Search results for: heterogeneous catalyst
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1440

Search results for: heterogeneous catalyst

120 The Misuse of Free Cash and Earnings Management: An Analysis of the Extent to Which Board Tenure Mitigates Earnings Management

Authors: Michael McCann

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Managerial theories propose that, in joint stock companies, executives may be tempted to waste excess free cash on unprofitable projects to keep control of resources. In order to conceal their projects' poor performance, they may seek to engage in earnings management. On the one hand, managers may manipulate earnings upwards in order to post ‘good’ performances and safeguard their position. On the other, since managers pursuit of unrewarding investments are likely to lead to low long-term profitability, managers will use negative accruals to reduce current year’s earnings, smoothing earnings over time in order to conceal the negative effects. Agency models argue that boards of directors are delegated by shareholders to ensure that companies are governed properly. Part of that responsibility is ensuring the reliability of financial information. Analyses of the impact of board characteristics, particularly board independence on the misuse of free cash flow and earnings management finds conflicting evidence. However, existing characterizations of board independence do not account for such directors gaining firm-specific knowledge over time, influencing their monitoring ability. Further, there is little analysis of the influence of the relative experience of independent directors and executives on decisions surrounding the use of free cash. This paper contributes to this literature regarding the heterogeneous characteristics of boards by investigating the influence of independent director tenure on earnings management and the relative tenures of independent directors and Chief Executives. A balanced panel dataset comprising 51 companies across 11 annual periods from 2005 to 2015 is used for the analysis. In each annual period, firms were classified as conducting earnings management if they had discretionary accruals in the bottom quartile (downwards) and top quartile (upwards) of the distributed values for the sample. Logistical regressions were conducted to determine the marginal impact of independent board tenure and a number of control variables on the probability of conducting earnings management. The findings indicate that both absolute and relative measures of board independence and experience do not have a significant impact on the likelihood of earnings management. It is the level of free cash flow which is the major influence on the probability of earnings management. Higher free cash flow increases the probability of earnings management significantly. The research also investigates whether board monitoring of earnings management is contingent on the level of free cash flow. However, the results suggest that board monitoring is not amplified when free cash flow is higher. This suggests that the extent of earnings management in companies is determined by a range of company, industry and situation-specific factors.

Keywords: corporate governance, boards of directors, agency theory, earnings management

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119 Assessment of Socio-Cultural Sustainability: A Comparative Analysis of Two Neighborhoods in Kolkata Metropolitan Area

Authors: Tanima Bhattacharya, Joy Sen

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To transform a space into a better livable and sustainable zone, United Nations Summit in New York 2015, has decided upon 17 sustainable development goals (SDGs) that approach directly to achieve inclusive, people-centric, sustainable developments. Though sustainability has been majorly constructed by four pillars, namely, Ecological, Economic, Social and Cultural, but it is essentially reduced to economic and ecological consideration in the context of developing countries. Therefore, in most cases planning has reduced its ambit to concentrate around the tangible infrastructure, ignoring the fundamentals of socio-cultural heritage. With the accentuating hype of infrastructural augmentation, lack of emphasis of traditional concerns like ethnicity and social connection have further diluted the situation, disintegrating cultural continuity. As cultural continuity lacks its cohesion, it’s growing absence increasingly acts as a catalyst to degrade the heritage structures, spaces around and linking these structures, and the ability of stakeholders in identifying themselves rooted in that particular space. Hence, this paper will argue that sustainability depends on the people and their interaction with their surroundings, their culture and livelihood. The interaction between people and their surroundings strengthen community building and social interaction that abides by stakeholders reverting back to their roots. To assess the socio-cultural sustainability of the city of Kolkata, two study areas are selected, namely, an old settlement from the northern part of the city of Kolkata (KMA), imbued with social connection, age-old cultural and ethnic bonding and, another cluster of new high-rises coming up in the Newtown area having portions of planned city extension on the eastern side of the city itself. Whereas, Newtown prioritizes the surging post-industrial trends of economic aspiration and ecological aspects of urban sustainability; the former settlements of northern Kolkata still continue to represent the earliest community settlement of the British-colonial-cum native era and even the pre-colonial era, permeated with socio-cultural reciprocation. Thus, to compare and assess the inlayed organizational structure of both the spaces in the two cases, selected areas have been surveyed to portray their current imageability. The argument of this paper is structured in 5parts. First, an introduction of the idea has been forwarded, Secondly, a literature review has been conducted to ground the proposed ideas, Thirdly, methodology has been discussed and appropriate case study areas have been selected, Fourthly, surveys and analyses has been forwarded and lastly, the paper has arrived at a set of conclusions by suggesting a threefold development to create happy, healthy and sustainable community.

Keywords: art innovation, current scenario assessment, heritage, imageability, socio-cultural sustainability

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118 Coupling Strategy for Multi-Scale Simulations in Micro-Channels

Authors: Dahia Chibouti, Benoit Trouette, Eric Chenier

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With the development of micro-electro-mechanical systems (MEMS), understanding fluid flow and heat transfer at the micrometer scale is crucial. In the case where the flow characteristic length scale is narrowed to around ten times the mean free path of gas molecules, the classical fluid mechanics and energy equations are still valid in the bulk flow, but particular attention must be paid to the gas/solid interface boundary conditions. Indeed, in the vicinity of the wall, on a thickness of about the mean free path of the molecules, called the Knudsen layer, the gas molecules are no longer in local thermodynamic equilibrium. Therefore, macroscopic models based on the continuity of velocity, temperature and heat flux jump conditions must be applied at the fluid/solid interface to take this non-equilibrium into account. Although these macroscopic models are widely used, the assumptions on which they depend are not necessarily verified in realistic cases. In order to get rid of these assumptions, simulations at the molecular scale are carried out to study how molecule interaction with walls can change the fluid flow and heat transfers at the vicinity of the walls. The developed approach is based on a kind of heterogeneous multi-scale method: micro-domains overlap the continuous domain, and coupling is carried out through exchanges of information between both the molecular and the continuum approaches. In practice, molecular dynamics describes the fluid flow and heat transfers in micro-domains while the Navier-Stokes and energy equations are used at larger scales. In this framework, two kinds of micro-simulation are performed: i) in bulk, to obtain the thermo-physical properties (viscosity, conductivity, ...) as well as the equation of state of the fluid, ii) close to the walls to identify the relationships between the slip velocity and the shear stress or between the temperature jump and the normal temperature gradient. The coupling strategy relies on an implicit formulation of the quantities extracted from micro-domains. Indeed, using the results of the molecular simulations, a Bayesian regression is performed in order to build continuous laws giving both the behavior of the physical properties, the equation of state and the slip relationships, as well as their uncertainties. These latter allow to set up a learning strategy to optimize the number of micro simulations. In the present contribution, the first results regarding this coupling associated with the learning strategy are illustrated through parametric studies of convergence criteria, choice of basis functions and noise of input data. Anisothermic flows of a Lennard Jones fluid in micro-channels are finally presented.

Keywords: multi-scale, microfluidics, micro-channel, hybrid approach, coupling

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117 Integration of Gravity and Seismic Methods in the Geometric Characterization of a Dune Reservoir: Case of the Zouaraa Basin, NW Tunisia

Authors: Marwa Djebbi, Hakim Gabtni

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Gravity is a continuously advancing method that has become a mature technology for geological studies. Increasingly, it has been used to complement and constrain traditional seismic data and even used as the only tool to get information of the sub-surface. In fact, in some regions the seismic data, if available, are of poor quality and hard to be interpreted. Such is the case for the current study area. The Nefza zone is part of the Tellian fold and thrust belt domain in the north west of Tunisia. It is essentially made of a pile of allochthonous units resulting from a major Neogene tectonic event. Its tectonic and stratigraphic developments have always been subject of controversies. Considering the geological and hydrogeological importance of this area, a detailed interdisciplinary study has been conducted integrating geology, seismic and gravity techniques. The interpretation of Gravity data allowed the delimitation of the dune reservoir and the identification of the regional lineaments contouring the area. It revealed the presence of three gravity lows that correspond to the dune of Zouara and Ouchtata separated along with a positive gravity axis espousing the Ain Allega_Aroub Er Roumane axe. The Bouguer gravity map illustrated the compartmentalization of the Zouara dune into two depressions separated by a NW-SE anomaly trend. This constitution was confirmed by the vertical derivative map which showed the individualization of two depressions with slightly different anomaly values. The horizontal gravity gradient magnitude was performed in order to determine the different geological features present in the studied area. The latest indicated the presence of NE-SW parallel folds according to the major Atlasic direction. Also, NW-SE and EW trends were identified. The maxima tracing confirmed this direction by the presence of NE-SW faults, mainly the Ghardimaou_Cap Serrat accident. The quality of the available seismic sections and the absence of borehole data in the region, except few hydraulic wells that been drilled and showing the heterogeneity of the substratum of the dune, required the process of gravity modeling of this challenging area that necessitates to be modeled for the geometrical characterization of the dune reservoir and determine the different stratigraphic series underneath these deposits. For more detailed and accurate results, the scale of study will be reduced in coming research. A more concise method will be elaborated; the 4D microgravity survey. This approach is considered as an expansion of gravity method and its fourth dimension is time. It will allow a continuous and repeated monitoring of fluid movement in the subsurface according to the micro gal (μgall) scale. The gravity effect is a result of a monthly variation of the dynamic groundwater level which correlates with rainfall during different periods.

Keywords: 3D gravity modeling, dune reservoir, heterogeneous substratum, seismic interpretation

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116 Making the Neighbourhood: Analyzing Mapping Procedures to Deal with Plurality and Conflict

Authors: Barbara Roosen, Oswald Devisch

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Spatial projects are often contested. Despite participatory trajectories in official spatial development processes, citizens engage often by their power to say no. Participatory mapping helps to produce more legible and democratic ways of decision-making. It has proven its value in producing a multitude of knowledges and views, for individuals and community groups and local stakeholders to imagine desired and undesired futures and to give them the rhetorical power to present their views throughout the development process. From this perspective, mapping works as a social process in which individuals and groups share their knowledge, learn from each other and negotiate their relationship with each other as well as with space and power. In this way, these processes eventually aim to activate communities to intervene in cooperation in real problems. However, these are fragile and bumpy processes, sometimes leading to (local) conflict and intractable situations. Heterogeneous subjectivities and knowledge that become visible during the mapping process and which are contested by members of the community, is often the first trigger. This paper discusses a participatory mapping project conducted in a residential subdivision in Flanders to provide a deeper understanding of how or under which conditions the mapping process could moderate discordant situations amongst inhabitants, local organisations and local authorities, towards a more constructive outcome. In our opinion, this implies a thorough documentation and presentation of the different steps of the mapping process to design and moderate an open and transparent dialogue. The mapping project ‘Make the Neighbourhood’, is set up in the aftermath of a socio-spatial design intervention in the neighbourhood that led to polarization within the community. To start negotiation between the diverse claims that came to the fore, we co-create a desired future map of the neighbourhood together with local organisations and inhabitants as a way to engage them in the development of a new spatial development plan for the area. This mapping initiative set up a new ‘common’ goal or concern, as a first step to bridge the gap that we experienced between different sociocultural groups, bottom-up and top-down initiatives and between professionals and non-professionals. An atlas of elements (materials), an atlas of actors with different roles and an atlas of ways of cooperation and organisation form the work and building material of the future neighbourhood map, assembled in two co-creation sessions. Firstly, we will consider how the mapping procedures articulate the plurality of claims and agendas. Secondly, we will elaborate upon how social relations and spatialities are negotiated and reproduced during the different steps of the map making. Thirdly, we will reflect on the role of the rules, format, and structure of the mapping process in moderating negotiations between much divided claims. To conclude, we will discuss the challenges of visualizing the different steps of mapping process as a strategy to moderate tense negotiations in a more constructive direction in the context of spatial development processes.

Keywords: conflict, documentation, participatory mapping, residential subdivision

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115 Female Fans in Global Football Governance: A Call for Change

Authors: Yaron Covo, Tamar Kofman, Shira Palti

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Over the recent decades, debates about the engagement of fans in football governance have focused on the club level and national level, emphasizing the significance of fans’ involvement in increasing the connection of clubs with the community, and in safeguarding the transparency, accountability, and clubs’ financial stability. This paper will offer a different conceptual justification for providing fans with access to decision-making processes in football. First, it will suggest that the participation of fans is necessary for addressing discriminatory practices against women in football stadiums. Second, it will argue that fans’ involvement in football governance is important not only at the club and national level but also at the global level, relying on the principles of Global Administrative Law. In contemporary men’s football, female fans face different forms of discrimination. Iranian women are still prohibited from attending football games at the domestic level; In Saudi Arabia, female fans are only permitted to enter designated family areas; Qatar – the host of the 2022 FIFA world cup – requires women to attend matches wearing modest clothing. Similarly, in Turkey, Lebanon, UAE, and Algeria, women face cultural barriers when attending men’s football games. In other countries, female fans suffer from subtle discrimination, including micro-aggressions, misogyny, sexism, and noninstitutionalized exclusion. Despite the vital role of fans in world football and the importance of football for many women’s lives, little has been done to address this problem. While FIFA recognizes that these discriminatory practices contradict its statutes, this recognition fails to materialize into meaningful change. This paper will argue that FIFA’s omission stems from two interrelated characteristics of world football: (1) the ultra-masculine nature of the game; (2) the insufficient recognition of fans’ significance. While fans have been given a voice in various football bodies on the domestic level, FIFA has yet to allow the representation of fans as stakeholders in world football governance. Since fans are a more heterogeneous group than players, the voices of those fans who do not fit the ultra-masculine model are not heard. Thus, by focusing mainly on male players, FIFA reproduces the hegemonic masculinity that feeds back into fan dynamics and marginalizes female fans. To rectify this problem, we will call on FIFA to provide fans and female fans in particular, with voice mechanisms and access to decision-making processes. In addition to its impact on the formation of fans’ identities, such a move will allow fans to demand better enforcement of existing anti-discrimination norms and new regulations to address their needs. The literature has yet to address the relationship between fans’ gender discrimination and global football governance. Building on Global Administrative Law scholarship and feminist theories, this paper will aim to fill this gap.

Keywords: fans, FIFA, football governance, gender discrimination, global administrative law, human rights

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114 Ant and Spider Diversity in a Rural Landscape of the Vhembe Biosphere, South Africa

Authors: Evans V. Mauda, Stefan H. Foord, Thinandavha C. Munyai

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The greatest threat to biodiversity is a loss of habitat through landscape fragmentation and attrition. Land use changes are therefore among the most immediate drivers of species diversity. Urbanization and agriculture are the main drivers of habitat loss and transformation in the Savanna biomes of South Africa. Agricultural expansion and the intensification in particular, take place at the expense of biodiversity and will probably be the primary driver of biodiversity loss in this century. Arthropods show measurable behavioural responses to changing land mosaics at the smallest scale and heterogeneous environments are therefore predicted to support more complex and diverse biological assemblages. Ants are premier soil turners, channelers of energy and dominate insect fauna, while spiders are a mega-diverse group that can regulate other invertebrate populations. This study aims to quantify the response of these two taxa in a rural-urban mosaic of a rapidly developing communal area. The study took place in and around two villages in the north-eastern corner of South Africa. Two replicates for each of the dominant land use categories, viz. urban settlements, dryland cultivation and cattle rangelands, were set out in each of the villages and sampled during the dry and wet seasons for a total of 2 villages × 3 land use categories × 2 seasons = 24 assemblages. Local scale variables measured included vertical and horizontal habitat structure as well as structural and chemical composition of the soil. Ant richness was not affected by land use but local scale variables such as vertical vegetation structure (+) and leaf litter cover (+), although vegetation complexity at lower levels was negatively associated with ant richness. However, ant richness was largely shaped by regional and temporal processes invoking the importance of dispersal and historical processes. Spider species richness was mostly affected by land use and local conditions highlighting their landscape elements. Spider richness did not vary much between villages and across seasons and seems to be less dependent on context or history. There was a considerable amount of variation in spider richness that was not explained and this could be related to factors which were not measured in this study such as temperature and competition. For both ant and spider assemblages the constrained ordination explained 18 % of variation in these taxa. Three environmental variables (leaf litter cover, active carbon and rock cover) were important in explaining ant assemblage structure, while two (sand and leaf litter cover) were important for spider assemblage structure. This study highlights the importance of disturbance (land use activities) and leaf litter with the associated effects on ant and spider assemblages across the study area.

Keywords: ants, assemblages, biosphere, diversity, land use, spiders, urbanization

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113 Spectroscopy and Electron Microscopy for the Characterization of CdSxSe1-x Quantum Dots in a Glass Matrix

Authors: C. Fornacelli, P. Colomban, E. Mugnaioli, I. Memmi Turbanti

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When semiconductor particles are reduced in scale to nanometer dimension, their optical and electro-optical properties strongly differ from those of bulk crystals of the same composition. Since sampling is often not allowed concerning cultural heritage artefacts, the potentialities of two non-invasive techniques, such as Raman and Fiber Optic Reflectance Spectroscopy (FORS), have been investigated and the results of the analysis on some original glasses of different colours (from yellow to orange and deep red) and periods (from the second decade of the 20th century to present days) are reported in the present study. In order to evaluate the potentialities of the application of non-invasive techniques to the investigation of the structure and distribution of nanoparticles dispersed in a glass matrix, Scanning Electron Microscopy (SEM) and energy-disperse spectroscopy (EDS) mapping, together with Transmission Electron Microscopy (TEM) and Electron Diffraction Tomography (EDT) have also been used. Raman spectroscopy allows a fast and non-destructive measure of the quantum dots composition and size, thanks to the evaluation of the frequencies and the broadening/asymmetry of the LO phonons bands, respectively, though the important role of the compressive strain arising from the glass matrix and the possible diffusion of zinc from the matrix to the nanocrystals should be taken into account when considering the optical-phonons frequency values. The incorporation of Zn has been assumed by an upward shifting of the LO band related to the most abundant anion (S or Se), while the role of the surface phonons as well as the confinement-induced scattering by phonons with a non-zero wavevectors on the Raman peaks broadening has been verified. The optical band gap varies from 2.42 eV (pure CdS) to 1.70 eV (CdSe). For the compositional range between 0.5≤x≤0.2, the presence of two absorption edges has been related to the contribution of both pure CdS and the CdSxSe1-x solid solution; this particular feature is probably due to the presence of unaltered cubic zinc blende structures of CdS that is not taking part to the formation of the solid solution occurring only between hexagonal CdS and CdSe. Moreover, the band edge tailing originating from the disorder due to the formation of weak bonds and characterized by the Urbach edge energy has been studied and, together with the FWHM of the Raman signal, has been assumed as a good parameter to evaluate the degree of topological disorder. SEM-EDS mapping showed a peculiar distribution of the major constituents of the glass matrix (fluxes and stabilizers), especially concerning those samples where a layered structure has been assumed thanks to the spectroscopic study. Finally, TEM-EDS and EDT were used to get high-resolution information about nanocrystals (NCs) and heterogeneous glass layers. The presence of ZnO NCs (< 4 nm) dispersed in the matrix has been verified for most of the samples, while, for those samples where a disorder due to a more complex distribution of the size and/or composition of the NCs has been assumed, the TEM clearly verified most of the assumption made by the spectroscopic techniques.

Keywords: CdSxSe1-x, EDT, glass, spectroscopy, TEM-EDS

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112 Inconsistent Effects of Landscape Heterogeneity on Animal Diversity in an Agricultural Mosaic: A Multi-Scale and Multi-Taxon Investigation

Authors: Chevonne Reynolds, Robert J. Fletcher, Jr, Celine M. Carneiro, Nicole Jennings, Alison Ke, Michael C. LaScaleia, Mbhekeni B. Lukhele, Mnqobi L. Mamba, Muzi D. Sibiya, James D. Austin, Cebisile N. Magagula, Themba’alilahlwa Mahlaba, Ara Monadjem, Samantha M. Wisely, Robert A. McCleery

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A key challenge for the developing world is reconciling biodiversity conservation with the growing demand for food. In these regions, agriculture is typically interspersed among other land-uses creating heterogeneous landscapes. A primary hypothesis for promoting biodiversity in agricultural landscapes is the habitat heterogeneity hypothesis. While there is evidence that landscape heterogeneity positively influences biodiversity, the application of this hypothesis is hindered by a need to determine which components of landscape heterogeneity drive these effects and at what spatial scale(s). Additionally, whether diverse taxonomic groups are similarly affected is central for determining the applicability of this hypothesis as a general conservation strategy in agricultural mosaics. Two major components of landscape heterogeneity are compositional and configurational heterogeneity. Disentangling the roles of each component is important for biodiversity conservation because each represents different mechanisms underpinning variation in biodiversity. We identified a priori independent gradients of compositional and configurational landscape heterogeneity within an extensive agricultural mosaic in north-eastern Swaziland. We then tested how bird, dung beetle, ant and meso-carnivore diversity responded to compositional and configurational heterogeneity across six different spatial scales. To determine if a general trend could be observed across multiple taxa, we also tested which component and spatial scale was most influential across all taxonomic groups combined, Compositional, not configurational, heterogeneity explained diversity in each taxonomic group, with the exception of meso-carnivores. Bird and ant diversity was positively correlated with compositional heterogeneity at fine spatial scales < 1000 m, whilst dung beetle diversity was negatively correlated to compositional heterogeneity at broader spatial scales > 1500 m. Importantly, because of these contrasting effects across taxa, there was no effect of either component of heterogeneity on the combined taxonomic diversity at any spatial scale. The contrasting responses across taxonomic groups exemplify the difficulty in implementing effective conservation strategies that meet the requirements of diverse taxa. To promote diverse communities across a range of taxa, conservation strategies must be multi-scaled and may involve different strategies at varying scales to offset the contrasting influences of compositional heterogeneity. A diversity of strategies are likely key to conserving biodiversity in agricultural mosaics, and we have demonstrated that a landscape management strategy that only manages for heterogeneity at one particular scale will likely fall short of management objectives.

Keywords: agriculture, biodiversity, composition, configuration, heterogeneity

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111 Revolution through Rhythm: Anti Caste and Subaltern Dimensions in Indian Rap

Authors: Nithin Raj Adithyan

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Rap music is a popular genre that features strong beats and rhythmic words. It was created by American disc jockeys and urban Black performers in the late 1970s. Additionally, it carries on West African oral traditions that were introduced to the Americas by Africans who were held as slaves and have impacted the narrative and rhythmic components of rap. Initially introduced in India in the late 1990s as mere entertainment, rap lacked the politicized undertones that it developed in the United States. However, recent years have witnessed a transformation, with Indian rap evolving into a vital tool for marginalized communities—particularly Dalits, Muslims, and tribal groups—to voice grievances against historical injustices, systemic discrimination, and caste-based oppression. This paper examines Indian rap's evolution into a potent medium for subaltern resistance, drawing from its origins in the black ghettos of America, where rap emerged as social commentary and an anti-racial political voice. Historically, music has served as an essential medium for subaltern groups in India to assert their identities and reclaim agency. Indian rap, in its current form, amplifies this function by offering a compelling platform to address issues of caste oppression, socio-economic marginalization, and symbolic exclusion. This paper examines how contemporary Indian rappers, often from Dalit and lower-caste backgrounds, leverage their art to confront systemic injustices and amplify voices that have historically been silenced. By analyzing key artists and their lyrics, this paper highlights the ways in which rap critiques the pervasive caste system, challenges social hierarchies, and fosters a sense of identity and solidarity among subaltern groups. This study uses Gayatri Spivak’s concept of “strategic essentialism” to explore how Indian rap fosters shared subaltern identity, uniting voices across regional and cultural divides. By situating Indian rap within the global hip-hop movement, the paper highlights how it contributes a unique perspective to global narratives of resilience and resistance, adapting international influences to articulate local struggles. Ultimately, this research highlights Indian rap’s role as a catalyst for change, examining its critique of caste violence, economic marginalization, and social exclusion and demonstrating how it contributes to the anti-caste movement. Through a close reading of this subaltern dimension of rap, the paper illuminates how Indian rap fosters identity, solidarity, and resistance, affirming the genre’s potential as a transformative force within the global legacy of hip-hop as an expression of subaltern agency and social dissent.

Keywords: caste oppression, hip-hop/rap, resistance, subaltern

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110 To Access the Knowledge, Awareness and Factors Associated With Diabetes Mellitus in Buea, Cameroon

Authors: Franck Acho

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This is a chronic metabolic disorder which is a fast-growing global problem with a huge social, health, and economic consequences. It is estimated that in 2010 there were globally 285 million people (approximately 6.4% of the adult population) suffering from this disease. This number is estimated to increase to 430 million in the absence of better control or cure. An ageing population and obesity are two main reasons for the increase. Diabetes mellitus is a chronic heterogeneous metabolic disorder with a complex pathogenesis. It is characterized by elevated blood glucose levels or hyperglycemia, which results from abnormalities in either insulin secretion or insulin action or both. Hyperglycemia manifests in various forms with a varied presentation and results in carbohydrate, fat, and protein metabolic dysfunctions. Long-term hyperglycemia often leads to various microvascular and macrovascular diabetic complications, which are mainly responsible for diabetes-associated morbidity and mortality. Hyperglycemia serves as the primary biomarker for the diagnosis of diabetes as well. Furthermore, it has been shown that almost 50% of the putative diabetics are not diagnosed until 10 years after onset of the disease, hence the real prevalence of global diabetes must be astronomically high. This study was conducted in a locality to access the level of knowledge, awareness and risk factors associated with people leaving with diabetes mellitus. A month before the screening was to be conducted, a health screening in some selected churches and on the local community radio as well as on relevant WhatsApp groups were advertised. A general health talk was delivered by the head of the screening unit to all attendees who were all educated on the procedure to be carried out with benefits and any possible discomforts after which the attendee’s consent was obtained. Evaluation of the participants for any leads to the diabetes selected for the screening was done by taking adequate history and physical examinations such as excessive thirst, increased urination, tiredness, hunger, unexplained weight loss, feeling irritable or having other mood changes, having blurry vision, having slow-healing sores, getting a lot of infections, such as gum, skin and vaginal infections. Out of the 94 participants the finding show that 78 were females and 16 were males, 70.21% of participants with diabetes were between the ages of 60-69yrs.The study found that only 10.63% of respondents declared a good level of knowledge of diabetes. Out of 3 symptoms of diabetes analyzed in this study, high blood sugar (58.5%) and chronic fatigue (36.17%) were the most recognized. Out of 4 diabetes risk factors analyzed in this study, obesity (21.27%) and unhealthy diet (60.63%) were the most recognized diabetes risk factors, while only 10.6% of respondents indicated tobacco use. The diabetic foot was the most recognized diabetes complication (50.57%), but some the participants indicated vision problems (30.8%),or cardiovascular diseases (20.21%) as diabetes complications.

Keywords: diabetes mellitus, non comunicable disease, general health talk, hyperglycemia

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109 An Unified Model for Longshore Sediment Transport Rate Estimation

Authors: Aleksandra Dudkowska, Gabriela Gic-Grusza

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Wind wave-induced sediment transport is an important multidimensional and multiscale dynamic process affecting coastal seabed changes and coastline evolution. The knowledge about sediment transport rate is important to solve many environmental and geotechnical issues. There are many types of sediment transport models but none of them is widely accepted. It is bacause the process is not fully defined. Another problem is a lack of sufficient measurment data to verify proposed hypothesis. There are different types of models for longshore sediment transport (LST, which is discussed in this work) and cross-shore transport which is related to different time and space scales of the processes. There are models describing bed-load transport (discussed in this work), suspended and total sediment transport. LST models use among the others the information about (i) the flow velocity near the bottom, which in case of wave-currents interaction in coastal zone is a separate problem (ii) critical bed shear stress that strongly depends on the type of sediment and complicates in the case of heterogeneous sediment. Moreover, LST rate is strongly dependant on the local environmental conditions. To organize existing knowledge a series of sediment transport models intercomparisons was carried out as a part of the project “Development of a predictive model of morphodynamic changes in the coastal zone”. Four classical one-grid-point models were studied and intercompared over wide range of bottom shear stress conditions, corresponding with wind-waves conditions appropriate for coastal zone in polish marine areas. The set of models comprises classical theories that assume simplified influence of turbulence on the sediment transport (Du Boys, Meyer-Peter & Muller, Ribberink, Engelund & Hansen). It turned out that the values of estimated longshore instantaneous mass sediment transport are in general in agreement with earlier studies and measurements conducted in the area of interest. However, none of the formulas really stands out from the rest as being particularly suitable for the test location over the whole analyzed flow velocity range. Therefore, based on the models discussed a new unified formula for longshore sediment transport rate estimation is introduced, which constitutes the main original result of this study. Sediment transport rate is calculated based on the bed shear stress and critical bed shear stress. The dependence of environmental conditions is expressed by one coefficient (in a form of constant or function) thus the model presented can be quite easily adjusted to the local conditions. The discussion of the importance of each model parameter for specific velocity ranges is carried out. Moreover, it is shown that the value of near-bottom flow velocity is the main determinant of longshore bed-load in storm conditions. Thus, the accuracy of the results depends less on the sediment transport model itself and more on the appropriate modeling of the near-bottom velocities.

Keywords: bedload transport, longshore sediment transport, sediment transport models, coastal zone

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108 The Photovoltaic Panel at End of Life: Experimental Study of Metals Release

Authors: M. Tammaro, S. Manzo, J. Rimauro, A. Salluzzo, S. Schiavo

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The solar photovoltaic (PV) modules are considered to have a negligible environmental impact compared to the fossil energy. Therefore also the waste management and the corresponding potential environmental hazard needs to be considered. The case of the photovoltaic panel is unique because the time lag from the manufacturing to the decommissioning as waste usually takes 25-30 years. Then the environmental hazard associated with end life of PV panels has been largely related to their metal contents. The principal concern regards the presence of heavy metals as Cd in thin film (TF) modules or Pb and Cr in crystalline silicon (c-Si) panels. At the end of life of PV panels, these dangerous substances could be released in the environment, if special requirements for their disposal are not adopted. Nevertheless, in literature, only a few experimental study about metal emissions from silicon crystalline/thin film panels and the corresponding environmental effect are present. As part of a study funded by the Italian national consortium for the waste collection and recycling (COBAT), the present work was aimed to analyze experimentally the potential release into the environment of hazardous elements, particularly metals, from PV waste. In this paper, for the first time, eighteen releasable metals a large number of photovoltaic panels, by c-Si and TF, manufactured in the last 30 years, together with the environmental effects by a battery of ecotoxicological tests, were investigated. Leaching tests are conducted on the crushed samples of PV module. The test is conducted according to Italian and European Standard procedure for hazard assessment of the granular waste and of the sludge. The sample material is shaken for 24 hours in HDPE bottles with an overhead mixer Rotax 6.8 VELP at indoor temperature and using pure water (18 MΩ resistivity) as leaching solution. The liquid-to-solid ratio was 10 (L/S=10, i.e. 10 liters of water per kg of solid). The ecotoxicological tests were performed in the subsequent 24 hours. A battery of toxicity test with bacteria (Vibrio fisheri), algae (Pseudochirneriella subcapitata) and crustacea (Daphnia magna) was carried out on PV panel leachates obtained as previously described and immediately stored in dark and at 4°C until testing (in the next 24 hours). For understand the actual pollution load, a comparison with the current European and Italian benchmark limits was performed. The trend of leachable metal amount from panels in relation to manufacturing years was then highlighted in order to assess the environmental sustainability of PV technology over time. The experimental results were very heterogeneous and show that the photovoltaic panels could represent an environmental hazard. The experimental results showed that the amounts of some hazardous metals (Pb, Cr, Cd, Ni), for c-Si and TF, exceed the law limits and they are a clear indication of the potential environmental risk of photovoltaic panels "as a waste" without a proper management.

Keywords: photovoltaic panel, environment, ecotoxicity, metals emission

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107 Role of Calcination Treatment on the Structural Properties and Photocatalytic Activity of Nanorice N-Doped TiO₂ Catalyst

Authors: Totsaporn Suwannaruang, Kitirote Wantala

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The purposes of this research were to synthesize titanium dioxide photocatalyst doped with nitrogen (N-doped TiO₂) by hydrothermal method and to test the photocatalytic degradation of paraquat under UV and visible light illumination. The effect of calcination treatment temperature on their physical and chemical properties and photocatalytic efficiencies were also investigated. The characterizations of calcined N-doped TiO₂ photocatalysts such as specific surface area, textural properties, bandgap energy, surface morphology, crystallinity, phase structure, elements and state of charges were investigated by Brunauer, Emmett, Teller (BET) and Barrett, Joyner, Halenda (BJH) equations, UV-Visible diffuse reflectance spectroscopy (UV-Vis-DRS) by using the Kubelka-Munk theory, Wide-angle X-ray scattering (WAXS), Focussed ion beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), respectively. The results showed that the effect of calcination temperature was significant on surface morphology, crystallinity, specific surface area, pore size diameter, bandgap energy and nitrogen content level, but insignificant on phase structure and oxidation state of titanium (Ti) atom. The N-doped TiO₂ samples illustrated only anatase crystalline phase due to nitrogen dopant in TiO₂ restrained the phase transformation from anatase to rutile. The samples presented the nanorice-like morphology. The expansion on the particle was found at 650 and 700°C of calcination temperature, resulting in increased pore size diameter. The bandgap energy was determined by Kubelka-Munk theory to be in the range 3.07-3.18 eV, which appeared slightly lower than anatase standard (3.20 eV), resulting in the nitrogen dopant could modify the optical absorption edge of TiO₂ from UV to visible light region. The nitrogen content was observed at 100, 300 and 400°C only. Also, the nitrogen element disappeared at 500°C onwards. The nitrogen (N) atom can be incorporated in TiO₂ structure with the interstitial site. The uncalcined (100°C) sample displayed the highest percent paraquat degradation under UV and visible light irradiation due to this sample revealed both the highest specific surface area and nitrogen content level. Moreover, percent paraquat removal significantly decreased with increasing calcination treatment temperature. The nitrogen content level in TiO₂ accelerated the rate of reaction with combining the effect of the specific surface area that generated the electrons and holes during illuminated with light. Therefore, the specific surface area and nitrogen content level demonstrated the important roles in the photocatalytic activity of paraquat under UV and visible light illumination.

Keywords: restraining phase transformation, interstitial site, chemical charge state, photocatalysis, paraquat degradation

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106 Fractional, Component and Morphological Composition of Ambient Air Dust in the Areas of Mining Industry

Authors: S.V. Kleyn, S.Yu. Zagorodnov, А.А. Kokoulina

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Technogenic emissions of the mining and processing complex are characterized by a high content of chemical components and solid dust particles. However, each industrial enterprise and the surrounding area have features that require refinement and parameterization. Numerous studies have shown the negative impact of fine dust PM10 and PM2.5 on the health, as well as the possibility of toxic components absorption, including heavy metals by dust particles. The target of the study was the quantitative assessment of the fractional and particle size composition of ambient air dust in the area of impact by primary magnesium production complex. Also, we tried to describe the morphology features of dust particles. Study methods. To identify the dust emission sources, the analysis of the production process has been carried out. The particulate composition of the emissions was measured using laser particle analyzer Microtrac S3500 (covered range of particle size is 20 nm to 2000 km). Particle morphology and the component composition were established by electron microscopy by scanning microscope of high resolution (magnification rate - 5 to 300 000 times) with X-ray fluorescence device S3400N ‘HITACHI’. The chemical composition was identified by X-ray analysis of the samples using an X-ray diffractometer XRD-700 ‘Shimadzu’. Determination of the dust pollution level was carried out using model calculations of emissions in the atmosphere dispersion. The calculations were verified by instrumental studies. Results of the study. The results demonstrated that the dust emissions of different technical processes are heterogeneous and fractional structure is complicated. The percentage of particle sizes up to 2.5 micrometres inclusive was ranged from 0.00 to 56.70%; particle sizes less than 10 microns inclusive – 0.00 - 85.60%; particle sizes greater than 10 microns - 14.40% -100.00%. During microscopy, the presence of nanoscale size particles has been detected. Studied dust particles are round, irregular, cubic and integral shapes. The composition of the dust includes magnesium, sodium, potassium, calcium, iron, chlorine. On the base of obtained results, it was performed the model calculations of dust emissions dispersion and establishment of the areas of fine dust РМ 10 and РМ 2.5 distribution. It was found that the dust emissions of fine powder fractions PM10 and PM2.5 are dispersed over large distances and beyond the border of the industrial site of the enterprise. The population living near the enterprise is exposed to the risk of diseases associated with dust exposure. Data are transferred to the economic entity to make decisions on the measures to minimize the risks. Exposure and risks indicators on the health are used to provide named patient health and preventive care to the citizens living in the area of negative impact of the facility.

Keywords: dust emissions, еxposure assessment, PM 10, PM 2.5

Procedia PDF Downloads 261
105 De-Securitizing Identity: Narrative (In)Consistency in Periods of Transition

Authors: Katerina Antoniou

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When examining conflicts around the world, it is evident that the majority of intractable conflicts are steeped in identity. Identity seems to be not only a causal variable for conflict, but also a catalytic parameter for the process of reconciliation that follows ceasefire. This paper focuses on the process of identity securitization that occurs between rival groups of heterogeneous collective identities – ethnic, national or religious – as well as on the relationship between identity securitization and the ability of the groups involved to reconcile. Are securitized identities obstacles to the process of reconciliation, able to hinder any prospects of peace? If the level to which an identity is securitized is catalytic to a conflict’s discourse and settlement, then which factors act as indicators of identity de-securitization? The level of an in-group’s identity securitization can be estimated through a number of indicators, one of which is narrative. The stories, views and stances each in-group adopts in relation to its history of conflict and relation with their rival out-group can clarify whether that specific in-group feels victimized and threatened or safe and ready to reconcile. Accordingly, this study discusses identity securitization through narrative in relation to intractable conflicts. Are there conflicts around the world that, despite having been identified as intractable, stagnated or insoluble, show signs of identity de-securitization through narrative? This inquiry uses the case of the Cyprus conflict and its partitioned societies to present official narratives from the two communities and assess whether these narratives have transformed, indicating a less securitized in-group identity for the Greek and Turkish Cypriots. Specifically, the study compares the official historical overviews presented by each community’s Ministry of Foreign Affairs website and discusses the extent to which the two official narratives present a securitized collective identity. In addition, the study will observe whether official stances by the two communities – as adopted by community leaders – have transformed to depict less securitization over time. Additionally, the leaders’ reflection of popular opinion is evaluated through recent opinion polls from each community. Cyprus is currently experiencing renewed optimism for reunification, with the leaders of its two communities engaging in rigorous negotiations, and with rumors calling for a potential referendum for reunification to be taking place even as early as within 2016. Although leaders’ have shown a shift in their rhetoric and have moved away from narratives of victimization, this is not the case for the official narratives used by their respective ministries of foreign affairs. The study’s findings explore whether this narrative inconsistency proves that Cyprus is transitioning towards reunification, or whether the leaders are risking sending a securitized population to the polls to reject a potential reunification. More broadly, this study suggests that in the event that intractable conflicts might be moving towards viable peace, in-group narratives--official narratives in particular--can act as indicators of the extent to which rival entities have managed to reconcile.

Keywords: conflict, identity, narrative, reconciliation

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104 Effect of Compaction Method on the Mechanical and Anisotropic Properties of Asphalt Mixtures

Authors: Mai Sirhan, Arieh Sidess

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Asphaltic mixture is a heterogeneous material composed of three main components: aggregates; bitumen and air voids. The professional experience and scientific literature categorize asphaltic mixture as a viscoelastic material, whose behavior is determined by temperature and loading rate. Properties characterization of the asphaltic mixture used under the service conditions is done by compacting and testing cylindric asphalt samples in the laboratory. These samples must resemble in a high degree internal structure of the mixture achieved in service, and the mechanical characteristics of the compacted asphalt layer in the pavement. The laboratory samples are usually compacted in temperatures between 140 and 160 degrees Celsius. In this temperature range, the asphalt has a low degree of strength. The laboratory samples are compacted using the dynamic or vibrational compaction methods. In the compaction process, the aggregates tend to align themselves in certain directions that lead to anisotropic behavior of the asphaltic mixture. This issue has been studied in the Strategic Highway Research Program (SHRP) research, that recommended using the gyratory compactor based on the assumption that this method is the best in mimicking the compaction in the service. In Israel, the Netivei Israel company is considering adopting the Gyratory Method as a replacement for the Marshall method used today. Therefore, the compatibility of the Gyratory Method for the use with Israeli asphaltic mixtures should be investigated. In this research, we aimed to examine the impact of the compaction method used on the mechanical characteristics of the asphaltic mixtures and to evaluate the degree of anisotropy in relation to the compaction method. In order to carry out this research, samples have been compacted in the vibratory and gyratory compactors. These samples were cylindrically cored both vertically (compaction wise) and horizontally (perpendicular to compaction direction). These models were tested under dynamic modulus and permanent deformation tests. The comparable results of the tests proved that: (1) specimens compacted by the vibratory compactor had higher dynamic modulus values than the specimens compacted by the gyratory compactor (2) both vibratory and gyratory compacted specimens had anisotropic behavior, especially in high temperatures. Also, the degree of anisotropy is higher in specimens compacted by the gyratory method. (3) Specimens compacted by the vibratory method that were cored vertically had the highest resistance to rutting. On the other hand, specimens compacted by the vibratory method that were cored horizontally had the lowest resistance to rutting. Additionally (4) these differences between the different types of specimens rise mainly due to the different internal arrangement of aggregates resulting from the compaction method. (5) Based on the initial prediction of the performance of the flexible pavement containing an asphalt layer having characteristics based on the results achieved in this research. It can be concluded that there is a significant impact of the compaction method and the degree of anisotropy on the strains that develop in the pavement, and the resistance of the pavement to fatigue and rutting defects.

Keywords: anisotropy, asphalt compaction, dynamic modulus, gyratory compactor, mechanical properties, permanent deformation, vibratory compactor

Procedia PDF Downloads 118
103 Interfacial Reactions between Aromatic Polyamide Fibers and Epoxy Matrix

Authors: Khodzhaberdi Allaberdiev

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In order to understand the interactions on the interface polyamide fibers and epoxy matrix in fiber- reinforced composites were investigated industrial aramid fibers: armos, svm, terlon using individual epoxy matrix components, epoxies: diglycidyl ether of bisphenol A (DGEBA), three- and diglycidyl derivatives of m, p-amino-, m, p-oxy-, o, m,p-carboxybenzoic acids, the models: curing agent, aniline and the compound, that depict of the structure the primary addition reaction the amine to the epoxy resin, N-di (oxyethylphenoxy) aniline. The chemical structure of the surface of untreated and treated polyamide fibers analyzed using Fourier transform infrared spectroscopy (FTIR). The impregnation of fibers with epoxy matrix components and N-di (oxyethylphenoxy) aniline has been carried out by heating 150˚C (6h). The optimum fiber loading is at 65%.The result a thermal treatment is the covalent bonds formation , derived from a combined of homopolymerization and crosslinking mechanisms in the interfacial region between the epoxy resin and the surface of fibers. The reactivity of epoxy resins on interface in microcomposites (MC) also depends from processing aids treated on surface of fiber and the absorbance moisture. The influences these factors as evidenced by the conversion of epoxy groups values in impregnated with DGEBA of the terlons: industrial, dried (in vacuum) and purified samples: 5.20 %, 4.65% and 14.10%, respectively. The same tendency for svm and armos fibers is observed. The changes in surface composition of these MC were monitored by X-ray photoelectron spectroscopy (XPS). In the case of the purified fibers, functional groups of fibers act as well as a catalyst and curing agent of epoxy resin. It is found that the value of the epoxy groups conversion for reinforced formulations depends on aromatic polyamides nature and decreases in the order: armos >svm> terlon. This difference is due of the structural characteristics of fibers. The interfacial interactions also examined between polyglycidyl esters substituted benzoic acids and polyamide fibers in the MC. It is found that on interfacial interactions these systems influences as well as the structure and the isomerism of epoxides. The IR-spectrum impregnated fibers with aniline showed that the polyamide fibers appreciably with aniline do not react. FTIR results of treated fibers with N-di (oxyethylphenoxy) aniline fibers revealed dramatically changes IR-characteristic of the OH groups of the amino alcohol. These observations indicated hydrogen bondings and covalent interactions between amino alcohol and functional groups of fibers. This result also confirms appearance of the exo peak on Differential Scanning Calorimetry (DSC) curve of the MC. Finally, the theoretical evaluation non-covalent interactions between individual epoxy matrix components and fibers has been performed using the benzanilide and its derivative contaning the benzimidazole moiety as a models of terlon and svm,armos, respectively. Quantum-topological analysis also demonstrated the existence hydrogen bond between amide group of models and epoxy matrix components.All the results indicated that on the interface polyamide fibers and epoxy matrix exist not only covalent, but and non-covalent the interactions during the preparation of MC.

Keywords: epoxies, interface, modeling, polyamide fibers

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102 Thermo-Mechanical Processing Scheme to Obtain Micro-Duplex Structure Favoring Superplasticity in an As-Cast and Homogenized Medium Alloyed Nickel Base Superalloy

Authors: K. Sahithya, I. Balasundar, Pritapant, T. Raghua

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Ni-based superalloy with a nominal composition Ni-14% Cr-11% Co-5.8% Mo-2.4% Ti-2.4% Nb-2.8% Al-0.26 % Fe-0.032% Si-0.069% C (all in wt %) is used as turbine discs in a variety of aero engines. Like any other superalloy, the primary processing of the as-cast superalloy poses a major challenge due to its complex alloy chemistry. The challenge was circumvented by characterizing the different phases present in the material, optimizing the homogenization treatment, identifying a suitable thermomechanical processing window using dynamic materials modeling. The as-cast material was subjected to homogenization at 1200°C for a soaking period of 8 hours and quenched using different media. Water quenching (WQ) after homogenization resulted in very fine spherical γꞌ precipitates of sizes 30-50 nm, whereas furnace cooling (FC) after homogenization resulted in bimodal distribution of precipitates (primary gamma prime of size 300nm and secondary gamma prime of size 5-10 nm). MC type primary carbides that are stable till the melting point of the material were found in both WQ and FC samples. Deformation behaviour of both the materials below (1000-1100°C) and above gamma prime solvus (1100-1175°C) was evaluated by subjecting the material to series of compression tests at different constant true strain rates (0.0001/sec-1/sec). An in-detail examination of the precipitate dislocation interaction mechanisms carried out using TEM revealed precipitate shearing and Orowan looping as the mechanisms governing deformation in WQ and FC, respectively. Incoherent/semi coherent gamma prime precipitates in the case of FC material facilitates better workability of the material, whereas the coherent precipitates in WQ material contributed to higher resistance to deformation of the material. Both the materials exhibited discontinuous dynamic recrystallization (DDRX) above gamma prime solvus temperature. The recrystallization kinetics was slower in the case of WQ material. Very fine grain boundary carbides ( ≤ 300 nm) retarded the recrystallisation kinetics in WQ. Coarse carbides (1-5 µm) facilitate particle stimulated nucleation in FC material. The FC material was cogged (primary hot working) 1120˚C, 0.03/sec resulting in significant grain refinement, i.e., from 3000 μm to 100 μm. The primary processed material was subjected to intensive thermomechanical deformation subsequently by reducing the temperature by 50˚C in each processing step with intermittent heterogenization treatment at selected temperatures aimed at simultaneous coarsening of the gamma prime precipitates and refinement of the gamma matrix grains. The heterogeneous annealing treatment carried out, resulted in gamma grains of 10 μm and gamma prime precipitates of 1-2 μm. Further thermo mechanical processing of the material was carried out at 1025˚C to increase the homogeneity of the obtained micro-duplex structure.

Keywords: superalloys, dynamic material modeling, nickel alloys, dynamic recrystallization, superplasticity

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101 Re-Development and Lost Industrial History: Darling Harbour of Sydney

Authors: Ece Kaya

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Urban waterfront re-development is a well-established phenomenon internationally since 1960s. In cities throughout the world, old industrial waterfront land is being redeveloped into luxury housing, offices, tourist attractions, cultural amenities and shopping centres. These developments are intended to attract high-income residents, tourists and investors to the city. As urban waterfronts are iconic places for the cities and catalyst for further development. They are often referred as flagship project. In Sydney, the re-development of industrial waterfront has been exposed since 1980s with Darling Harbour Project. Darling Harbour waterfront used to be the main arrival and landing place for commercial and industrial shipping until 1970s. Its urban development has continued since the establishment of the city. It was developed as a major industrial and goods-handling precinct in 1812. This use was continued by the mid-1970s. After becoming a redundant industrial waterfront, the area was ripe for re-development in 1984. Darling Harbour is now one of the world’s fascinating waterfront leisure and entertainment destinations and its transformation has been considered as a success story. It is a contradictory statement for this paper. Data collection was carried out using an extensive archival document analysis. The data was obtained from Australian Institute of Architects, City of Sydney Council Archive, Parramatta Heritage Office, Historic Houses Trust, National Trust, and University of Sydney libraries, State Archive, State Library and Sydney Harbour Foreshore Authority Archives. Public documents, primarily newspaper articles and design plans, were analysed to identify possible differences in motives and to determine the process of implementation of the waterfront redevelopments. It was also important to obtain historical photographs and descriptions to understand how the waterfront had been altered. Sites maps in different time periods have been identified to understand what kind of changes happened on the urban landscape and how the developments affected areas. Newspaper articles and editorials have been examined in order to discover what aspects of the projects reflected the history and heritage. The thematic analysis of the archival data helped determine Darling Harbour is a historically important place as it had represented a focal point for Sydney's industrial growth and the cradle of industrial development in European Australia. It has been found that the development area was designated in order to be transformed to a place for tourist, education, recreational, entertainment, cultural and commercial activities and as a result little evidence remained of its industrial past. This paper aims to discuss the industrial significance of Darling Harbour and to explain the changes on its industrial landscape. What is absent now is the layer of its history that creates the layers of meaning to the place so its historic industrial identity is effectively lost.

Keywords: historical significance, industrial heritage, industrial waterfront, re-development

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100 Composition and Catalytic Behaviour of Biogenic Iron Containing Materials Obtained by Leptothrix Bacteria Cultivation in Different Growth Media

Authors: M. Shopska, D. Paneva, G. Kadinov, Z. Cherkezova-Zheleva, I. Mitov

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The iron containing materials are used as catalysts in different processes. The chemical methods of their synthesis use toxic and expensive chemicals; sophisticated devices; energy consumption processes that raise their cost. Besides, dangerous waste products are formed. At present time such syntheses are out of date and wasteless technologies are indispensable. The bioinspired technologies are consistent with the ecological requirements. Different microorganisms participate in the biomineralization of the iron and some phytochemicals are involved, too. The methods for biogenic production of iron containing materials are clean, simple, nontoxic, realized at ambient temperature and pressure, cheaper. The biogenic iron materials embrace different iron compounds. Due to their origin these substances are nanosized, amorphous or poorly crystalline, porous and have number of useful properties like SPM, high magnetism, low toxicity, biocompatibility, absorption of microwaves, high surface area/volume ratio, active sites on the surface with unusual coordination that distinguish them from the bulk materials. The biogenic iron materials are applied in the heterogeneous catalysis in different roles - precursor, active component, support, immobilizer. The application of biogenic iron oxide materials gives rise to increased catalytic activity in comparison with those of abiotic origin. In our study we investigated the catalytic behavior of biomasses obtained by cultivation of Leptothrix bacteria in three nutrition media – Adler, Fedorov, and Lieske. The biomass composition was studied by Moessbauer spectroscopy and transmission IRS. Catalytic experiments on CO oxidation were carried out using in situ DRIFTS. Our results showed that: i) the used biomasses contain α-FeOOH, γ-FeOOH, γ-Fe2O3 in different ratios; ii) the biomass formed in Adler medium contains γ-FeOOH as main phase. The CO conversion was about 50% as evaluated by decreased integrated band intensity in the gas mixture spectra during the reaction. The main phase in the spent sample is γ-Fe2O3; iii) the biomass formed in Lieske medium contains α-FeOOH. The CO conversion was about 20%. The main phase in the spent sample is α-Fe2O3; iv) the biomass formed in Fedorov medium contains γ-Fe2O3 as main phase. CO conversion in the test reaction was about 19%. The results showed that the catalytic activity up to 200°C resulted predominantly from α-FeOOH and γ-FeOOH. The catalytic activity at temperatures higher than 200°C was due to the formation of γ-Fe2O3. The oxyhydroxides, which are the principal compounds in the biomass, have low catalytic activity in the used reaction; the maghemite has relatively good catalytic activity; the hematite has activity commensurate with that of the oxyhydroxides. Moreover it can be affirmed that catalytic activity is inherent in maghemite, which is obtained by transformation of the biogenic lepidocrocite, i.e. it has biogenic precursor.

Keywords: nanosized biogenic iron compounds, catalytic behavior in reaction of CO oxidation, in situ DRIFTS, Moessbauer spectroscopy

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99 Bacterial Diversity in Human Intestinal Microbiota and Correlations with Nutritional Behavior, Physiology, Xenobiotics Intake and Antimicrobial Resistance in Obese, Overweight and Eutrophic Individuals

Authors: Thais O. de Paula, Marjorie R. A. Sarmiento, Francis M. Borges, Alessandra B. Ferreira-Machado, Juliana A. Resende, Dioneia E. Cesar, Vania L. Silva, Claudio G. Diniz

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Obesity is currently a worldwide public health threat, being considered a pandemic multifactorial disease related to the human gut microbiota (GM). Add to that GM is considered an important reservoir of antimicrobial resistance genes (ARG) and little is known on GM and ARG in obesity, considering the altered physiology and xenobiotics intake. As regional and social behavior may play important roles in GM modulation, and most of the studies are based on small sample size and various methodological approaches resulting in difficulties for data comparisons, this study was focused on the investigation of GM bacterial diversity in obese (OB), overweight (OW) and eutrophic individuals (ET) considering their nutritional, clinical and social characteristics; and comparative screening of AGR related to their physiology and xenobiotics intake. Microbial community was accessed by FISH considering phyla as a taxonomic level, and PCR-DGGE followed by dendrograms evaluation (UPGMA method) from fecal metagenome of 72 volunteers classified according to their body mass index (BMI). Nutritional, clinical, social parameters and xenobiotics intake were recorded for correlation analysis. The fecal metagenome was also used as template for PCR targeting 59 different ARG. Overall, 62% of OB were hypertensive, and 12% or 4% were, regarding the OW and ET individuals. Most of the OB were rated as low income (80%). Lower relative bacterial densities were observed in the OB compared to ET for almost all studied taxa (p < 0.05) with Firmicutes/Bacteroidetes ratio increased in the OB group. OW individuals showed a bacterial density representative of GM more likely to the OB. All the participants were clustered in 3 different groups based on the PCR-DGGE fingerprint patterns (C1, C2, C3), being OB mostly grouped in C1 (83.3%) and ET mostly grouped in C3 (50%). The cluster C2 showed to be transitional. Among 27 ARG detected, a cluster of 17 was observed in all groups suggesting a common core. In general, ARG were observed mostly within OB individuals followed by OW and ET. The ratio between ARG and bacterial groups may suggest that AGR were more related to enterobacteria. Positive correlations were observed between ARG and BMI, calories and xenobiotics intake (especially use of sweeteners). As with nutritional and clinical characteristics, our data may suggest that GM of OW individuals behave in a heterogeneous pattern, occasionally more likely to the OB or to the ET. Regardless the regional and social behaviors of our population, the methodological approaches in this study were complementary and confirmatory. The imbalance of GM over the health-disease interface in obesity is a matter of fact, but its influence in host's physiology is still to be clearly elucidated to help understanding the multifactorial etiology of obesity. Although the results are in agreement with observations that GM is altered in obesity, the altered physiology in OB individuals seems to be also associated to the increased xenobiotics intake and may interfere with GM towards antimicrobial resistance, as observed by the fecal metagenome and ARG screening. Support: FAPEMIG, CNPQ, CAPES, PPGCBIO/UFJF.

Keywords: antimicrobial resistance, bacterial diversity, gut microbiota, obesity

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98 The Problem of the Use of Learning Analytics in Distance Higher Education: An Analytical Study of the Open and Distance University System in Mexico

Authors: Ismene Ithai Bras-Ruiz

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Learning Analytics (LA) is employed by universities not only as a tool but as a specialized ground to enhance students and professors. However, not all the academic programs apply LA with the same goal and use the same tools. In fact, LA is formed by five main fields of study (academic analytics, action research, educational data mining, recommender systems, and personalized systems). These fields can help not just to inform academic authorities about the situation of the program, but also can detect risk students, professors with needs, or general problems. The highest level applies Artificial Intelligence techniques to support learning practices. LA has adopted different techniques: statistics, ethnography, data visualization, machine learning, natural language process, and data mining. Is expected that any academic program decided what field wants to utilize on the basis of his academic interest but also his capacities related to professors, administrators, systems, logistics, data analyst, and the academic goals. The Open and Distance University System (SUAYED in Spanish) of the University National Autonomous of Mexico (UNAM), has been working for forty years as an alternative to traditional programs; one of their main supports has been the employ of new information and communications technologies (ICT). Today, UNAM has one of the largest network higher education programs, twenty-six academic programs in different faculties. This situation means that every faculty works with heterogeneous populations and academic problems. In this sense, every program has developed its own Learning Analytic techniques to improve academic issues. In this context, an investigation was carried out to know the situation of the application of LA in all the academic programs in the different faculties. The premise of the study it was that not all the faculties have utilized advanced LA techniques and it is probable that they do not know what field of study is closer to their program goals. In consequence, not all the programs know about LA but, this does not mean they do not work with LA in a veiled or, less clear sense. It is very important to know the grade of knowledge about LA for two reasons: 1) This allows to appreciate the work of the administration to improve the quality of the teaching and, 2) if it is possible to improve others LA techniques. For this purpose, it was designed three instruments to determinate the experience and knowledge in LA. These were applied to ten faculty coordinators and his personnel; thirty members were consulted (academic secretary, systems manager, or data analyst, and coordinator of the program). The final report allowed to understand that almost all the programs work with basic statistics tools and techniques, this helps the administration only to know what is happening inside de academic program, but they are not ready to move up to the next level, this means applying Artificial Intelligence or Recommender Systems to reach a personalized learning system. This situation is not related to the knowledge of LA, but the clarity of the long-term goals.

Keywords: academic improvements, analytical techniques, learning analytics, personnel expertise

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97 Efficient Treatment of Azo Dye Wastewater with Simultaneous Energy Generation by Microbial Fuel Cell

Authors: Soumyadeep Bhaduri, Rahul Ghosh, Rahul Shukla, Manaswini Behera

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The textile industry consumes a substantial amount of water throughout the processing and production of textile fabrics. The water eventually turns into wastewater, where it acts as an immense damaging nuisance due to its dye content. Wastewater streams contain a percentage ranging from 2.0% to 50.0% of the total weight of dye used, depending on the dye class. The management of dye effluent in textile industries presents a formidable challenge to global sustainability. The current focus is on implementing wastewater treatment technology that enable the recycling of wastewater, reduce energy usage and offset carbon emissions. Microbial fuel cell (MFC) is a device that utilizes microorganisms as a bio-catalyst to effectively treat wastewater while also producing electricity. The MFC harnesses the chemical energy present in wastewater by oxidizing organic compounds in the anodic chamber and reducing an electron acceptor in the cathodic chamber, thereby generating electricity. This research investigates the potential of MFCs to tackle this challenge of azo dye removal with simultaneously generating electricity. Although MFCs are well-established for wastewater treatment, their application in dye decolorization with concurrent electricity generation remains relatively unexplored. This study aims to address this gap by assessing the effectiveness of MFCs as a sustainable solution for treating wastewater containing azo dyes. By harnessing microorganisms as biocatalysts, MFCs offer a promising avenue for environmentally friendly dye effluent management. The performance of MFCs in treating azo dyes and generating electricity was evaluated by optimizing the Chemical Oxygen Demand (COD) and Hydraulic Retention Time (HRT) of influent. COD and HRT values ranged from 1600 mg/L to 2400 mg/L and 5 to 9 days, respectively. Results showed that the maximum open circuit voltage (OCV) reached 648 mV at a COD of 2400 mg/L and HRT of 5 days. Additionally, maximum COD removal of 98% and maximum color removal of 98.91% were achieved at a COD of 1600 mg/L and HRT of 9 days. Furthermore, the study observed a maximum power density of 19.95 W/m3 at a COD of 2400 mg/L and HRT of 5 days. Electrochemical analysis, including linear sweep voltammetry (LSV), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were done to find out the response current and internal resistance of the system. To optimize pH and dye concentration, pH values were varied from 4 to 10, and dye concentrations ranged from 25 mg/L to 175 mg/L. The highest voltage output of 704 mV was recorded at pH 7, while a dye concentration of 100 mg/L yielded the maximum output of 672 mV. This study demonstrates that MFCs offer an efficient and sustainable solution for treating azo dyes in textile industry wastewater, while concurrently generating electricity. These findings suggest the potential of MFCs to contribute to environmental remediation and sustainable development efforts on a global scale.

Keywords: textile wastewater treatment, microbial fuel cell, renewable energy, sustainable wastewater treatment

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96 Pricing Effects on Equitable Distribution of Forest Products and Livelihood Improvement in Nepalese Community Forestry

Authors: Laxuman Thakuri

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Despite the large number of in-depth case studies focused on policy analysis, institutional arrangement, and collective action of common property resource management; how the local institutions take the pricing decision of forest products in community forest management and what kinds of effects produce it, the answers of these questions are largely silent among the policy-makers and researchers alike. The study examined how the local institutions take the pricing decision of forest products in the lowland community forestry of Nepal and how the decisions affect to equitable distribution of benefits and livelihood improvement which are also objectives of Nepalese community forestry. The study assumes that forest products pricing decisions have multiple effects on equitable distribution and livelihood improvement in the areas having heterogeneous socio-economic conditions. The dissertation was carried out at four community forests of lowland, Nepal that has characteristics of high value species, matured-experience of community forest management and better record-keeping system of forest products production, pricing and distribution. The questionnaire survey, individual to group discussions and direct field observation were applied for data collection from the field, and Lorenz curve, gini-coefficient, χ²-text, and SWOT (Strong, Weak, Opportunity, and Threat) analysis were performed for data analysis and results interpretation. The dissertation demonstrates that the low pricing strategy of high-value forest products was supposed crucial to increase the access of socio-economically weak households, and to and control over the important forest products such as timber, but found counter productive as the strategy increased the access of socio-economically better-off households at higher rate. In addition, the strategy contradicts to collect a large-scale community fund and carry out livelihood improvement activities as per the community forestry objectives. The crucial part of the study is despite the fact of low pricing strategy; the timber alone contributed large part of community fund collection. The results revealed close relation between pricing decisions and livelihood objectives. The action research result shows that positive price discrimination can slightly reduce the prevailing inequality and increase the fund. However, it lacks to harness the full price of forest products and collects a large-scale community fund. For broader outcomes of common property resource management in terms of resource sustainability, equity, and livelihood opportunity, the study suggests local institutions to harness the full price of resource products with respect to the local market.

Keywords: community, equitable, forest, livelihood, socioeconomic, Nepal

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95 Chemical Modifications of Three Underutilized Vegetable Fibres for Improved Composite Value Addition and Dye Absorption Performance

Authors: Abayomi O. Adetuyi, Jamiu M. Jabar, Samuel O. Afolabi

Abstract:

Vegetable fibres are classes of fibres of low density, biodegradable and non-abrasive that are largely abundant fibre materials with specific properties and mostly found/ obtained in plants on earth surface. They are classified into three categories, depending on the part of the plant from which they are gotten from namely: fruit, Blast and Leaf fibre. Ever since four/five millennium B.C, attention has been focussing on the commonest and highly utilized cotton fibre obtained from the fruit of cotton plants (Gossypium spp), for the production of cotton fabric used in every home today. The present study, therefore, focused on the ability of three underutilized vegetable (fruit) fibres namely: coir fiber (Eleas coniferus), palm kernel fiber and empty fruit bunch fiber (Elias guinensis) through chemical modifications for better composite value addition performance to polyurethane form and dye adsorption. These fibres were sourced from their parents’ plants, identified and cleansed with 2% hot detergent solution 1:100, rinsed in distilled water and oven-dried to constant weight, before been chemically modified through alkali bleaching, mercerization and acetylation. The alkali bleaching involves treating 0.5g of each fiber material with 100 mL of 2% H2O2 in 25 % NaOH solution with refluxing for 2 h. While that of mercerization and acetylation involves the use of 5% sodium hydroxide NaOH solution for 2 h and 10% acetic acid- acetic anhydride 1:1 (v/v) (CH3COOH) / (CH3CO)2O solution with conc. H2SO4 as catalyst for 1 h, respectively on the fibres. All were subsequently washed thoroughly with distilled water and oven dried at 105 0C for 1 h. These modified fibres were incorporated as composite into polyurethane form and used in dye adsorption study of indigo. The first two treatments led to fiber weight reduction, while the acidified acetic anhydride treatment gave the fibers weight increment. All the treated fibers were found to be of less hydrophilic nature, better mechanical properties, higher thermal stabilities as well as better adsorption surfaces/capacities than the untreated ones. These were confirmed by gravimetric analysis, Instron Universal Testing Machine, Thermogravimetric Analyser and the Scanning Electron Microscope (SEM) respectively. The fiber morphology of the modified fibers showed smoother surfaces than unmodified fibres.The empty fruit bunch fibre and the coconut coir fibre are better than the palm kernel fibres as reinforcers for composites or as adsorbents for waste-water treatment. Acetylation and alkaline bleaching treatment improve the potentials of the fibres more than mercerization treatment. Conclusively, vegetable fibres, especially empty fruit bunch fibre and the coconut coir fibre, which are cheap, abundant and underutilized, can replace the very costly powdered activated carbon in wastewater treatment and as reinforcer in foam.

Keywords: chemical modification, industrial application, value addition, vegetable fibre

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94 Photocatalytic Properties of Pt/Er-KTaO3

Authors: Anna Krukowska, Tomasz Klimczuk, Adriana Zaleska-Medynska

Abstract:

Photoactive materials have attracted attention due to their potential application in the degradation of environmental pollutants to non-hazardous compounds in an eco-friendly route. Among semiconductor photocatalysts, tantalates such as potassium tantalate (KTaO3) is one of the excellent functional photomaterial. However, tantalates-based materials are less active under visible-light irradiation, the enhancement in photoactivity could be improved with the modification of opto-eletronic properties of KTaO3 by doping rare earth metal (Er) and further photodeposition of noble metal nanoparticles (Pt). Inclusion of rare earth element in orthorhombic structure of tantalate can generate one high-energy photon by absorbing two or more incident low-energy photons, which convert visible-light and infrared-light into the ultraviolet-light to satisfy the requirement of KTaO3 photocatalysts. On the other hand, depositions of noble metal nanoparticles on the surface of semiconductor strongly absorb visible-light due to their surface plasmon resonance, in which their conducting electrons undergo a collective oscillation induced by electric field of visible-light. Furthermore, the high dispersion of Pt nanoparticles, which will be obtained by photodeposition process is additional important factor to improve the photocatalytic activity. The present work is aimed to study the effect of photocatalytic process of the prepared Er-doped KTaO3 and further incorporation of Pt nanoparticles by photodeposition. Moreover, the research is also studied correlations between photocatalytic activity and physico-chemical properties of obtained Pt/Er-KTaO3 samples. The Er-doped KTaO3 microcomposites were synthesized by a hydrothermal method. Then photodeposition method was used for Pt loading over Er-KTaO3. The structural and optical properties of Pt/Er-KTaO3 photocatalytic were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD), volumetric adsorption method (BET), UV-Vis absorption measurement, Raman spectroscopy and luminescence spectroscopy. The photocatalytic properties of Pt/Er-KTaO3 microcomposites were investigated by degradation of phenol in aqueous phase as model pollutant under visible and ultraviolet-light irradiation. Results of this work show that all the prepared photocatalysis exhibit low BET surface area, although doping of the bare KTaO3 with rare earth element (Er) presents a slight increase in this value. The crystalline structure of Pt/Er-KTaO3 powders exhibited nearly identical positions for the main peak at about 22,8o and the XRD pattern could be assigned to an orthorhombic distorted perovskite structure. The Raman spectra of obtained semiconductors confirmed demonstrating perovskite-like structure. The optical absorption spectra of Pt nanoparticles exhibited plasmon absorption band for main peaks at about 216 and 264 nm. The addition of Pt nanoparticles increased photoactivity compared to Er-KTaO3 and pure KTaO3. Summary optical properties of KTaO3 change with its doping Er-element and further photodeposition of Pt nanoparticles.

Keywords: heterogeneous photocatalytic, KTaO3 photocatalysts, Er3+ ion doping, Pt photodeposition

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93 Disability in the Course of a Chronic Disease: The Example of People Living with Multiple Sclerosis in Poland

Authors: Milena Trojanowska

Abstract:

Disability is a phenomenon for which meanings and definitions have evolved over the decades. This became the trigger to start a project to answer the question of what disability constitutes in the course of an incurable chronic disease. The chosen research group are people living with multiple sclerosis.The contextual phase of the research was participant observation at the Polish Multiple Sclerosis Society, the largest NGO in Poland supporting people living with MS and their relatives. The research techniques used in the project are (in order of implementation): group interviews with people living with MS and their relatives, narrative interviews, asynchronous technique, participant observation during events organised for people living with MS and their relatives.The researcher is currently conducting follow-up interviews, as inaccuracies in the respondents' narratives were identified during the data analysis. Interviews and supplementary research techniques were used over the four years of the research, and the researcher also benefited from experience gained from 12 years of working with NGOs (diaries, notes). The research was carried out in Poland with the participation of people living in this country only.The research has been based on grounded theory methodology in a constructivist perspectivedeveloped by Kathy Charmaz. The goal was to follow the idea that research must be reliable, original, and useful. The aim was to construct an interpretive theory that assumes temporality and the processualityof social life. TheAtlas.ti software was used to collect research material and analyse it. It is a program from the CAQDAS(Computer-Assisted Qualitative Data Analysis Software) group.Several key factors influencing the construction of a disability identity by people living with multiple sclerosis was identified:-course of interaction with significant relatives,- the expectation of identification with disability (expressed by close relatives),- economic profitability (pension, allowances),- institutional advantages (e.g. parking card),- independence and autonomy (not equated with physical condition, but access to adapted infrastructure and resources to support daily functioning),- the way a person with MS construes the meaning of disability,- physical and mental state,- medical diagnosis of illness.In addition, it has been shown that making an assumption about the experience of disability in the course of MS is a form of cognitive reductionism leading to further phenomenon such as: the expectation of the person with MS to construct a social identity as a person with a disability (e.g. giving up work), the occurrence of institutional inequalities. It can also be a determinant of the choice of a life strategy that limits social and individual functioning, even if this necessity is not influenced by the person's physical or psychological condition.The results of the research are important for the development of knowledge about the phenomenon of disability. It indicates the contextuality and complexity of the disability phenomenon, which in the light of the research is a set of different phenomenon of heterogeneous nature and multifaceted causality. This knowledge can also be useful for institutions and organisations in the non-governmental sector supporting people with disabilities and people living with multiple sclerosis.

Keywords: disability, multiple sclerosis, grounded theory, poland

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

Authors: Lishuang Ma

Abstract:

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

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

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91 Allylation of Active Methylene Compounds with Cyclic Baylis-Hillman Alcohols: Why Is It Direct and Not Conjugate?

Authors: Karim Hrratha, Khaled Essalahb, Christophe Morellc, Henry Chermettec, Salima Boughdiria

Abstract:

Among the carbon-carbon bond formation types, allylation of active methylene compounds with cyclic Baylis-Hillman (BH) alcohols is a reliable and widely used method. This reaction is a very attractive tool in organic synthesis of biological and biodiesel compounds. Thus, in view of an insistent and peremptory request for an efficient and straightly method for synthesizing the desired product, a thorough analysis of various aspects of the reaction processes is an important task. The product afforded by the reaction of active methylene with BH alcohols depends largely on the experimental conditions, notably on the catalyst properties. All experiments reported that catalysis is needed for this reaction type because of the poor ability of alcohol hydroxyl group to be as a suitable leaving group. Within the catalysts, several transition- metal based have been used such as palladium in the presence of acid or base and have been considered as reliable methods. Furthemore, acid catalysts such as BF3.OEt2, BiX3 (X= Cl, Br, I, (OTf)3), InCl3, Yb(OTf)3, FeCl3, p-TsOH and H-montmorillonite have been employed to activate the C-C bond formation through the alkylation of active methylene compounds. Interestingly a report of a smoothly process for the ability of 4-imethyaminopyridine(DMAP) to catalyze the allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol appeared recently. However, the reaction mechanism remains ambiguous, since the C- allylation process leads to an unexpected product (noted P1), corresponding to a direct allylation instead of conjugate allylation, which involves the most electrophilic center according to the electron withdrawing group CO effect. The main objective of the present theoretical study is to better understand the role of the DMAP catalytic activity as well as the process leading to the end- product (P1) for the catalytic reaction of a cyclic BH alcohol with active methylene compounds. For that purpose, we have carried out computations of a set of active methylene compounds varying by R1 and R2 toward the same alcohol, and we have attempted to rationalize the mechanisms thanks to the acid–base approach, and conceptual DFT tools such as chemical potential, hardness, Fukui functions, electrophilicity index and dual descriptor, as these approaches have shown a good prediction of reactions products.The present work is then organized as follows: In a first part some computational details will be given, introducing the reactivity indexes used in the present work, then Section 3 is dedicated to the discussion of the prediction of the selectivity and regioselectivity. The paper ends with some concluding remarks. In this work, we have shown, through DFT method at the B3LYP/6-311++G(d,p) level of theory that: The allylation of active methylene compounds with cyclic BH alcohol is governed by orbital control character. Hence the end- product denoted P1 is generated by direct allylation.

Keywords: DFT calculation, gas phase pKa, theoretical mechanism, orbital control, charge control, Fukui function, transition state

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