of leaves powder in 80 % methanol. The analysis of phenolic compounds was carried out using thin-layer chromatography (TLC).The anti-inflammatory activity was determined by studying the plasmical membrane stabilization and albumin denaturation inhibition, the hemostatic activity was evaluated by measuring the plasma in the blood. Results: Quantitative determination of total flavonoids reveals that AHMeOH is rich in flavonoids (16 ± 0.88 μg Q / mg extract) and polyphenols (20 ± 0.20 μg AG / mg extract). about anti-inflammatory activity, the tests show that AHMeOH has a significant effect (P≤0.05) of inhibiting hypotonic-induced hemolysis with concentrations (100 and 200 μg / ml) with 77.55 and 90% respectively, and heat-induced hemolysis with percentages 81.75% and 87.44% respectively with significant difference (P ≤0.05). The obtained results with this plant reveal that the inhibition of denaturation of albumin is dose dependent. The concentration of 400 μg / ml gives denaturation inhibition of 81.00 ± 17.70% and the concentration 600 μg / ml gives an effect of 82.95 ± 17.40%. Regarding the haemostatic activity our extract with the doses 10 mg / ml, 20 mg / ml and 30 mg / ml confer a decrease of the plasma recalcification time in the tube, these concentrations could prolong the time of coagulation significantly compared to the control (P≤0.001). This result is an interesting indication in favor of haemostatic activity of AHMeOH. Conclusion: Atriplex Halimus has a strong anti-inflammatory activity and constitutes a potential source for the development of new treatments.Keywords: albumin, atriplex halimus, hemostatic activity, methanolic extract
Procedia PDF Downloads 762491 The Effect of Super-Plasticizer and Ultra-sonic Process on the Carbon Nano Tubes Dispersion in Combination with Nano Silica in Cement Composites to Enhance Its Mechanical Properties
Authors: M.S. El-Feky, Passant Youssef, Mohamed I. Serag
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nowadays, nanotechnology is the main trend of research in different areas due to the new potential of using nanometer materials sized less than 100nm. Nanomaterials are needed in cement composites to act as bridging for Nano and micro-cracks to increase tensile strength, reduce the permeability of gases and water in concrete to solve corrosion problem, react with excess Calcium Hydroxide, produce additional C-S-H, act as filler materials to densify the cement matrix and increase its mechanical properties. The present study focuses on the effectiveness of super-plasticizers and ultrasonic processing on the dispersion of Carbon Nanotube at first in water and then in cement composites in combination with Nano silica to enhance the mechanical properties of cement composites. A qualitative analysis using a compressive strength test is conducted with a view to investigate the influence of different dispersion techniques on the mechanical properties of cement composites containing Carbon Nanotube (CNT) and Nano Silica (NS) particles with different percentages. In addition, micro-structural analysis was carried out to understand the surface morphology and microstructure of cement composites with different dosages of NS addition. The investigational study results showed that the combination of NS with a low amount of CNT had a positive effect on the hydration reaction; on the other hand, the combination of CNT and a high amount of NS had a negative effect on the hydration reaction. The compressive strength can be improved by optimum combination 0.02% CNT and 1% NS with gain in strength by 72% and 35% after 7 and 28 days compared to control samples; these results were with an agreement with the morphology structure of composites using microstructure analysis.Keywords: nano silica, dispersion, sonication, carbon nano tubes
Procedia PDF Downloads 1462490 Transcriptome Analysis of Dry and Soaked Tomato (Solanum lycopersicum) Seeds in Response to Fast Neutron Irradiation
Authors: Yujie Zhou, Hee-Seong Byun, Sang-In Bak, Eui-Joon Kil, Kyung Joo Min, Vivek Chavan, Won Kyong Cho, Sukchan Lee, Seung-Woo Hong, Tae-Sun Park
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Fast neutron irradiation (FNI) can cause mutations on plant genome but, in the most of cases, these irradiated plants have not shown significant characteristics phenotypically. In this study, we utilized RNA-Seq to generate a high-resolution transcriptome map of the tomato (Solanum lycopersicum) genome effected by FNI. To quantify the different transcription levels in tomato irradiated by FNI, tomato seeds were irradiated by using MC-50 cyclotron (KIRAMS, Korea) for 0, 30 and 90 minutes, respectively. To investigate the effects on the pre-soaking condition, experimental groups were divided into dry and soaked seeds, which were soaked for 8 hours before irradiation. There was no noticeable difference in the percentage germination (PG) among dry seeds, while irradiated soaked seeds have about 10 % lower PG compared to the unirradiated control group. Using whole transcriptome sequencing by HiSeq 2000, we analyzed the differential gene expression in response to different time of FNI in dry and soaked seeds. More than 1.4 million base pair reads were mapped onto the tomato reference genome and the expression pattern differences between irradiated and unirradiated seeds were assessed. In 0, 30 and 90 minutes irradiation, 12,135, 28,495 and 28,675 transcripts were generated, respectively. Gene ontology analysis suggested the different enrichment of transcripts involved in response to different FNI. The present study showed that FNI effects on plant gene expression, which can become a new parameters for evaluating the responses against FNI on plants. In addition, the comparative analysis of differentially expressed genes in D and S seeds by FNI will also give us a chance to deep explore novel candidate genes for FNI, which could be a good model system to understand the mechanisms behind the adaption of plant to space biology research.Keywords: tomato (solanum lycopersicum), fast neutron irradiation, RNA-sequence, transcriptome expression
Procedia PDF Downloads 3192489 Geography Undergraduates 360⁰ Academic Peer Learning And Mentoring 2021 – 2023: A Pilot Study
Authors: N. Ayob, N. C. Nkosi, R. P. Burger, S. J. Piketh, F. Letlaila, O. Maphosa
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South African higher tertiary institution have been faced with high dropout rates. About 50 to 60% of first years drop out to due to various reasons one being inadequate academic support. Geography 111 (GEOG 111) module is historically known for having below 50% pass rate, high dropout rate and identified as a first year risk module. For the first time GEOG 111 (2021) on the Mahikeng Campus admitted 150 students pursuing more than 6 different qualifications (BA and BSc) from the Humanities Faculty and FNAS. First year students had difficulties transitioning from secondary to tertiary institutions as we shifted to remote learning while we navigate through the Covid-19 pandemic. The traditional method of teaching does not encourage students to help each other. With remote learning we do not have control over what the students share and perhaps this can be a learning opportunity to embrace peer learning and change the manner in which we assess the students. The purpose of this pilot study was to assist GEOG111 students with academic challenges whilst improving their University experience. This was a qualitative study open to all GEOG111, repeaters, students who are not confident in their Geographical knowledge and never did Geography at high school level. The selected 9 Golden Key International Honour Society Geography mentors attended an academic mentor training program with module lecturers. About 17.6% of the mentees did not have a geography background however, 94% of the mentees passed, 1 mentee had a mark of 38%. 11 of the participants had a mark >60% with one student that excelled 70%. It is evident that mentorship helped students reach their academic potential. Peer learning and mentoring are associated with improved academic performance and allows the students to take charge of their learning and academic experience. Thus an important element as we transform pedagogies at higher learning institutions.Keywords: geography, risk module, peer mentoring, peer learning
Procedia PDF Downloads 1552488 Analgesic, Toxicity and Anti-Pyretic Activities of Methanolic Extract from Hyoscyamus albus Leaves in Albinos Rats
Authors: Yahia Massinissa, Henhouda Affaf, Yahia Mouloud
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The aim of this study was to investigate the toxicity; analgesic and anti-pyretic properties of standardized HA methanolic extract (HAMeOH) in vivo. The acute toxicity study was performed on rats while adopting the OECD-420 Guidelines (fixed dose procedure). Assessment of analgesic activity was performed in rats with two analgesic models. One was acetic acid induced writhing response and the other formalin-induced paw licking. The anti-pyretic effect was tested by brewer’s yeast induced fever in rats. For the acute toxicity test, the higher dose administration of 2000 mg/kg bw. of Hyoscyamus albus did not produce any toxic signs or deaths in rats. There were no significant differences (p>0.05) in the body and organ weights between control and treated groups. The (LD50) of Hyoscyamus albus was higher than 2000 g/kg bw. In subacute toxicity study, no mortality and toxic signs were observed with the doses of 100 and 200 mg/kg bw. of extracts of for 28 consecutive days. These analgesic experimental results indicated that HAMeOH (100 mg/kg and 200 mg/kg) decreased the acetic acid-induced writhing responses and HAMeOH (100 mg/kg and 200 mg/kg) decreased the licking time in the second phase of the formalin test. Moreover, in the model of yeast induced elevation of the body temperature HAMeOH showed dose-dependent lowering of the body temperature up to 3h at both the doses these results obtained, were comparable to that of paracetamol. The present findings indicate that the leaves of Hyoscyamus albus L. possess potent analgesic and antipyretic activity.Keywords: Hyoscyamus albus, methanolic extract, toxicity, analgesic activity, antipyretic activity, formalin test
Procedia PDF Downloads 3382487 State of Emergency in Turkey (July 2016-July 2018): A Case of Utilization of Law as a Political Instrument
Authors: Neslihan Cetin
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In this study, we will aim to analyze how the period of the state of emergency in Turkey lead to gaps in law and the formation of areas in which there was a complete lack of supervision. The state of emergency that was proclaimed following the coup attempt of July 15, 2016, continued until July 18, 2018, that is to say, 2 years, without taking into account whether the initial circumstances persisted. As part of this work, we claim that the state of emergency provided the executive power with important tools for governing, which it took constant use. We can highlight how the concern for security at the center of the basic considerations of the people in a city was exploited as a foundation by the military power in Turkey to interfere in the political, legal, and social spheres. The constitutions of 1924, 1961, and 1982 entrusted the army with the role of protector of the integrity of the state. This became an instrument at the hands of the military to legitimize their interventions in the name of public security. Its interventions in the political field are indeed politically motivated. The constitution, the legislative, and regulatory systems are modified and monopolized by the military power that dominates the legislative, regulatory, and judicial power, leading to a state of exception. With the political convulsions over a decade, the government was able to usurp the instrument called the state of exception. In particular, the decree-laws of the state of emergency, which the executive makes frequent and generally abusive use, became instruments in the hands of the government to take measures that it wishes to escape from the rules and the pre-established control mechanisms. Thus the struggle against the political opposition becomes more unbalanced and destructive. To this must also be added the ineffectiveness of ex-post controls and domestic remedies. This research allows us to stress how a legal concept, such as ‘the state of emergency’ can be politically exploited to make it a legal weapon that continues to produce victims.Keywords: constitutional law, state of emergency, rule of law, instrumentalization of law
Procedia PDF Downloads 1432486 Factors Affecting Entrepreneurial Behavior and Performance of Youth Entrepreneurs in Malaysia
Authors: Mohd Najib Mansor, Nur Syamilah Md. Noor, Abdul Rahim Anuar, Shazida Jan Mohd Khan, Ahmad Zubir Ibrahim, Badariah Hj Din, Abu Sufian Abu Bakar, Kalsom Kayat, Wan Nurmahfuzah Jannah Wan Mansor
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This study aimed and focused on the behavior of youth entrepreneurs’ especially entrepreneurial self-efficacy and the performance in micro SMEs in Malaysia. Entrepreneurship development calls for support from various quarters, and mostly the need exists to initiate a youth entrepreneurship culture and drive amongst the youth in the society. Although backed up by the government and non-government organizations, micro-entrepreneurs are still facing challenges which greatly delay their progress, growth and consequently their input towards economic advancement. Micro-entrepreneurs are confronted with unique difficulties such as uncertainty, innovation, and evolution. Reviews on the development of entrepreneurial characteristics such as need for achievement, internal locus of control, risk-taking and innovation and have been recognized as highly associated with entrepreneurial behavior. The data in this study was obtained from the Department of Statistics, Malaysia. A random sampling of 830 respondents was distributed to 14 states that involve of micro-entrepreneurs. The study adopted a quantitative approach whereby a set of questionnaire was used to gather data. Multiple regression analysis was chosen as a method of analysis testing. The result of this study is expected to provide insight into the factor affecting entrepreneurial behavior and performance of youth entrepreneurs in micro SMEs. The finding showed that the Malaysian youth entrepreneurs do not have the entrepreneurial self-efficacy within themselves in order to accomplish greater success in their business venture. The establishment of entrepreneurial schools to allow our youth to be exposed to entrepreneurship from an early age and the development of special training focuses on the creation of business network so that the continuous entrepreneurial culture is crafted.Keywords: youth entrepreneurs, micro entrepreneurs, entrepreneurial self-efficacy, entrepreneurial performance
Procedia PDF Downloads 3022485 Organic Contaminant Degradation Using H₂O₂ Activated Biochar with Enhanced Persistent Free Radicals
Authors: Kalyani Mer
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Hydrogen peroxide (H₂O₂) is one of the most efficient and commonly used oxidants in in-situ chemical oxidation (ISCO) of organic contaminants. In the present study, we investigated the activation of H₂O₂ by heavy metal (nickel and lead metal ions) loaded biochar for phenol degradation in an aqueous solution (concentration = 100 mg/L). It was found that H₂O₂ can be effectively activated by biochar, which produces hydroxyl (•OH) radicals owing to an increase in the formation of persistent free radicals (PFRs) on biochar surface. Ultrasound treated (30s duration) biochar, chemically activated by 30% phosphoric acid and functionalized by diethanolamine (DEA) was used for the adsorption of heavy metal ions from aqueous solutions. It was found that modified biochar could remove almost 60% of nickel in eight hours; however, for lead, the removal efficiency reached up to 95% for the same time duration. The heavy metal loaded biochar was further used for the degradation of phenol in the absence and presence of H₂O₂ (20 mM), within 4 hours of reaction time. The removal efficiency values for phenol in the presence of H₂O₂ were 80.3% and 61.9%, respectively, by modified biochar loaded with nickel and lead metal ions. These results suggested that the biochar loaded with nickel exhibits a better removal capacity towards phenol than the lead loaded biochar when used in H₂O₂ based oxidation systems. Meanwhile, control experiments were set in the absence of any activating biochar, and the removal efficiency was found to be 19.1% when only H₂O₂ was added in the reaction solution. Overall, the proposed approach serves a dual purpose of using biochar for heavy metal ion removal and treatment of organic contaminants by further using the metal loaded biochar for H₂O₂ activation in ISCO processes.Keywords: biochar, ultrasound, heavy metals, in-situ chemical oxidation, chemical activation
Procedia PDF Downloads 1352484 Exploration of FOMO, or the 'Fear of Missing out' and the Use of Mindfulness and Values-Based Interventions for Alleviating Its Effects and Bolstering Well-Being
Authors: Chasity O'Connell
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The use of social media and networking sites play a significant role in the lives of adolescents and adults. While research supports that social support and connectedness in general is beneficial; the nature of communication and interaction through social media and its subsequent benefits and impacts could be arguably different. As such, this research aims to explore a specific facet of social media interaction called fear of missing out, or 'FOMO' and investigate its relationship within the context of life stressors, social media usage, anxiety and depressive-symptoms, mindfulness, and psychological well-being. FOMO is the 'uneasy and sometimes all-consuming feeling that you’re missing out—that your peers are doing, in the know about, or in possession of more or something better than you'. Research suggests that FOMO can influence an individual’s level of engagement with friends and social media consumption, drive decisions on participating in various online or offline activities, and ultimately impact mental health. This study hopes to explore the potentially mitigating influence of mindfulness and values-based interventions in reducing the discomfort and distress that can accompany FOMO and increase the sense of psychological well-being in allowing for a more thoughtful and deliberate engagement in life. This study will include an intervention component wherein participants (comprised of university students and adults in the community) will partake in a six-week, group-based intervention focusing on learning practical mindfulness skills and values-exploration exercises (along with a waitlist control group). In doing so, researchers hope to understand if interventions centered on increasing one’s awareness of the present moment and one’s internal values impact decision-making and well-being with regard to social interaction and relationships.Keywords: FOMO, mindfulness, values, stress, psychological well-being, intervention, distress
Procedia PDF Downloads 1942483 Adaptive Responses of Carum copticum to in vitro Salt Stress
Authors: R. Razavizadeh, F. Adabavazeh, M. Rezaee Chermahini
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Salinity is one of the most widespread agricultural problems in arid and semi-arid areas that limits the plant growth and crop productivity. In this study, the salt stress effects on protein, reducing sugar, proline contents and antioxidant enzymes activities of Carum copticum L. under in vitro conditions were studied. Seeds of C. copticum were cultured in Murashige and Skoog (MS) medium containing 0, 25, 50, 100 and 150 mM NaCl and calli were cultured in MS medium containing 1 μM 2, 4-dichlorophenoxyacetic acid, 4 μM benzyl amino purine and different levels of NaCl (0, 25, 50, 100 and 150 mM). After NaCl treatment for 28 days, the proline and reducing sugar contents of shoots, roots and calli increased significantly in relation to the severity of the salt stress. The highest amount of proline and carbohydrate were observed at 150 and 100 mM NaCl, respectively. The reducing sugar accumulation in shoots was the highest as compared to roots, whereas, proline contents did not show any significant difference in roots and shoots under salt stress. The results showed significant reduction of protein contents in seedlings and calli. Based on these results, proteins extracted from the shoots, roots and calli of C. copticum treated with 150 mM NaCl showed the lowest contents. The positive relationships were observed between activity of antioxidant enzymes and the increase in stress levels. Catalase, ascorbate peroxidase and superoxide dismutase activity increased significantly under salt concentrations in comparison to the control. These results suggest that the accumulation of proline and sugars, and activation of antioxidant enzymes play adaptive roles in the adaptation of seedlings and callus of C. copticum to saline conditions.Keywords: antioxidant enzymes, Carum copticum, organic solutes, salt stress
Procedia PDF Downloads 2822482 Place of Radiotherapy in the Treatment of Intracranial Meningiomas: Experience of the Cancer Center Emir Abdelkader of Oran Algeria
Authors: Taleb L., Benarbia M., Boutira F. M., Allam H., Boukerche A.
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Introduction and purpose of the study: Meningiomas are the most common non-glial intracranial tumors in adults, accounting for approximately 30% of all central nervous system tumors. The aim of our study is to determine the epidemiological, clinical, therapeutic, and evolutionary characteristics of a cohort of patients with intracranial meningioma treated with radiotherapy at the Emir Abdelkader Cancer Center in Oran. Material and methods: This is a retrospective study of 44 patients during the period from 2014 to 2020. The overall survival and relapse-free survival curves were calculated using the Kaplan-Meier method. Results and statistical analysis: The median age of the patients was 49 years [21-76 years] with a clear female predominance (sex ratio=2.4). The average diagnostic delay was seven months [2 to 24 months], the circumstances of the discovery of which were dominated by headaches in 54.5% of cases (n=24), visual disturbances in 40.9% (n=18), and motor disorders in 15.9% (n=7). The seat of the tumor was essentially at the level of the base of the skull in 52.3% of patients (n=23), including 29.5% (n=13) at the level of the cavernous sinus, 27.3% (n=12) at the parasagittal level and 20.5% (n=9) at the convexity. The diagnosis was confirmed surgically in 36 patients (81.8%) whose anatomopathological study returned in favor of grades I, II, and III in respectively 40.9%, 29.5%, and 11.4% of the cases. Radiotherapy was indicated postoperatively in 45.5% of patients (n=20), exclusive in 27.3% (n=12) and after tumor recurrence in 27.3% of cases (n=18). The irradiation doses delivered were as follows: 50 Gy (20.5%), 54 Gy (65.9%), and 60 Gy (13.6%). With a median follow-up of 69 months, the probabilities of relapse-free survival and overall survival at three years are 93.2% and 95.4%, respectively, whereas they are 71.2% and 80.7% at five years. Conclusion: Meningiomas are common primary brain tumors. Most often benign but can also progress aggressively. Their treatment is essentially surgical, but radiotherapy retains its place in specific situations, allowing good tumor control and overall survival.Keywords: diagnosis, meningioma, surgery, radiotherapy, survival
Procedia PDF Downloads 1002481 Sensitivity Analysis of the Thermal Properties in Early Age Modeling of Mass Concrete
Authors: Farzad Danaei, Yilmaz Akkaya
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In many civil engineering applications, especially in the construction of large concrete structures, the early age behavior of concrete has shown to be a crucial problem. The uneven rise in temperature within the concrete in these constructions is the fundamental issue for quality control. Therefore, developing accurate and fast temperature prediction models is essential. The thermal properties of concrete fluctuate over time as it hardens, but taking into account all of these fluctuations makes numerical models more complex. Experimental measurement of the thermal properties at the laboratory conditions also can not accurately predict the variance of these properties at site conditions. Therefore, specific heat capacity and the heat conductivity coefficient are two variables that are considered constant values in many of the models previously recommended. The proposed equations demonstrate that these two quantities are linearly decreasing as cement hydrates, and their value are related to the degree of hydration. The effects of changing the thermal conductivity and specific heat capacity values on the maximum temperature and the time it takes for concrete to reach that temperature are examined in this study using numerical sensibility analysis, and the results are compared to models that take a fixed value for these two thermal properties. The current study is conducted in 7 different mix designs of concrete with varying amounts of supplementary cementitious materials (fly ash and ground granulated blast furnace slag). It is concluded that the maximum temperature will not change as a result of the constant conductivity coefficient, but variable specific heat capacity must be taken into account, also about duration when a concrete's central node reaches its max value again variable specific heat capacity can have a considerable effect on the final result. Also, the usage of GGBFS has more influence compared to fly ash.Keywords: early-age concrete, mass concrete, specific heat capacity, thermal conductivity coefficient
Procedia PDF Downloads 772480 Radon-222 Concentration and Potential Risk to Workers of Al-Jalamid Phosphate Mines, North Province, Saudi Arabia
Authors: El-Said. I. Shabana, Mohammad S. Tayeb, Maher M. T. Qutub, Abdulraheem A. Kinsara
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Usually, phosphate deposits contain 238U and 232Th in addition to their decay products. Due to their different pathways in the environment, the 238U/232Th activity concentration ratio usually found to be greater than unity in phosphate sediments. The presence of these radionuclides creates a potential need to control exposure of workers in the mining and processing activities of the phosphate minerals in accordance with IAEA safety standards. The greatest dose to workers comes from exposure to radon, especially 222Rn from the uranium series, and has to be controlled. In this regard, radon (222Rn) was measured in the atmosphere (indoor and outdoor) of Al-Jalamid phosphate-mines working area using a portable radon-measurement instrument RAD7, in a purpose of radiation protection. Radon was measured in 61 sites inside the open phosphate mines, the phosphate upgrading facility (offices and rooms of the workers, and in some open-air sites) and in the dwellings of the workers residence-village that lies at about 3 km from the mines working area. The obtained results indicated that the average indoor radon concentration was about 48.4 Bq/m3. Inside the upgrading facility, the average outdoor concentrations were 10.8 and 9.7 Bq/m3 in the concentrate piles and crushing areas, respectively. It was 12.3 Bq/m3 in the atmosphere of the open mines. These values are comparable with the global average values. Based on the average values, the annual effective dose due to radon inhalation was calculated and risk estimates have been done. The average annual effective dose to workers due to the radon inhalation was estimated by 1.32 mSv. The potential excess risk of lung cancer mortality that could be attributed to radon, when considering the lifetime exposure, was estimated by 53.0x10-4. The results have been discussed in detail.Keywords: dosimetry, environmental monitoring, phosphate deposits, radiation protection, radon
Procedia PDF Downloads 2722479 Hands-off Parking: Deep Learning Gesture-based System for Individuals with Mobility Needs
Authors: Javier Romera, Alberto Justo, Ignacio Fidalgo, Joshue Perez, Javier Araluce
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Nowadays, individuals with mobility needs face a significant challenge when docking vehicles. In many cases, after parking, they encounter insufficient space to exit, leading to two undesired outcomes: either avoiding parking in that spot or settling for improperly placed vehicles. To address this issue, the following paper presents a parking control system employing gestural teleoperation. The system comprises three main phases: capturing body markers, interpreting gestures, and transmitting orders to the vehicle. The initial phase is centered around the MediaPipe framework, a versatile tool optimized for real-time gesture recognition. MediaPipe excels at detecting and tracing body markers, with a special emphasis on hand gestures. Hands detection is done by generating 21 reference points for each hand. Subsequently, after data capture, the project employs the MultiPerceptron Layer (MPL) for indepth gesture classification. This tandem of MediaPipe's extraction prowess and MPL's analytical capability ensures that human gestures are translated into actionable commands with high precision. Furthermore, the system has been trained and validated within a built-in dataset. To prove the domain adaptation, a framework based on the Robot Operating System (ROS), as a communication backbone, alongside CARLA Simulator, is used. Following successful simulations, the system is transitioned to a real-world platform, marking a significant milestone in the project. This real vehicle implementation verifies the practicality and efficiency of the system beyond theoretical constructs.Keywords: gesture detection, mediapipe, multiperceptron layer, robot operating system
Procedia PDF Downloads 1002478 Formulation and Evaluation of Silibilin Loaded PLGA Nanoparticles for Cancer Therapy
Authors: Priya Patel, Paresh Patel, Mihir Raval
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Silibinin, a flavanone as an antimicrotubular agent used in the treatment of cancer, was encapsulated in nanoparticles (NPs) of poly (lactide-co-glycolide) (PLGA) polymer using the spray-drying technique. The effects of various experimental parameters were optimized by box-behnken experimental design. Production yield, encapsulation efficiency and dissolution study along with characterization by scanning electron microscopy, DSC, FTIR followed by bioavailability study. Particle size and zeta potential were evaluated by using zetatrac particle size analyzer. Experimental design it was evaluated that inlet temperature and polymer concentration influence on the drug release. Feed flow rate impact on particle size. Results showed that spray drying technique yield 149 nm indicate nanosize range. The small size of the nanoparticle resulted in an enhanced cellular entry and greater bioavailability. Entrapment efficiency was found between 89.35% and 98.36%. Zeta potential shows good stability index of nanoparticle formulation. The in vitro release studies indicated the silibinin loaded PLGA nanoparticles provide controlled drug release over a period of 32 h. Pharmacokinetic studies demonstrated that after oral administration of silibinin-loaded PLGA nanoparticles to rats at a dose of 10 mg/kg, relative bioavailability was enhanced about 8.85-fold, compared to silibinin suspension as control hence, this investigation demonstrated the potential of the experimental design in understanding the effect of the formulation variables on the quality of silibinin loaded PLGA nanoparticles. These results describe an effective strategy of silibinin loaded PLGA nanoparticles and might provide a promising approach against the cancer.Keywords: silibinin, cancer, nanoparticles, PLGA, bioavailability
Procedia PDF Downloads 4292477 Development of an Autonomous Automated Guided Vehicle with Robot Manipulator under Robot Operation System Architecture
Authors: Jinsiang Shaw, Sheng-Xiang Xu
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This paper presents the development of an autonomous automated guided vehicle (AGV) with a robot arm attached on top of it within the framework of robot operation system (ROS). ROS can provide libraries and tools, including hardware abstraction, device drivers, libraries, visualizers, message-passing, package management, etc. For this reason, this AGV can provide automatic navigation and parts transportation and pick-and-place task using robot arm for typical industrial production line use. More specifically, this AGV will be controlled by an on-board host computer running ROS software. Command signals for vehicle and robot arm control and measurement signals from various sensors are transferred to respective microcontrollers. Users can operate the AGV remotely through the TCP / IP protocol and perform SLAM (Simultaneous Localization and Mapping). An RGBD camera and LIDAR sensors are installed on the AGV, using these data to perceive the environment. For SLAM, Gmapping is used to construct the environment map by Rao-Blackwellized particle filter; and AMCL method (Adaptive Monte Carlo localization) is employed for mobile robot localization. In addition, current AGV position and orientation can be visualized by ROS toolkit. As for robot navigation and obstacle avoidance, A* for global path planning and dynamic window approach for local planning are implemented. The developed ROS AGV with a robot arm on it has been experimented in the university factory. A 2-D and 3-D map of the factory were successfully constructed by the SLAM method. Base on this map, robot navigation through the factory with and without dynamic obstacles are shown to perform well. Finally, pick-and-place of parts using robot arm and ensuing delivery in the factory by the mobile robot are also accomplished.Keywords: automated guided vehicle, navigation, robot operation system, Simultaneous Localization and Mapping
Procedia PDF Downloads 1492476 Stem Cell Differentiation Toward Secretory Progenitors after Intestinal Ischemia-Reperfusion in a Rat is Accompanied by Inhibited Notch Signaling Cascade
Authors: Igor Sukhotnik
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Objectives: Notch signaling is thought to act to drive cell versification in the lining of the small intestine. When Notch signaling is blocked, proliferation ceases, and epithelial cells become secretory. The purpose of the present study was to evaluate the role of Notch signaling pathway in stem cell differentiation in a rat model of intestinal ischemia-reperfusion (IR). Methods: Male Sprague-Dawley rats were randomly divided into four experimental groups: Sham-24 and Sham-48 rats underwent laparotomy and were killed 24 or 48 h later, respectively; IR-24 and IR-48 rats underwent occlusion of SMA and portal vein for 30 min followed by 24 or 48 h of reperfusion, respectively. Notch-related gene and protein expression were determined using Real Time PCR, Western blotting and immunohistochemistry. Wax histology and immunohistochemistry was used to determine cell differentiation toward absorptive (enterocytes) or secretory progenitors (goblet cells, enteroendocrine cells or Paneth cells). Results: IR-48 rats exhibited a significant decrease in Notch-1 protein expression (Western blot) that was coincided with a significant decrease in the number of Notch-1 positive cells (immunohistochemistry) in jejunum and ileum as well as Hes-1 positive cells in jejunum and ileum compared to Sham-48 rats. A significant down-regulation of Notch signaling related genes and proteins in IR animals was accompanied by a significant increase in the number of goblet and Paneth cells and decreased number of absorptive cells compared to control rats. Conclusions: Forty-eight hours following intestinal IR in rats, inhibited Notch signaling pathway was accompanied by intestinal stem cells differentiation toward secretory progenitors.Keywords: Intestine, notch, ischemia-reperfusion, cell differentiation, secretory
Procedia PDF Downloads 582475 The Impact of Sedimentary Heterogeneity on Oil Recovery in Basin-plain Turbidite: An Outcrop Analogue Simulation Case Study
Authors: Bayonle Abiola Omoniyi
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In turbidite reservoirs with volumetrically significant thin-bedded turbidites (TBTs), thin-pay intervals may be underestimated during calculation of reserve volume due to poor vertical resolution of conventional well logs. This paper demonstrates the strong control of bed-scale sedimentary heterogeneity on oil recovery using six facies distribution scenarios that were generated from outcrop data from the Eocene Itzurun Formation, Basque Basin (northern Spain). The variable net sand volume in these scenarios serves as a primary source of sedimentary heterogeneity impacting sandstone-mudstone ratio, sand and shale geometry and dimensions, lateral and vertical variations in bed thickness, and attribute indices. The attributes provided input parameters for modeling the scenarios. The models are 20-m (65.6 ft) thick. Simulation of the scenarios reveals that oil production is markedly enhanced where degree of sedimentary heterogeneity and resultant permeability contrast are low, as exemplified by Scenarios 1, 2, and 3. In these scenarios, bed architecture encourages better apparent vertical connectivity across intervals of laterally continuous beds. By contrast, low net-to-gross Scenarios 4, 5, and 6, have rapidly declining oil production rates and higher water cut with more oil effectively trapped in low-permeability layers. These scenarios may possess enough lateral connectivity to enable injected water to sweep oil to production well; such sweep is achieved at a cost of high-water production. It is therefore imperative to consider not only net-to-gross threshold but also facies stack pattern and related attribute indices to better understand how to effectively manage water production for optimum oil recovery from basin-plain reservoirs.Keywords: architecture, connectivity, modeling, turbidites
Procedia PDF Downloads 242474 Alternative (In)Security: Using Photovoice Research Methodology to Explore Refugee Anxieties in Lebanon
Authors: Jessy Abouarab
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For more than half a century, international norms related to refugee security and protection have proliferated, yet their role in alleviating war’s negative impacts on human life remains limited. The impact of refugee-security processes often manifests asymmetrically within populations. Many issues and people get silenced due to narrow security policies that focus either on abstract threat containment and refugee control or refugee protection and humanitarian aid. (In)security practices are gendered and experienced. Examining the case study of Syrian refugees in Lebanon, this study explores the gendered impact of refugee security mechanisms on local realities. A transnational feminist approach will be used to position this research in relation to existing studies in the field of security and the refugee-protection regime, highlighting the social, cultural, legal, and political barriers to gender equality in the areas of violence, rights, and social inclusion. Through Photovoice methodology, the Syrian refugees’ (in)securities in Lebanon were given visibility by enabling local volunteers to record and reflect their realities through pictures, at the same time voice the participants’ anxieties and recommendations to reach normative policy change. This Participatory Action Research approach helped participants observe the structural barriers and lack of culturally inclusive refugee services that hinder security, increase discrimination, stigma, and poverty. The findings have implications for a shift of the refugee protection mechanisms to a community-based approach in ways that extend beyond narrow security policies that hinder women empowerment and raise vulnerabilities such as gendered exploitation, abuse, and neglect.Keywords: gender, (in)security, Lebanon, refugee, Syrian refugees, women
Procedia PDF Downloads 1432473 Applications of Forensics/DNA Tools in Combating Gender-Based Violence: A Case Study in Nigeria
Authors: Edeaghe Ehikhamenor, Jennifer Nnamdi
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Introduction: Gender-based violence (GBV) was a well-known global crisis before the COVID-19 pandemic. The pandemic burden only intensified the crisis. With prevailing lockdowns, increased poverty due to high unemployment, especially affecting females, and other mobility restrictions that have left many women trapped with their abusers, plus isolation from social contact and support networks, GBV cases spiraled out of control. Prevalence of economic with cultural disparity, which is greatly manifested in Nigeria, is a major contributory factor to GBV. This is made worst by religious adherents where the females are virtually relegated to the background. Our societal approaches to investigations and sanctions to culprits have not sufficiently applied forensic/DNA tools in combating these major vices. Violence against women or some rare cases against men can prevent them from carrying out their duties regardless of the position they hold. Objective: The main objective of this research is to highlight the origin of GBV, the victims, types, contributing factors, and the applications of forensics/DNA tools and remedies so as to minimize GBV in our society. Methods: Descriptive information was obtained through the search on our daily newspapers, electronic media, google scholar websites, other authors' observations and personal experiences, plus anecdotal reports. Results: Findings from our exploratory searches revealed a high incidence of GBV with very limited or no applications of Forensics/DNA tools as an intervening mechanism to reduce GBV in Nigeria. Conclusion: Nigeria needs to develop clear-cut policies on forensics/DNA tools in terms of institutional framework to develop a curriculum for the training of all stakeholders to fast-track justice for victims of GBV so as to serve as a deterrent to other culprits.Keywords: gender-based violence, forensics, DNA, justice
Procedia PDF Downloads 842472 N-Heterocyclic Carbene Based Dearomatized Iridium Complex as an Efficient Catalyst towards Carbon-Carbon Bond Formation via Hydrogen Borrowing Strategy
Authors: Mandeep Kaur, Jitendra K. Bera
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The search for atom-economical and green synthetic methods for the synthesis of functionalized molecules has attracted much attention. Metal ligand cooperation (MLC) plays a pivotal role in organometallic catalysis to activate C−H, H−H, O−H, N−H and B−H bonds through reversible bond breaking and bond making process. Towards this goal, a bifunctional N─heterocyclic carbene (NHC) based pyridyl-functionalized amide ligand precursor, and corresponding dearomatized iridium complex was synthesized. The NMR and UV/Vis acid titration study have been done to prove the proton response nature of the iridium complex. Further, the dearomatized iridium complex explored as a catalyst on the platform of MLC via dearomatzation/aromatization mode of action towards atom economical α and β─alkylation of ketones and secondary alcohols by using primary alcohols through hydrogen borrowing methodology. The key features of the catalysis are high turnover frequency (TOF) values, low catalyst loading, low base loading and no waste product. The greener syntheses of quinoline, lactone derivatives and selective alkylation of drug molecules like pregnenolone and testosterone were also achieved successfully. Another structurally similar iridium complex was also synthesized with modified ligand precursor where a pendant amide unit was absent. The inactivity of this analogue iridium complex towards catalysis authenticated the participation of proton responsive imido sidearm of the ligand to accelerate the catalytic reaction. The mechanistic investigation through control experiments, NMR and deuterated labeling study, authenticate the borrowing hydrogen strategy.Keywords: C-C bond formation, hydrogen borrowing, metal ligand cooperation (MLC), n-heterocyclic carbene
Procedia PDF Downloads 1802471 Biophysical Study of the Interaction of Harmalol with Nucleic Acids of Different Motifs: Spectroscopic and Calorimetric Approaches
Authors: Kakali Bhadra
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Binding of small molecules to DNA and recently to RNA, continues to attract considerable attention for developing effective therapeutic agents for control of gene expression. This work focuses towards understanding interaction of harmalol, a dihydro beta-carboline alkaloid, with different nucleic acid motifs viz. double stranded CT DNA, single stranded A-form poly(A), double-stranded A-form of poly(C)·poly(G) and clover leaf tRNAphe by different spectroscopic, calorimetric and molecular modeling techniques. Results of this study converge to suggest that (i) binding constant varied in the order of CT DNA > poly(C)·poly(G) > tRNAphe > poly(A), (ii) non-cooperative binding of harmalol to poly(C)·poly(G) and poly(A) and cooperative binding with CT DNA and tRNAphe, (iii) significant structural changes of CT DNA, poly(C)·poly(G) and tRNAphe with concomitant induction of optical activity in the bound achiral alkaloid molecules, while with poly(A) no intrinsic CD perturbation was observed, (iv) the binding was predominantly exothermic, enthalpy driven, entropy favoured with CT DNA and poly(C)·poly(G) while it was entropy driven with tRNAphe and poly(A), (v) a hydrophobic contribution and comparatively large role of non-polyelectrolytic forces to Gibbs energy changes with CT DNA, poly(C)·poly(G) and tRNAphe, and (vi) intercalated state of harmalol with CT DNA and poly(C)·poly(G) structure as revealed from molecular docking and supported by the viscometric data. Furthermore, with competition dialysis assay it was shown that harmalol prefers hetero GC sequences. All these findings unequivocally pointed out that harmalol prefers binding with ds CT DNA followed by ds poly(C)·poly(G), clover leaf tRNAphe and least with ss poly(A). The results highlight the importance of structural elements in these natural beta-carboline alkaloids in stabilizing different DNA and RNA of various motifs for developing nucleic acid based better therapeutic agents.Keywords: calorimetry, docking, DNA/RNA-alkaloid interaction, harmalol, spectroscopy
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