Search results for: structures & structural stability

Authors: Su Mon Saw, Joe Rothnagel

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Short open reading frames (sORFs) located in 5’UTR of mRNAs are known as uORFs. Characterization of uORF-encoded peptides (uPEPs) i.e., a subset of short open reading frame encoded peptides (sPEPs) and their translation regulation lead to understanding of causes of genetic disease, proteome complexity and development of treatments. Existence of uORFs within cellular proteome could be detected by LC-MS/MS. The ability of uORF to be translated into uPEP and achievement of uPEP identification will allow uPEP’s characterization, structures, functions, subcellular localization, evolutionary maintenance (conservation in human and other species) and abundance in cells. It is hypothesized that a subset of sORFs are translatable and that their encoded sPEPs are functional and are endogenously expressed contributing to the eukaryotic cellular proteome complexity. This project aimed to investigate whether sORFs encode functional peptides. Liquid chromatography-mass spectrometry (LC-MS) and bioinformatics were thus employed. Due to probable low abundance of sPEPs and small in sizes, the need for efficient peptide enrichment strategies for enriching small proteins and depleting the sub-proteome of large and abundant proteins is crucial for identifying sPEPs. Low molecular weight proteins were extracted using SDS-PAGE from Human Embryonic Kidney (HEK293) cells and Strong Cation Exchange Chromatography (SCX) from secreted HEK293 cells. Extracted proteins were digested by trypsin to peptides, which were detected by LC-MS/MS. The MS/MS data obtained was searched against Swiss-Prot using MASCOT version 2.4 to filter out known proteins, and all unmatched spectra were re-searched against human RefSeq database. ProteinPilot v5.0.1 was used to identify sPEPs by searching against human RefSeq, Vanderperre and Human Alternative Open Reading Frame (HaltORF) databases. Potential sPEPs were analyzed by bioinformatics. Since SDS PAGE electrophoresis could not separate proteins <20kDa, this could not identify sPEPs. All MASCOT-identified peptide fragments were parts of main open reading frame (mORF) by ORF Finder search and blastp search. No sPEP was detected and existence of sPEPs could not be identified in this study. 13 translated sORFs in HEK293 cells by mass spectrometry in previous studies were characterized by bioinformatics. Identified sPEPs from previous studies were <100 amino acids and <15 kDa. Bioinformatics results showed that sORFs are translated to sPEPs and contribute to proteome complexity. uPEP translated from uORF of SLC35A4 was strongly conserved in human and mouse while uPEP translated from uORF of MKKS was strongly conserved in human and Rhesus monkey. Cross-species conserved uORFs in association with protein translation strongly suggest evolutionary maintenance of coding sequence and indicate probable functional expression of peptides encoded within these uORFs. Translation of sORFs was confirmed by mass spectrometry and sPEPs were characterized with bioinformatics.

Keywords: bioinformatics, HEK293 cells, liquid chromatography-mass spectrometry, ProteinPilot, Strong Cation Exchange Chromatography, SDS-PAGE, sPEPs

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Authors: M. Markova, E. Filova, O. Kaplan, R. Matejka, L. Bacakova

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The porcine pericardium is used as a material for cardiac and aortic valves substitutes. Current biological aortic heart valve prosthesis have a limited lifetime period because they undergo degeneration. In order to make them more biocompatible and prolong their lifetime it is necessary to reseed the decellularized prostheses with endothelial cells and with valve interstitial cells. The endothelialization of the prosthesis-surface may be supported by suitable chemical surface modification of the prosthesis. The aim of this study is to prepare bioactive fibrin layers which would both support endothelialization of porcine pericardium and enhance differentiation and maturation of the endothelial cells seeded. As a material for surface adjustments we used layers of fibrin with/without heparin and some of them with adsorbed or chemically bound FGF2, VEGF or their combination. Fibrin assemblies were prepared in 24-well cell culture plate and were seeded with HSVEC (Human Saphenous Vein Endothelial Cells) at a density of 20,000 cells per well in EGM-2 medium with 0.5% FS and without heparin, without FGF2 and without VEGF; medium was supplemented with aprotinin (200 U/mL). As a control, surface polystyrene (PS) was used. Fibrin was also used as homogeneous impregnation of the decellularized porcine pericardium throughout the scaffolds. Morphology, density, and viability of the seeded endothelial cells were observed from micrographs after staining the samples by LIVE/DEAD cytotoxicity/viability assay kit on the days 1, 3, and 7. Endothelial cells were immunocytochemically stained for proteins involved in cell adhesion, i.e. alphaV integrin, vinculin, and VE-cadherin, markers of endothelial cells differentiation and maturation, i.e. von Willebrand factor and CD31, and for extracellular matrix proteins typically produced by endothelial cells, i.e. type IV collagen and laminin. The staining intensities were subsequently quantified using a software. HSVEC cells grew on each of the prepared surfaces better than on control surface. They reached confluency. The highest cell densities were obtained on the surface of fibrin with heparin and both grow factors used together. Intensity of alphaV integrins staining was highest on samples with remained fibrin layer, i.e. on layers with lower cell densities, i.e. on fibrin without heparin. Vinculin staining was apparent, but was rather diffuse, on fibrin with both FGF2 and VEGF and on control PS. Endothelial cells on all samples were positively stained for von Willebrand factor and CD31. VE-cadherin receptors clusters were best developed on fibrin with heparin and growth factors. Significantly stronger staining of type IV collagen was observed on fibrin with heparin and both growth factors. Endothelial cells on all samples produced laminin-1. Decellularized pericardium was homogeneously filled with fibrin structures. These fibrin-modified pericardium samples will be further seeded with cells and cultured in a bioreactor. Fibrin layers with/without heparin and with adsorbed or chemically bound FGF2, VEGF or their combination are good surfaces for endothelialization of cardiovascular prostheses or porcine pericardium based heart valves. Supported by the Ministry of Health, grants No15-29153A and 15-32497A, and the Grant Agency of the Czech Republic, project No. P108/12/G108.

Keywords: aortic valves prosthesis, FGF2, heparin, HSVEC cells, VEGF

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Authors: J. Desbrieres, M. Popa, C. Peptu, S. Bacaita

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Because of their favorable properties (non-toxicity, biodegradability, mucoadhesivity etc.), polysaccharides were studied as biomaterials and as pharmaceutical excipients in drug formulations. These formulations may be produced in a wide variety of forms including hydrogels, hydrogel based particles (or capsules), films etc. In these formulations, the polysaccharide based materials are able to provide local delivery of loaded therapeutic agents but their delivery can be rapid and not easily time-controllable due to, particularly, the burst effect. This leads to a loss in drug efficiency and lifetime. To overcome the consequences of burst effect, systems involving liposomes incorporated into polysaccharide hydrogels may appear as a promising material in tissue engineering, regenerative medicine and drug loading systems. Liposomes are spherical self-closed structures, composed of curved lipid bilayers, which enclose part of the surrounding solvent into their structure. The simplicity of production, their biocompatibility, the size and similar composition of cells, the possibility of size adjustment for specific applications, the ability of hydrophilic or/and hydrophobic drug loading make them a revolutionary tool in nanomedicine and biomedical domain. Drug delivery systems were developed as hydrogels containing chitosan or carboxymethylcellulose (CMC) as polysaccharides and gelatin (GEL) as polypeptide, and phosphatidylcholine or phosphatidylcholine/cholesterol liposomes able to accurately control this delivery, without any burst effect. Hydrogels based on CMC were covalently crosslinked using glutaraldehyde, whereas chitosan based hydrogels were double crosslinked (ionically using sodium tripolyphosphate or sodium sulphate and covalently using glutaraldehyde). It has been proven that the liposome integrity is highly protected during the crosslinking procedure for the formation of the film network. Calcein was used as model active matter for delivery experiments. Multi-Lamellar vesicles (MLV) and Small Uni-Lamellar Vesicles (SUV) were prepared and compared. The liposomes are well distributed throughout the whole area of the film, and the vesicle distribution is equivalent (for both types of liposomes evaluated) on the film surface as well as deeper (100 microns) in the film matrix. An obvious decrease of the burst effect was observed in presence of liposomes as well as a uniform increase of calcein release that continues even at large time scales. Liposomes act as an extra barrier for calcein release. Systems containing MLVs release higher amounts of calcein compared to systems containing SUVs, although these liposomes are more stable in the matrix and diffuse with difficulty. This difference comes from the higher quantity of calcein present within the MLV in relation with their size. Modeling of release kinetics curves was performed and the release of hydrophilic drugs may be described by a multi-scale mechanism characterized by four distinct phases, each of them being characterized by a different kinetics model (Higuchi equation, Korsmeyer-Peppas model etc.). Knowledge of such models will be a very interesting tool for designing new formulations for tissue engineering, regenerative medicine and drug delivery systems.

Keywords: controlled and delayed release, hydrogels, liposomes, polysaccharides

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Authors: David Tennison

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Epistemic injustice, an injustice done to a person specifically in their capacity as a “knower”, is a subtle form of discrimination, yet its effects can be as dehumanizing and damaging as more overt forms of discrimination. The lens of epistemic injustice has, in recent years, been fruitfully applied to the field of healthcare, examining questions of agency, power, credibility and belief in doctor-patient interactions. Contested illness patients (e.g., those with illnesses lacking scientific consensuses such as fibromyalgia (FM), Myalgic Encephalomyelitis/ Chronic Fatigue Syndrome (ME/CFS) and Long Covid) face higher levels of scrutiny than other patient groups and are often disbelieved or dismissed when their ailments cannot be easily imaged or tested for- often encapsulated by the expression “it’s all in your head”. Using the case study of FM, the trials of contested illness patients in healthcare can be conceptualized in terms of epistemic injustice, and what is going wrong in these doctor-patient relationships can be effectively diagnosed. This case study also helps reveal epistemic dysfunction (structural epistemic issues embedded in the healthcare system), how this relates to stigma identity-based prejudice, and how the healthcare system upholds existing societal hierarchies and disenfranchises the most vulnerable. In the modern landscape, where cases of these chronic illnesses are not only on the rise but future pandemics threaten to add to their number, this conversation is crucial for the well-being of patients and providers. This presentation will cover what epistemic injustice is and how it can be applied to the politics of the doctor-patient interaction on a micro level and the politics of the healthcare system more broadly. Contested illnesses will be explored in terms of how the “contested” label causes the patient to experience disease stigma and lowers their credibility in healthcare and across other aspects of life. This will be explored in tandem with a discussion of existing identity-based prejudice in the healthcare system and how social identities (such as those of gender, race, and socioeconomic status) intersect with the contested illness label. The effects of epistemic injustice, which include worsening patients’ symptoms of mental health and potentially disenfranchising them from the healthcare system altogether, will be presented alongside the potential ethical quandaries this poses for providers. Finally, issues with the way healthcare appointments and the modern NHS function will be explored in terms of epistemic injustice and solutions to improve doctor-patient communication and patient care will be discussed. The relationship between contested illness patients and healthcare providers is notoriously poor, and while this can mean frustration or feelings of unfulfillment in providers, the negative effects for patients are much more severe. The purpose of this research, then, is to highlight these issues and suggest ways in which to improve the healthcare experience for these patients, along with improving doctor-patient communication and mending the doctor-patient relationship in a tangible and realistic way. This research also aims to provoke important conversations about belief and hierarchy in medical settings and how these aspects intersect with identity prejudices.

Keywords: epistemic injustice, fibromyalgia, contested illnesses, chronic illnesses, doctor-patient relationships, philosophy of medicine

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Authors: Eleni Karasavvidou

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Social and anthropological research, parallel to Gender Studies, highlighted the relationship between social structures and symbolic forms as an important field of interaction and recording of 'social trends.' Since the study of representations can contribute to the understanding of the social functions and power relations, they encompass. This ‘mirage,’ however, has not only to do with the representations themselves but also with the ways they are received and the film or critical narratives that are established as dominant or alternative. Cinema and the criticism of its cultural products are no exception. Even in the rapidly changing media landscape of the 21st century, movies remain an integral and widespread part of popular culture, making films an extremely powerful means of 'legitimizing' or 'delegitimizing' visions of domination and commonsensical gender stereotypes throughout society. And yet it is film criticism, the 'language per se,' that legitimizes, reinforces, rewards and reproduces (or at least ignores) the stereotypical depictions of female roles that remain common in the realm of film images. This creates the need for this issue to have emerged (also) in academic research questioning gender criteria in film reviews as part of the effort for an inclusive art and society. Qualitative content analysis is used to examine female roles in selected Oscar-nominated films against their reviews from leading websites and newspapers. This method was chosen because of the complex nature of the depictions in the films and the narratives they evoke. The films were divided into basic scenes depicting social functions, such as love and work relationships, positions of power and their function, which were analyzed by content analysis, with borrowings from structuralism (Gennette) and the local/universal images of intercultural philology (Wierlacher). In addition to the measurement of the general ‘representation-time’ by gender, other qualitative characteristics were also analyzed, such as: speaking time, sayings or key actions, overall quality of the character's action in relation to the development of the scenario and social representations in general, as well as quantitatively (insufficient number of female lead roles, fewer key supporting roles, relatively few female directors and people in the production chain and how they might affect screen representations. The quantitative analysis in this study was used to complement the qualitative content analysis. Then the focus shifted to the criteria of film criticism and to the rhetorical narratives that exclude or highlight in relation to gender identities and functions. In the criteria and language of film criticism, stereotypes are often reproduced or allegedly overturned within the framework of apolitical "identity politics," which mainly addresses the surface of a self-referential cultural-consumer product without connecting it more deeply with the material and cultural life. One of the prime examples of this failure is the Bechtel Test, which tracks whether female characters speak in a film regardless of whether women's stories are represented or not in the films analyzed. If perceived unbiased male filmmakers still fail to tell truly feminist stories, the same is the case with the criteria of criticism and the related interventions.

Keywords: representations, context analysis, reviews, sexist stereotypes

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Authors: Thanduxolo Elford Fana

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Rationale and Purpose: Performance management and development system are central to effective and efficient service delivery, especially in highly labour intensive sectors such as South African public health. Performance management and development systems seek to ensure that good employee performance is rewarded accordingly, while those who underperform are developed so that they can reach their full potential. An effective and efficiently implemented performance management system motivates and improves employee engagement. The purpose of this study is to examine the implementation of the performance management and development system and the challenges that are encountered during its implementation in the Eastern Cape Provincial Department of Health. Methods: A qualitative research approach and a case study design was adopted in this study. The primary data were collected through observations, focus group discussions with employees, a group interview with shop stewards, and in-depth interviews with supervisors and managers, from April 2019 to September 2019. There were 45 study participants. In-depth interviews were held with 10 managers at facility level, which included chief executive officer, chief medical officer, assistant director’s in human resources management, patient admin, operations, finance, and two area manager and two operation managers nursing. A group interview was conducted with five shop stewards and an in-depth interview with one shop steward from the group. Five focus group discussions were conducted with clinical and non-clinical staff. The focus group discussions were supplemented with an in-depth interview with one person from each group in order to counter the group effect. Observations included moderation committee, contracting, and assessment meetings. Findings: The study shows that the performance management and development system was not properly implemented. There was non-compliance to performance management and development system policy guidelines in terms of time lines for contracting, evaluation, payment of incentives to good performers, and management of poor performance. The study revealed that the system is ineffective in raising the performance of employees and unable to assist employees to grow. The performance bonuses were no longer paid to qualifying employees. The study also revealed that lack of capacity and commitment, poor communication, constant policy changes, financial constraints, weak and highly bureaucratic management structures, union interference were challenges that were encountered during the implementation of the performance management and development system. Lastly, employees and supervisors were rating themselves three irrespective of how well or bad they performed. Conclusion: Performance management is regarded as vital to improved performance of the health workforce and healthcare service delivery among populations. Effective implementation of performance management and development system depends on well-capacitated and unbiased management at facility levels. Therefore, there is an urgent need to improve communication, link performance management to rewards, and capacitate staff on performance management and development system, as it is key to improved public health sector outcomes or performance.

Keywords: challenges, implementation, performance management and development system, public hospital

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Authors: Jasna Hrncic

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Poor family relations predict depression, but also to other mental health issues. Mediating effect of self-efficacy and differentiation of self and moderating effect of decreased accessibility and/or success of other adaptive and defensive mechanisms for overcoming social disadvantages could explain depression as a specific outcome of dysfunctional family relations. The present study analyzes the mediation effect of self-efficacy and differentiation of self from poor family functioning to depressive symptoms and the moderation effect of deprivation of liberty on the listed mediation effect. Deprivation of liberty has, as a general consequence, a decreased accessibility and/or success of many adaptive and defensive mechanisms. It is hypothesized that: 1) self-efficacy and differentiation of self will mediate between family functioning and depressiveness in the total sample, and 2) deprivation of liberty will moderate the stated relations. Cross-sectional study was conducted among 323 male juveniles in Serbia divided in three groups: 98 adolescents deprived of their liberty due to antisocial behavior (incarcerated antisocial group - IAG), 121 adolescents with antisocial behavior in their natural setting (antisocial control group - CAG) and 105 adolescents in general population (general control group - CGG). The CAG was included along with GCG to control the possible influence that comorbidity of antisocial behavior and depressiveness could have on results. Instruments for family relations assessment were: for a whole family of origin the emotional exchange scale and individuation scale from GRADIR by Knezevic, and for a relationship with mother PCS-YSR and CRPBI by barber, and intimacy, rejection, sacrifice, punishment, demands, control and internal control by Opacic and Kos. Differentiation of self (DOS) is measured by emotional self scale (Opacic), self-efficacy (SE) by general incompetence scale by Bezinovic, and depression by BDI (Back), CES-D (Radloff) and D6R (Momirovic). Two-path structural equation modeling based on most commonly reported fit indices, showed that the mediation model had unfavorable fit to our data for total sample [(χ2 (1, N = 324) = 13.73); RMSEA= .20 (90% CI= [.12, .30]); CFI= .98; NFI= .97; AIC=31.73]. Path model provided an adequate fit to the data only for AIG - and not to the data from ACG and GCG. SE and DOS mediated the relationship between PFF and depressiveness. Test of the indirect effects revealed that 23.85% of PFF influences on depressiveness is mediated by these two mediators (the quotient of mediated effect = .24). Test of specific indirect effects showed that SE mediates 22.17%, while DOS mediates 1.67% of PFF influence on depressiveness. Lack of expected mediation effect could be explained by missing other potential mediators (i.e., relationship with that father, social skills, self-esteem) and lower variability of both predictor and criterion variable due to their low levels on the whole sample and on control subsamples. Results suggested that inaccessibility and/or successfulness of other adaptive and defensive mechanisms for overcoming social disadvantages has a strong impact on the mediation effect of self/efficacy and differentiation of self from poor family functioning to depressive symptoms. Further researches could include other potential mediators and a sample of clinically depressed people.

Keywords: antisocial behavior, mediating effect, moderating effect, natural setting, incarceration

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Authors: Anand R. Nair, Markus Trenker

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Lifting body concepts were conceived as early as 1917 and patented by Roy Scroggs. It was an idea of using the fuselage as a lift producing body with no or small wings. Many of these designs were developed and even flight tested between 1920’s to 1970’s, but it was not pursued further for commercial flight as at lower airspeeds, such a configuration was incapable to produce sufficient lift for the entire aircraft. The concept presented in this contribution is combining the lifting body design along with a fixed wing to maximise the lift produced by the aircraft. Conventional aircraft fuselages are designed to be aerodynamically efficient, which is to minimise the drag; however, these fuselages produce very minimal or negligible lift. For the design of an unmanned fixed wing transport aircraft, many of the restrictions which are present for commercial aircraft in terms of fuselage design can be excluded, such as windows for the passengers/pilots, cabin-environment systems, emergency exits, and pressurization systems. This gives new flexibility to design fuselages which are unconventionally shaped to contribute to the lift of the aircraft. The two lifting body concepts presented in this contribution are targeting different applications: For a fast cargo delivery drone, the fuselage is based on a scaled airfoil shape with a cargo capacity of 500 kg for euro pallets. The aircraft has a span of 14 m and reaches 1500 km at a cruising speed of 90 m/s. The aircraft could also easily be adapted to accommodate pilot and passengers with modifications to the internal structures, but pressurization is not included as the service ceiling envisioned for this type of aircraft is limited to 10,000 ft. The next concept to be investigated is called a multi-purpose drone, which incorporates a different type of lifting body and is a much more versatile aircraft as it will have a VTOL capability. The aircraft will have a wingspan of approximately 6 m and flight speeds of 60 m/s within the same service ceiling as the fast cargo delivery drone. The multi-purpose drone can be easily adapted for various applications such as firefighting, agricultural purposes, surveillance, and even passenger transport. Lifting body designs are not a new concept, but their effectiveness in terms of cargo transportation has not been widely investigated. Due to their enhanced lift producing capability, lifting body designs enable the reduction of the wing area and the overall weight of the aircraft. This will, in turn, reduce the thrust requirement and ultimately the fuel consumption. The various designs proposed in this contribution will be based on the general aviation category of aircrafts and will be focussed on unmanned methods of operation. These unmanned fixed-wing transport drones will feature appropriate cargo loading/unloading concepts which can accommodate large size cargo for efficient time management and ease of operation. The various designs will be compared in performance to their conventional counterpart to understand their benefits/shortcomings in terms of design, performance, complexity, and ease of operation. The majority of the performance analysis will be carried out using industry relevant standards in computational fluid dynamics software packages.

Keywords: lifting body concept, computational fluid dynamics, unmanned fixed-wing aircraft, cargo drone

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Authors: Weili Jiang, Simon Cadavid Lopera, Klaus Drechsler

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Fuel cell vehicle has become the most competitive solution for the transportation sector in the hydrogen economy. Type IV pressure vessel is currently the most popular and widely developed technology for the on-board storage, based on their high reliability and relatively low cost. Due to the stringent requirement on mechanical performance, the pressure vessel is subject to great amount of composite material, a major cost driver for the hydrogen tanks. Evidently, the optimization of composite layup design shows great potential in reducing the overall material usage, yet requires comprehensive understanding on underlying mechanisms as well as the influence of different design parameters on mechanical performance. Given the type of materials and manufacturing processes by which the type IV pressure vessels are manufactured, the design and optimization are a nuanced subject. The manifold of stacking sequence and fiber orientation variation possibilities have an out-standing effect on vessel strength due to the anisotropic property of carbon fiber composites, which make the design space high dimensional. Each variation of design parameters requires computational resources. Using finite element analysis to evaluate different designs is the most common method, however, the model-ing, setup and simulation process can be very time consuming and result in high computational cost. For this reason, it is necessary to build a reliable automation scheme to set up and analyze the di-verse composite layups. In this research, the simulation process of different tank designs regarding various parameters is conducted and automatized in a commercial finite element analysis framework Abaqus. Worth mentioning, the modeling of the composite overwrap is automatically generated using an Abaqus-Python scripting interface. The prediction of the winding angle of each layer and corresponding thickness variation on dome region is the most crucial step of the modeling, which is calculated and implemented using analytical methods. Subsequently, these different composites layups are simulated as axisymmetric models to facilitate the computational complexity and reduce the calculation time. Finally, the results are evaluated and compared regarding the ultimate tank strength. By automatically modeling, evaluating and comparing various composites layups, this system is applicable for the optimization of the tanks structures. As mentioned above, the mechanical property of the pressure vessel is highly dependent on composites layup, which requires big amount of simulations. Consequently, to automatize the simulation process gains a rapid way to compare the various designs and provide an indication of the optimum one. Moreover, this automation process can also be operated for creating a data bank of layups and corresponding mechanical properties with few preliminary configuration steps for the further case analysis. Subsequently, using e.g. machine learning to gather the optimum by the data pool directly without the simulation process.

Keywords: type IV pressure vessels, carbon composites, finite element analy-sis, automation of simulation process

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Authors: Jatinder Pal Singh, Harpreet Singh, Gagandeep Singh Digra, Mandeep Kaur Sidhu, Pawan Kumar

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Introduction: Ganglion cyst is a benign condition in which there is a cystic lesion in relation to a joint or a tendon sheath arising from myxoid degeneration of fibrous connective tissue. These can be unilocular or multilocular. In rare cases, there may be multiple ganglion cysts, known as cystic ganglionosis. They can occur at any age but are commonly seen in adults. Clinically they may be asymptomatic or present as swelling or mass effect in adjacent structures. These are common in extremities such as hands and feet. Case Presentation: 11-year-old female child presented with slowly progressive painless swelling of her right hand since the age of 4. Antenatal and perinatal history was unremarkable. Her family history was negative. She denies fever, malaise, morning stiffness, weight loss, fatigue, restriction of joint movements, or any sensory and motor deficit. Lab parameters were negative for inflammatory or infectious etiology. No other joint or extremity involvement was present. On physical examination, the swelling was present on the dorsum and palmer aspect of the right hand and wrist. They were non-tender on palpation without any motor or sensory deficit. MRI hand revealed multiple well-defined fluid signal intensity cystic appearing lesions in periarticular/intraarticular locations in relation to distal radio-ulnar, radio-carpal, intercarpal, carpometacarpal, metacarpophalangeal and interphalangeal joints as well as peritendinous location around flexor tendons more so in the region of wrist, palm, 1st and 5th digit and along extensor tendons in the region of wrist, largest one noted along flexor pollicis longus tendon in thenar region and along 1st digit measuring approx. 4.6 x 1.2 x 1.2 centimeter. Pressure erosions and bone remodelling were noted in the bases of the 2nd to 5th metacarpals, capitate, trapezoid, the distal shaft of 1st metacarpal, and proximal phalanx of 1st digit. Marrow edema was noted in the base and proximal shaft of the 4th metacarpal and proximal shaft of the 3rd metacarpal – likely stress or pressure related. The patient was advised of aspiration, but the family refused the procedure. Therefore the patient was kept on conservative treatment. Conclusion: Cystic ganglionosis is a rare condition with very few cases reported in the medical literature. Its prevalence and association are not known because of the rarity of this condition. It should be considered as an important differential in patients presenting with soft tissue swelling in extremities. Treatment option includes conservative management, aspiration, and surgery. Aspiration has a high recurrence rate. Although surgery has a low recurrence rate, it carries a high rate of complications. Imaging with MRI is essential for confirmation of the cystic nature of lesions and their relation with the joint capsules or tendons. This helps in differentiating from other soft tissue lesions and presurgical planning.

Keywords: radiology, rare, cystic ganglionosis, child

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Authors: Sergio Celaschi, Henrique Canavarro de Alencar, Claaudecir Biazoli

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Effluent quality is of the highest priority for compliance with the permit limits of environmental protection agencies and ensures the protection of their local water system. Of the pollutants monitored, the biochemical oxygen demand (BOD) posed one of the greatest challenges. This work presents a solution for wastewater treatment plants - WWTP’s ability to react to different situations and meet treatment goals. Delayed BOD5 results from the lab take 7 to 8 analysis days, hindered the WWTP’s ability to react to different situations and meet treatment goals. Reducing BOD turnaround time from days to hours is our quest. Such a solution is based on a system of two BOD bioreactors associated with Digital Twin (DT) and Machine Learning (ML) methodologies via an Internet of Things (IoT) platform to monitor and control a WWTP to support decision making. DT is a virtual and dynamic replica of a production process. DT requires the ability to collect and store real-time sensor data related to the operating environment. Furthermore, it integrates and organizes the data on a digital platform and applies analytical models allowing a deeper understanding of the real process to catch sooner anomalies. In our system of continuous time monitoring of the BOD suppressed by the effluent treatment process, the DT algorithm for analyzing the data uses ML on a chemical kinetic parameterized model. The continuous BOD monitoring system, capable of providing results in a fraction of the time required by BOD5 analysis, is composed of two thermally isolated batch bioreactors. Each bioreactor contains input/output access to wastewater sample (influent and effluent), hydraulic conduction tubes, pumps, and valves for batch sample and dilution water, air supply for dissolved oxygen (DO) saturation, cooler/heater for sample thermal stability, optical ODO sensor based on fluorescence quenching, pH, ORP, temperature, and atmospheric pressure sensors, local PLC/CPU for TCP/IP data transmission interface. The dynamic BOD system monitoring range covers 2 mg/L < BOD < 2,000 mg/L. In addition to the BOD monitoring system, there are many other operational WWTP sensors. The CPU data is transmitted/received to/from the digital platform, which in turn performs analyses at periodic intervals, aiming to feed the learning process. BOD bulletins and their credibility intervals are made available in 12-hour intervals to web users. The chemical kinetics ML algorithm is composed of a coupled system of four first-order ordinary differential equations for the molar masses of DO, organic material present in the sample, biomass, and products (CO₂ and H₂O) of the reaction. This system is solved numerically linked to its initial conditions: DO (saturated) and initial products of the kinetic oxidation process; CO₂ = H₂0 = 0. The initial values for organic matter and biomass are estimated by the method of minimization of the mean square deviations. A real case of continuous monitoring of BOD wastewater effluent quality is being conducted by deploying an IoT application on a large wastewater purification system located in S. Paulo, Brazil.

Keywords: effluent treatment, biochemical oxygen demand, continuous monitoring, IoT, machine learning

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Authors: Sajmina Khatun, Monika Pebam, Aravind Kumar Rengan

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Photothermal therapy, a subset of nanomedicine, takes advantage of light-absorbing agents to generate localized heat, selectively eradicating cancer cells. This innovative approach minimizes damage to healthy tissues and offers a promising avenue for targeted cancer treatment. Unlike conventional therapies, photothermal therapy harnesses the power of light to combat malignancies precisely and effectively, showcasing its potential to revolutionize cancer treatment paradigms. The combined strengths of nanomedicine and photothermal therapy signify a transformative shift toward more effective, targeted, and tolerable cancer treatments in the medical landscape. Utilizing natural products becomes instrumental in formulating diverse bioactive medications owing to their various pharmacological properties attributed to the existence of phenolic structures, triterpenoids, and similar compounds. Hyptis suaveolens, commonly known as pignut, stands as an aromatic herb within the Lamiaceae family and represents a valuable therapeutic plant. Flourishing in swamps and alongside tropical and subtropical roadsides, these noxious weeds impede the development of adjacent plants. Hyptis suaveolens ranks among the most globally distributed alien invasive species. The present investigation revealed that a versatile, biodegradable liposome nanosystem (HIL NPs), incorporating bioactive molecules from Hyptis suaveolens, exhibits effective bioavailability to cancer cells, enabling tumor ablation upon near-infrared (NIR) laser exposure. The components within the nanosystem, specifically the bioactive molecules from Hyptis, function as anticancer agents, aiding in the photothermal ablation of highly metastatic lung cancer cells. Despite being a prolific weed impeding neighboring plant growth, Hyptis suaveolens showcases therapeutic benefits through its bioactive compounds. The obtained HIL NPs, characterized as a photothermally active liposome nanosystem, demonstrate a pronounced fluorescence absorption peak in the NIR range and achieve a high photothermal conversion efficiency under NIR laser irradiation. Transmission electron microscopy (TEM) and particle size analysis reveal that HIL NPs possess a spherical shape with a size of 141 ± 30 nm. Moreover, in vitro assessments of HIL NPs against lung cancer cell lines (A549) indicate effective anticancer activity through a combined cytotoxic effect and hyperthermia. Tumor ablation is facilitated by apoptosis induced by the overexpression of ɣ-H2AX, arresting cancer cell proliferation. Consequently, the multifunctional and biodegradable nanosystem (HIL NPs), incorporating bioactive compounds from Hyptis, provides valuable perspectives for developing an innovative therapeutic strategy originating from a challenging weed. This approach holds promise for potential applications in both bioimaging and the combined use of phyto-photothermal therapy for cancer treatment.

Keywords: bioactive liposome, hyptis suaveolens, photothermal therapy, lung cancer

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Authors: Monika Saha, A. T. M. Hasan Zobeyer, Nasreen Jahan

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El Nino-Southern Oscillation (ENSO) is the interaction between atmosphere and ocean in tropical Pacific which causes inconsistent warm/cold weather in tropical central and eastern Pacific Ocean. Due to the impact of climate change, ENSO events are becoming stronger in recent times, and therefore it is very important to study the influence of ENSO in climate studies. Bangladesh, being in the low-lying deltaic floodplain, experiences the worst consequences due to flooding every year. To reduce the catastrophe of severe flooding events, non-structural measures such as flood forecasting can be helpful in taking adequate precautions and steps. Forecasting seasonal flood with a longer lead time of several months is a key component of flood damage control and water management. The objective of this research is to identify the possible strength of teleconnection between ENSO and river flow of Surma and examine the potential possibility of long lead flood forecasting in the wet season. Surma is one of the major rivers of Bangladesh and is a part of the Surma-Meghna river system. In this research, sea surface temperature (SST) has been considered as the ENSO index and the lead time is at least a few months which is greater than the basin response time. The teleconnection has been assessed by the correlation analysis between July-August-September (JAS) flow of Surma and SST of Nino 4 region of the corresponding months. Cumulative frequency distribution of standardized JAS flow of Surma has also been determined as part of assessing the possible teleconnection. Discharge data of Surma river from 1975 to 2015 is used in this analysis, and remarkable increased value of correlation coefficient between flow and ENSO has been observed from 1985. From the cumulative frequency distribution of the standardized JAS flow, it has been marked that in any year the JAS flow has approximately 50% probability of exceeding the long-term average JAS flow. During El Nino year (warm episode of ENSO) this probability of exceedance drops to 23% and while in La Nina year (cold episode of ENSO) it increases to 78%. Discriminant analysis which is known as 'Categoric Prediction' has been performed to identify the possibilities of long lead flood forecasting. It has helped to categorize the flow data (high, average and low) based on the classification of predicted SST (warm, normal and cold). From the discriminant analysis, it has been found that for Surma river, the probability of a high flood in the cold period is 75% and the probability of a low flood in the warm period is 33%. A synoptic parameter, forecasting index (FI) has also been calculated here to judge the forecast skill and to compare different forecasts. This study will help the concerned authorities and the stakeholders to take long-term water resources decisions and formulate policies on river basin management which will reduce possible damage of life, agriculture, and property.

Keywords: El Nino-Southern Oscillation, sea surface temperature, surma river, teleconnection, cumulative frequency distribution, discriminant analysis, forecasting index

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Authors: Ani Kojoyan

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The Syrian refugee crisis has been a matter of worldwide concern during the recent years. And though refugees’ problems are contextualized in terms of time and space, the refugee crisis still remains a global issue to discuss. Since the start of the conflict, Armenia has welcomed thousands of Syrian refugees too. Taking into consideration Armenia’s current socio-economic and geopolitical situation, the flow of refugees is a challenge both for the country and for refugees themselves. However, these people are not simply refugees from Syria, they are Syrian-Armenian refugees; people whose ancestors were survivals of the Armenian Genocide, perpetrated by the Ottoman Turks in 1915, people whose ancestors became refugees a century ago in Syria and now, ironically, a century later they follow their ancestors’ paths, turning into refugees themselves in their historical homeland, facing various difficulties, among them socio-economic, socio-ideological, and identity and gender issues, the latter being the main topic of discussion in the present paper. The situation presented above makes us discuss certain questions within this study: how do Syrian-Armenian refugees define themselves and their status? Which are their gender roles in the socio-economic context? How do social and economic challenges re-shape Syrian-Armenian women refugees’ identities? The study applies qualitative research methods of analysis, which includes semi-structured and in-depth interviews with 15 participants (18-25, 26-40 age groups), and two focus group works, involving 8 participants (18-35 age group) for each focus group activity. The activities were carried out in October 2016, Yerevan, Armenia. The study also includes Secondary Data Analysis. In addition, in order to centralize refugee women’s experiences and identity issues, the study adopts a qualitative lens from a feminist standpoint position. It is based on the assumption that human activity structures and limits understanding, and that the distorted comprehension of events or activities has emerged from the male-oriented dominant judgement which can be discovered through uncovering the understanding of the situation from women’s activity perspectives. The findings suggest that identity is dynamic, complex, over-changing and sensitive to time and space, gender and class. The process of re-shaping identity is even more complicated and multi-layered and is based on internal and external factors, conditioned by individual and collective needs and interests. Refugees are mostly considered as people who lost their identity in the past since they have no longer connection anywhere and try to find it in the present. In turn, female refugees, being a more vulnerable class, go through more complicated identity re-formulating discourse negotiations. They stand between the borders of the old and new, borders of lost and re-found selves, borders of creating and self-fashioning, between illusions and the challenging reality. Particularly, refugee women become more sensitive within the discourses of the private and the public domains: some of them try to create a ‘new-self’, creating their space in a new society, whereas others try to negotiate their affective/emotional labour within their own family domains.

Keywords: feminist standpoint position, gender, identity, refugee studies, Syrian-Armenian women refugees

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Authors: Fabienne Samyn, Pauline Tranchard, Sophie Duquesne, Emilie Goncalves, Bruno Estebe, Serge Boubigot

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Stringent fire safety regulations are enforced in the aeronautical industry due to the consequences that potential fire event on an aircraft might imply. This is so much true that the fire issue is considered right from the design of the aircraft structure. Due to the incorporation of an increasing amount of polymer matrix composites in replacement of more conventional materials like metals, the nature of the fire risks is changing. The choice of materials used is consequently of prime importance as well as the evaluation of its resistance to fire. The fire testing is mostly done using the so-called certification tests according to standards such as the ISO2685:1998(E). The latter describes a protocol to evaluate the fire resistance of structures located in fire zone (ability to withstand fire for 5min). The test consists in exposing an at least 300x300mm² sample to an 1100°C propane flame with a calibrated heat flux of 116kW/m². This type of test is time-consuming, expensive and gives access to limited information in terms of fire behavior of the materials (pass or fail test). Consequently, it can barely be used for material development purposes. In this context, the laboratory UMET in collaboration with industrial partners has developed a horizontal and a vertical small-scale instrumented fire benches for the characterization of the fire behavior of composites. The benches using smaller samples (no more than 150x150mm²) enables to cut downs costs and hence to increase sampling throughput. However, the main added value of our benches is the instrumentation used to collect useful information to understand the behavior of the materials. Indeed, measurements of the sample backside temperature are performed using IR camera in both configurations. In addition, for the vertical set up, a complete characterization of the degradation process, can be achieved via mass loss measurements and quantification of the gasses released during the tests. These benches have been used to characterize and study the fire behavior of aeronautical carbon/epoxy composites. The horizontal set up has been used in particular to study the performances and durability of protective intumescent coating on 2mm thick 2D laminates. The efficiency of this approach has been validated, and the optimized coating thickness has been determined as well as the performances after aging. Reductions of the performances after aging were attributed to the migration of some of the coating additives. The vertical set up has enabled to investigate the degradation process of composites under fire. An isotropic and a unidirectional 4mm thick laminates have been characterized using the bench and post-fire analyses. The mass loss measurements and the gas phase analyses of both composites do not present significant differences unlike the temperature profiles in the thickness of the samples. The differences have been attributed to differences of thermal conductivity as well as delamination that is much more pronounced for the isotropic composite (observed on the IR-images). This has been confirmed by X-ray microtomography. The developed benches have proven to be valuable tools to develop fire safe composites.

Keywords: aeronautical carbon/epoxy composite, durability, intumescent coating, small-scale ‘ISO 2685 like’ fire resistance test, X-ray microtomography

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Authors: Mihaela Beregoi, Horia Iovu, Cristina Busuioc, Alexandru Evanghelidis, Elena Matei, Monica Enculescu, Ionut Enculescu

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Nanomaterials field is very attractive for all researchers who are attempting to develop new devices with the same or improved properties than the micro-sized ones, while reducing the reagents and power consumptions. In this way, a wide range of nanomaterials were fabricated and integrated in applications for electronics, optoelectronics, solar cells, tissue reconstruction and drug delivery. Obviously, the most appealing ones are those dedicated to the medical domain. Different types of nano-sized materials, such as particles, fibers, films etc., can be synthesized by using physical, chemical or electrochemical methods. One of these techniques is electrospinning, which enable the production of fibers with nanometric dimensions by pumping a polymeric solution in a high electric field; due to the electrostatic charging and solvent evaporation, the precursor mixture is converted into nonwoven meshes with different fiber densities and mechanical properties. Moreover, polyaniline is a conducting polymer with interesting optical properties, suitable for displays and electrochromic windows. Otherwise, polyaniline is an electroactive polymer that can contract/expand by applying electric stimuli, due to the oxidation/reduction reactions which take place in the polymer chains. These two main properties can be exploited in order to synthesize smart materials that change their dimensions, exhibiting in the same time good electrochromic properties. In the context aforesaid, a poly(methyl metacrylate) solution was spun to get webs composed of fibers with diameter values between 500 nm and 1 µm. Further, the polymer meshes were covered with a gold layer in order to make them conductive and also appropriate as working electrode in an electrochemical cell. The gold shell was deposited by DC sputtering. Such metalized fibers can be transformed into smart materials by covering them with a thin layer of conductive polymer. Thus, the webs were coated with a polyaniline film by the electrochemical route, starting from and aqueous solution of aniline and sulfuric acid, where sulfuric acid acts as oxidant agent. For the polymerization of aniline, a saturated calomel electrode was employed as reference, a platinum plate as counter electrode and the gold covered webs as working electrode. Chronoamperometry was selected as deposition method for polyaniline, by modifying the deposition time. Metalized meshes with different fiber densities were used, the transmission ranging between 70 and 80 %. The morphological investigation showed that polyaniline layer has a granular structure for all deposition experiments. As well, some preliminary optical tests were done by using sulfuric acid as electrolyte, which revealed the modification of polyaniline colour from green to dark blue when applying a voltage. In conclusion, new multilayered materials were obtained by a simple approach: the merge of the electrospinning method benefits with polyaniline chemistry. This synthesis method allows the fabrication of structures with reproducible characteristics, suitable for display or tissue substituents.

Keywords: electrospinning, fibers, smart materials, polyaniline

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Authors: Mehwish Jawaad

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Purpose: The concept of GrSCM (Green Supply Chain Management) in the academic and research field is still thought to be in the development stage especially in Asian Emerging Economies. The purpose of this paper is to contribute significantly to the first wave of empirical investigation on GrSCM Practices and Firm Performance measures in Pakistan. The aim of this research is to develop a more holistic approach towards investigating the impact of Green Supply Chain Management Practices (Ecodesign, Internal Environmental Management systems, Green Distribution, Green Purchasing and Cooperation with Customers) on multiple dimensions of Firm Performance Measures (Economic Performance, Environmental Performance and Operational Performance) with a mediating role of Investment Recovery and Competitiveness. This paper also serves as an initiative to identify if the relationship between Investment Recovery and Firm Performance Measures is mediated by Competitiveness. Design/ Methodology/Approach: This study is based on survey Data collected from 272, ISO (14001) Certified Textile Firms Based in Lahore, Faisalabad, and Karachi which are involved in Spinning, Dyeing, Printing or Bleaching. A Theoretical model was developed incorporating the constructs representing Green Activities and Firm Performance Measures of a firm. The data was analyzed using Partial Least Square Structural Equation Modeling. Senior and Mid-level managers provided the data reflecting the degree to which their organizations deal with both internal and external stakeholders to improve the environmental sustainability of their supply chain. Findings: Of the 36 proposed Hypothesis, 20 are considered valid and significant. The statistics result reveal that GrSCM practices positively impact Environmental Performance followed by Economic and Operational Performance. Investment Recovery acts as a strong mediator between Intra organizational Green activities and performance outcomes. The relationship of Reverse Logistics influencing outcomes is significantly mediated by Competitiveness. The pressure originating from customers exert significant positive influence on the firm to adopt Green Practices consequently leading to higher outcomes. Research Contribution/Originality: Underpinning the Resource dependence theory and as a first wave of investigating the impact of Green Supply chain on performance outcomes in Pakistan, this study intends to make a prominent mark in the field of research. Investment and Competitiveness together are tested as a mediator for the first time in this arena. Managerial implications: Practitioner is provided with a framework for assessing the synergistic impact of GrSCM practices on performance. Upgradation of Accreditations and Audit Programs on regular basis are the need of the hour. Making the processes leaner with the sale of excess inventories and scrap helps the firm to work more efficiently and productively.

Keywords: economic performance, environmental performance, green supply chain management practices, operational performance, sustainability, a textile sector of Pakistan

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Authors: Sudip Kumar Sinha, Saptarshi Ghosh

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While there’s a perpetual buzz around zinc oxide (ZnO) superstructures for their unique optical features, the versatile material has been constantly utilized to manifest tailored electronic properties through rendition of distinct morphologies. And yet, the unorthodox approach of implementing the novel 1D nanostructures of ZnO (pristine or doped) for volatile sensing applications has ample scope to accommodate new unconventional morphologies. In the last two decades, solid-state sensors have attracted much curiosity for their relevance in identifying pollutant, toxic and other industrial gases. In particular gas sensors based on metal oxide semiconducting (wide Eg) nanomaterials have recently attracted intensive attention owing to their high sensitivity and fast response and recovery time. These materials when exposed to air, the atmospheric O2 dissociates and get absorb on the surface of the sensors by trapping the outermost shell electrons. Finally a depleted zone on the surface of the sensors is formed, that enhances the potential barrier height at grain boundary . Once a target gas is exposed to the sensor, the chemical interaction between the chemisorbed oxygen and the specific gas liberates the trapped electrons. Therefore altering the amount of adsorbate is a considerable approach to improve the sensitivity of any target gas/vapour molecule. Likewise, this study presents a spontaneous but self catalytic creation of Sn-doped ZnO hexagonal nanoprisms on Si (100) substrates through thermal evaporation-condensation method, and their subsequent deployment for volatile sensing. In particular, the sensors were utilized to detect molecules of ethanol, acetone and ammonia below their permissible exposure limits which returned sensitivities of around 85%, 80% and 50% respectively. The influence of Sn concentration on the growth, microstructural and optical properties of the nanoprisms along with its role in augmenting the sensing parameters has been detailed. The single-crystalline nanostructures have a typical diameter ranging from 300 to 500 nm and a length that extends up to few micrometers. HRTEM images confirmed the hexagonal crystallography for the nanoprisms, while SAED pattern asserted the single crystalline nature. The growth habit is along the low index <0001>directions. It has been seen that the growth mechanism of the as-deposited nanostructures are directly influenced by varying supersaturation ratio, fairly high substrate temperatures, and specified surface defects in certain crystallographic planes, all acting cooperatively decide the final product morphology. Room temperature photoluminescence (PL) spectra of this rod like structures exhibits a weak ultraviolet (UV) emission peak at around 380 nm and a broad green emission peak in the 505 nm regime. An estimate of the sensing parameters against dispensed target molecules highlighted the potential for the nanoprisms as an effective volatile sensing material. The Sn-doped ZnO nanostructures with unique prismatic morphology may find important applications in various chemical sensors as well as other potential nanodevices.

Keywords: gas sensor, HRTEM, photoluminescence, ultraviolet, zinc oxide

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Authors: Maria Ledinskaya

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This paper is part case study and part literature review. It seeks to introduce Agile, Lean, and Hybrid project management concepts from business, software development, and manufacturing fields to museum conservation by looking at their practical application on a recent conservation project at the Sainsbury Centre for Visual Arts. The author outlines the advantages of leaner and more agile conservation practices in today’s faster, less certain, and more budget-conscious museum climate where traditional project structures are no longer as relevant or effective. The Morris Collection Conservation Project was carried out in 2019-2021 in Norwich, UK, and concerned the remedial conservation of around 150 Abstract Constructivist artworks bequeathed to the Sainsbury Centre by private collectors Michael and Joyce Morris. It was a medium-sized conservation project of moderate complexity, planned and delivered in an environment with multiple known unknowns – unresearched collection, unknown conditions and materials, unconfirmed budget. The project was later impacted by the COVID-19 pandemic, introducing indeterminate lockdowns, budget cuts, staff changes, and the need to accommodate social distancing and remote communications. The author, then a staff conservator at the Sainsbury Centre who acted as project manager on the Morris Project, presents an incremental, iterative, and value-based approach to managing a conservation project in an uncertain environment. The paper examines the project from the point of view of Traditional, Agile, Lean, and Hybrid project management. The author argues that most academic writing on project management in conservation has focussed on a Traditional plan-driven approach – also known as Waterfall project management – which has significant drawbacks in today’s museum environment due to its over-reliance on prediction-based planning and its low tolerance to change. In the last 20 years, alternative Agile, Lean and Hybrid approaches to project management have been widely adopted in software development, manufacturing, and other industries, although their recognition in the museum sector has been slow. Using examples from the Morris Project, the author introduces key principles and tools of Agile, Lean, and Hybrid project management and presents a series of arguments on the effectiveness of these alternative methodologies in museum conservation, including the ethical and practical challenges to their implementation. These project management approaches are discussed in the context of consequentialist, relativist, and utilitarian developments in contemporary conservation ethics. Although not intentionally planned as such, the Morris Project had a number of Agile and Lean features which were instrumental to its successful delivery. These key features are identified as distributed decision-making, a co-located cross-disciplinary team, servant leadership, focus on value-added work, flexible planning done in shorter sprint cycles, light documentation, and emphasis on reducing procedural, financial, and logistical waste. Overall, the author’s findings point in favour of a hybrid model, which combines traditional and alternative project processes and tools to suit the specific needs of the project.

Keywords: agile project management, conservation, hybrid project management, lean project management, waterfall project management

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Authors: Isaiah Ifeanyichukwu Agbo

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Human speech is capable of serving many purposes. Power and control are not always exercised overtly by linguistic acts, but maybe enacted and exercised in the myriad of taken-for-granted actions of everyday life. Domination, power control, discrimination and mind control exist in human speech and may lead to asymmetrical power relations. In discourse, there are persuasive and manipulative linguistic acts that serve to establish solidarity and identification with the 'we group' and polarize with the 'they group'. Political discourse is crafted to defend and promote the problematic narrative of outright controversial events in a nation’s history thereby sustaining domination, marginalization, manipulation, inequalities and injustices, often without the dominated and marginalized group being aware of them. They are designed and positioned to serve the political and social needs of the producers. Political crisis speeches in Nigeria, just like in other countries concentrate on positive self-image, de-legitimization of political opponents, reframing accusation to one’s advantage, redefining problematic terms and adopting reversal strategy. In most cases, the people are ignorant of the hidden ideological positions encoded in the text. Few researches have been conducted adopting the frameworks of critical discourse analysis and systemic functional linguistics to investigate this situation in the political crisis speeches in Nigeria. In this paper, we focus attention on the analyses of the linguistic, semantic, and ideological elements in selected political crisis speeches in Nigeria to investigate if they create and sustain unequal power relations and manipulative tendencies from the perspectives of Critical Discourse Analysis (CDA) and Systemic Functional Linguistics (SFL). Critical Discourse Analysis unpacks both opaque and transparent structural relationships of power dominance, power relations and control as manifested in language. Critical discourse analysis emerged from a critical theory of language study which sees the use of language as a form of social practice where social relations are reproduced or contested and different interests are served. Systemic function linguistics relates the structure of texts to their function. Fairclough’s model of CDA and Halliday’s systemic functional approach to language study are adopted in this paper. This paper probes into language use that perpetuates inequalities. This study demystifies the hidden implicature of the selected political crisis speeches and reveals the existence of information that is not made explicit in what the political actors actually say. The analysis further reveals the ideological configurations present in the texts. These ideological standpoints are the basis for naturalizing implicit ideologies and hegemonic influence in the texts. The analyses of the texts further uncovered the linguistic and discursive strategies deployed by text producers to manipulate the unsuspecting members of the public both mentally and conceptually in order to enact, sustain and maintain unhealthy power relations at crisis times in the Nigerian political history.

Keywords: critical discourse analysis, language, political crisis, power relations, systemic functional linguistics

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Authors: Diego R. Boiarski, Camila M. Toigo, Thais M. Sobjak, Andrey F. P. Santos, Silvia Romao, Ana T. B. Guimaraes

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Anthropogenic activities promote changes in the community’s structures and decrease the species abundance of amphibians. Biological communities of fluvial systems are assemblies of organisms that have adapted to regional conditions, including the physical environment and food resources, and are further refined through interactions with other species. The aim of this study was to assess neurotoxic alterations and in the antioxidant system on tadpoles of Lithobates catesbeianus exposed to waters from Cascavel River, in the south of Brazil. A total of 420 L of water was collected from the Cascavel River, 140 L from each of the three different locations: Site 1 – headwater; Site 2 – stretch of the stream that runs through an urbanized area; Site 3 – a stretch from the rural area. Twelve tadpoles were acclimated in each aquarium (100 L of water) for seven days. The water from each aquarium was replaced with the ones sampled from the river, except the one from the control aquarium. After seven days, a portion of the liver was removed and conditioned for ChE, SOD, CAT and LPO analysis; other part of the tissue was conditioned for histological analysis. The statistical analysis performed was one-way ANOVA, followed by post-hoc Tukey-HSD test, and the multivariate principal components analysis. It was not observed any neurotoxic effect, but a slight increase in SOD activity and elevation of CAT activity in both urban and rural environment. A decrease in LPO reaction was detected, mainly among the tadpoles exposed to the waters from the rural area. The results of the present study demonstrate the alteration of the antioxidant system, as well as liver histopathologies in tadpoles exposed mainly to waters collected in urban and rural environments. These alterations may cause the reduction in the velocity of the metamorphosis process from the tadpoles. Further, were observed histological alterations, highlighting necrotic areas mainly among the animals exposed to urban waters. Those damages can lead to metabolic dysfunction, interfering with survival capacity, diminishing not only individual fitness but for the whole population. In the interpretation synthesis of all biomarkers, the cellular damage gradient is perceptible, characterized by the variables related to the antioxidant system, due to the flow direction of the stream. This result is indicative that along the course of the creek occurs dumping of organic material, which promoted an acute response upon tadpoles of L. catesbeianus. and it was also observed the difference in tissue damage between the experimental groups and the control group, the latter presenting histological alterations, but to a lesser degree than the animals exposed to the waters of the Cascavel river. These damages, caused by reactive oxygen species possibly resulting from the contamination by organic compounds, can lead the animals to a series of metabolic dysfunctions, interfering with its metamorphosis capacity. Interruption of metamorphosis may affect survival, which may impair its growth, development and reproduction, diminishing not only the fitness of each individual but in a long-term, to the entire population.

Keywords: American bullfrog, histopathology, oxidative stress, urban creeks pollution

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Authors: A. Knezović

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21st century has transformed the labor market landscape in a way of posing new and different demands on university graduates as well as university lecturers, which means that the knowledge and academic skills students acquire in the course of their studies should be applicable and transferable from the higher education context to their future professional careers. Given the context of the Languages for Specific Purposes (LSP) classroom, the teachers’ objective is not only to teach the language itself, but also to prepare students to use that language as a medium to develop generic skills and competences. These include media and information literacy, critical and creative thinking, problem-solving and analytical skills, effective written and oral communication, as well as collaborative work and social skills, all of which are necessary to make university graduates more competitive in everyday professional environments. On the other hand, due to limitations of time and large numbers of students in classes, the frequently topic-centered syllabus of LSP courses places considerable focus on acquiring the subject matter and specialist vocabulary instead of sufficient development of skills and competences required by students’ prospective employers. This paper intends to explore some of those issues as viewed both by LSP lecturers and by business professionals in their respective surveys. The surveys were conducted among more than 50 LSP lecturers at higher education institutions in Croatia, more than 40 HR professionals and more than 60 university graduates with degrees in economics and/or business working in management positions in mainly large and medium-sized companies in Croatia. Various elements of LSP course content have been taken into consideration in this research, including reading and listening comprehension of specialist texts, acquisition of specialist vocabulary and grammatical structures, as well as presentation and negotiation skills. The ability to hold meetings, conduct business correspondence, write reports, academic texts, case studies and take part in debates were also taken into consideration, as well as informal business communication, business etiquette and core courses delivered in a foreign language. The results of the surveys conducted among LSP lecturers will be analyzed with reference to what extent those elements are included in their courses and how consistently and thoroughly they are evaluated according to their course requirements. Their opinions will be compared to the results of the surveys conducted among professionals from a range of industries in Croatia so as to examine how useful and important they perceive the same elements of the LSP course content in their working environments. Such comparative analysis will thus show to what extent the syllabi of LSP courses meet the demands of the employment market when it comes to the students’ language skills and competences, as well as transferable skills. Finally, the findings will also be compared to the observations based on practical teaching experience and the relevant sources that have been used in this research. In conclusion, the ideas and observations in this paper are merely open-ended questions that do not have conclusive answers, but might prompt LSP lecturers to re-evaluate the content and objectives of their course syllabi.

Keywords: languages for specific purposes (LSP), language skills, topic-centred syllabus, transferable skills

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Authors: Paula Marín, Mohammad Saffari, Alvaro de Gracia, Luisa F. Cabeza, Svetlana Ushak

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Climate control represents an important issue when referring to energy consumption of buildings and associated expenses, both in installation or operation periods. The climate control of a building relies on several factors. Among them, localization, orientation, architectural elements, sources of energy used, are considered. In order to study the thermal behaviour of a building set up, the present study proposes the use of energy simulation program Energy Plus. In recent years, energy simulation programs have become important tools for evaluation of thermal/energy performance of buildings and facilities. Besides, the need to find new forms of passive conditioning in buildings for energy saving is a critical component. The use of phase change materials (PCMs) for heat storage applications has grown in importance due to its high efficiency. Therefore, the climatic conditions of Northern Chile: high solar radiation and extreme temperature fluctuations ranging from -10°C to 30°C (Calama city), low index of cloudy days during the year are appropriate to take advantage of solar energy and use passive systems in buildings. Also, the extensive mining activities in northern Chile encourage the use of large numbers of containers to harbour workers during shifts. These containers are constructed with lightweight construction systems, requiring heating during night and cooling during day, increasing the HVAC electricity consumption. The use of PCM can improve thermal comfort and reduce the energy consumption. The objective of this study was to evaluate the thermal and energy performance of containers of 2.5×2.5×2.5 m3, located in four cities of Chile: Antofagasta, Calama, Santiago, and Concepción. Lightweight envelopes, typically used in these building prototypes, were evaluated considering a container without PCM inclusion as the reference building and another container with PCM-enhanced envelopes as a test case, both of which have a door and a window in the same wall, orientated in two directions: North and South. To see the thermal response of these containers in different seasons, the simulations were performed considering a period of one year. The results show that higher energy savings for the four cities studied are obtained when the distribution of door and window in the container is in the north direction because of higher solar radiation incidence. The comparison of HVAC consumption and energy savings in % for north direction of door and window are summarised. Simulation results show that in the city of Antofagasta 47% of heating energy could be saved and in the cities of Calama and Concepción the biggest savings in terms of cooling could be achieved since PCM reduces almost all the cooling demand. Currently, based on simulation results, four containers have been constructed and sized with the same structural characteristics carried out in simulations, that are, containers with/without PCM, with door and window in one wall. Two of these containers will be placed in Antofagasta and two containers in a copper mine near to Calama, all of them will be monitored for a period of one year. The simulation results will be validated with experimental measurements and will be reported in the future.

Keywords: energy saving, lightweight construction, PCM, simulation

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Authors: Maari Sugawara

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This arts-based research is about "self-torture": the interplay of seemingly opposing elements of pain, pleasure, submission, and power. It asserts that "self-torture" can be considered a nontrivial mediation between the aesthetic and the sociopolitical. It explores what the author calls queered self-torture; "self-torture" marked by an ambivalence that allows the oppressed to resist, and their counter-valorization occasionally functions as therapeutic solutions to the problems they highlight and condense. The research goal is to deconstruct normative self-torture and propose queered self-torture as a fertile ground for considering the complexities of desire that allow the oppressed to practice freedom. While “self-torture” manifests in many societies, this research focuses on cultural and national identity in post-WWII Japan using this lens of self-torture, as masochism functions as the very basis for Japanese cultural and national identity to ensure self-preservation. This masochism is defined as an impulse to realize a sense of pride and construct an identity through the acceptance of subordination, shame, and humiliation in the face of an all-powerful Other; the dominant Euro-America. It could be argued that this self-torture is a result of Japanese cultural annihilation and the trauma of the nation's defeat to the US. This is the definition of "self-torturous thresholds," the author’s post-WWII Japan psycho-historical diagnosis; when this threshold is crossed, the oppressed begin to torture themselves; the oppressors no longer need to do anything to maintain their power. The oppressed are already oppressing themselves. The term "oppressed" here refers to Japanese individuals and residents of Japan who are subjected to oppressive “white” heteropatriarchal supremacist structures and values that serve colonialist interests. There are three stages in "self-torturous thresholds": (1) the oppressors no longer need to oppress because the oppressed voluntarily commit to self-torture; (2) the oppressed find pleasure in self-torture; and (3) the oppressed achieve queered self-torture, to achieve alternative futures. Using the conceptualization of "self-torture," this research examines and critiques pleasure, desire, capital, and power in postwar Japan, which enables the discussion of the data-colonizing “Moonshot Research and Development program”. If the oppressed want to divest from the habits of normative self-torture, which shape what is possible in both our present and future, we need methods to feel and know that the alternative results of self-torture are possible. Phase three will be enacted using Sarah Ahmed's queer methodology to reorient national and cultural identity away from heteronormativity. Through theoretical analysis, textual analysis, archival research, ethnographic interviews, and digital art projects, including experimental documentary as a method to capture the realities of the individuals who are practicing self-torture, this research seeks to reveal how self-torture may become not just a vehicle of pleasure but also a mode of critiquing power and achieving freedom. It seeks to encourage the imaginings of queer Japanese futures, where the marginalized survive Japan’s natural and man-made disasters and Japan’s Imperialist past and present rather than submitting to the country’s continued violence.

Keywords: arts-based research, Japanese studies, interdisciplinary arts, queer studies, cultural studies, popular culture, BDSM, sadomasochism, sexuality, VR, AR, digital art, visual arts, speculative fiction

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Authors: Mohua Dutta

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The primary aim of this research paper is to investigate the forced urban migration of Dalits in India who are fleeing caste persecution in rural areas. This paper examines the relationship between caste and rural-to-urban internal migration in India using a literary text, Rohinton Mistry’s A Fine Balance, highlighting the challenges faced by Dalits in rural areas that force them to migrate to urban areas. Despite the prevalence of such discussions in Dalit autobiographies written in vernacular languages, there is a lack of discussion regarding caste migration in Indian English Literature, including this present text, as evidenced by the existing critical interpretations of the novel, which this paper seeks to rectify. The primary research question is how urban migration affects caste system in India and why rural-to-urban caste migration occurs. The purpose of this paper is to better understand the reasons for Dalit migration, the challenges they face in rural and urban areas, and the lingering influence of caste in both rural and urban areas. The study reveals that the promise of mobility and emancipation provided by class operations drives rural-to-urban caste migration in India, but it also reveals that caste marginalization in rural areas is closely linked to class marginalization and other forms of subalternity in urban areas. Moreover, the caste system persists in urban areas as well, making Dalit migrants more vulnerable to social, political, and economic discrimination. The reason for this is that, despite changes in profession and urban migration, the trapped structure of caste capital and family networks exposes migrants to caste and class oppressions. To reach its conclusion, this study employs a variety of methodologies. Discourse analysis is used to investigate the current debates and narratives surrounding caste migration. Critical race theory, specifically intersectional theory and social constructivism, aids in comprehending the complexities of caste, class, and migration. Mistry's novel is subjected to textual analysis in order to identify and interpret references to caste migration. Secondary data, such as theoretical understanding of the caste system in operation and scholarly works on caste migration, are also used to support and strengthen the findings and arguments presented in the paper. The study concludes that rural-to-urban caste migration in India is primarily motivated by the promise of socioeconomic mobility and emancipation offered by urban spaces. However, the caste system persists in urban areas, resulting in the continued marginalisation and discrimination of Dalit migrants. The study also highlights the limitations of urban migration in providing true emancipation for Dalit migrants, as they remain trapped within caste and family network structures. Overall, the study raises awareness of the complexities surrounding caste migration and its impact on the lives of India's marginalised communities. This study contributes to the field of Migration Studies by shedding light on an often-overlooked issue: Dalit migration. It challenges existing literary critical interpretations by emphasising the significance of caste migration in Indian English Literature. The study also emphasises the interconnectedness of caste and class, broadening understanding of how these systems function in both rural and urban areas.

Keywords: rural-to-urban caste migration in india, internal migration in india, caste system in india, dalit movement in india, rooster coop of caste and class, urban poor as subalterns

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Authors: Desere Kokt

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Hospitality establishments worldwide are bearing the brunt of the effects of Covid-19. As the hospitality industry is looking to recover, emphasis is placed on rejuvenating the industry. This is especially pertinent for economic development in areas of high unemployment, such as the Free State province of South Africa. The province is not a main tourist area and thus depends on the influx of tourists. The province has great scenic beauty with many accommodation establishments that provide job opportunities to the local population. The two main economic hubs of the Free State province namely Bloemfontein and Clarens, were the focus of the investigation. The emphasis was on graded accommodation establishments as they must adhere to the quality principles of the Tourism Grading Council of South Africa (TGCSA) to obtain star grading. The hospitality industry is known for being labour intensive, and employees need to be available to cater for the needs of paying customers. This is referred to as ‘emotional labour’ and implies that employees need to manage their feelings and emotions as part of performing their jobs. The focus of this study was thus on psychological factors related to working in the hospitality industry – specifically psychological contract and psychological capital and its impact on the commitment of employees in graded accommodation establishments. Employee commitment can be explained as a psychological state that binds the individual to the organisation and involves a set of psychological relationships that include affective (emotions), normative (perceived obligation) and continuance (staying with the organisation) dimensions. Psychological contract refers to the reciprocal beliefs and expectations between the employer and the employee and consists of transactional and rational contracts. Transactional contracts are associated with the economic exchange, and contractional issues related to the employment contract and rational contracts relate to the social exchange between the employee and the organisation. Psychological capital refers to an individual’s positive psychology state of development that is characterised by self-efficiency (having confidence in doing one’s job), optimism (being positive and persevering towards achieving one’s goals), hope (expectations for goals to succeed) and resilience (bouncing back to attain success when beset by problems and adversity). The study employed a quantitative research approach, and a structured questionnaire was used to gather data from respondents. The study was conducted during the Covid-19 pandemic, which hampered the data gathering efforts of the researchers. Many accommodation establishments were either closed or temporarily closed, which meant that data gathering was an intensive and laborious process. The main researcher travelled to the various establishments to collect the data. Nine hospitality establishments participated in the study, and around 150 employees were targeted for data collection. Ninety-two (92) questionnaires were completed, which represents a response rate of 61%. Data were analysed using descriptive and inferential statistics, and partial least squares structural equation modelling (PLS-SEM) was applied to examine the relationship between the variables.

Keywords: employee commitment, hospitality industry, psychological contract, psychological capital

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Authors: V. Vsevolozhskaia

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Since 1990, energy-efficient development concepts have constituted both a turning point in civil engineering and a challenge for an environmentally friendly future. Energy and water currently play an essential role in the sustainable economic growth of the world in general and Russia in particular: the efficiency of the water supply system is the second most important parameter for energy consumption according to the British assessment method, while the water-energy nexus has been identified as a focus for accelerating sustainable growth and developing effective, innovative solutions. The activities considered in this study were aimed at organizing and executing the renovation of the property in residential buildings located in St. Petersburg, specifically buildings with local or federal historical heritage status under the control of the St. Petersburg Committee for the State Inspection and Protection of Historic and Cultural Monuments (KGIOP) and UNESCO. Even after reconstruction, these buildings still fall into energy efficiency class D. Russian Government Resolution No. 87 on the structure and required content of project documentation contains a section entitled ‘Measures to ensure compliance with energy efficiency and equipment requirements for buildings, structures, and constructions with energy metering devices’. Mention is made of the need to install collectors and meters, which only calculate energy, neglecting the main purpose: to make buildings more energy-efficient, potentially even energy efficiency class A. The least-explored aspects of energy-efficient technology in the Russian Federation remain the water balance and the possibility of implementing rain and meltwater collection systems. These modern technologies are used exclusively for new buildings due to a lack of government directive to create project documentation during the planning of major renovations and reconstruction that would include the collection and reuse of rainwater. Energy-efficient technology for rain and meltwater collection is currently applied only to new buildings, even though research has proved that using rainwater is safe and offers a huge step forward in terms of eco-efficiency analysis and water innovation. Where conservation is mandatory, making changes to protected sites is prohibited. In most cases, the protected site is the cultural heritage building itself, including the main walls and roof. However, the installation of a second water supply system and collection of rainwater would not affect the protected building itself. Water efficiency in St. Petersburg is currently considered only from the point of view of the installation that regulates the flow of the pipeline shutoff valves. The development of technical guidelines for the use of grey- and/or rainwater to meet the needs of residential buildings during reconstruction or renovation is not yet complete. The ideas for water treatment, collection and distribution systems presented in this study should be taken into consideration during the reconstruction or renovation of residential cultural heritage buildings under the protection of KGIOP and UNESCO. The methodology applied also has the potential to be extended to other cultural heritage sites in northern countries and lands with an average annual rainfall of over 600 mm to cover average toilet-flush needs.

Keywords: cultural heritage, energy efficiency, renovation, rainwater collection, reconstruction, water management, water supply

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Authors: A.H.Y. Lai, C. Teyra

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In Taiwan, there are 16 official indigenous groups, accounting for 2.3% of the total population. Like other indigenous populations worldwide, indigenous peoples in Taiwan have poorer mental health because of their history of oppression and colonisation. Amid the negative narratives, the ethnic identity of cultural minorities is their unique psychological and cultural asset. Moreover, positive socialisation is found to be related to strong ethnic identity. Based on Phinney’s theory on ethnic identity development and social support theory, this study adopted a strength-based approach conceptualising ethnic identity as the central organising principle that linked perceived social support and mental health among indigenous adults in Taiwan. Aims. Overall aim is to examine the effect of ethnic identity and social support on mental health. Specific aims were to examine : (1) the association between ethnic identity and mental health; (2) the association between perceived social support and mental health ; (3) the indirect effect of ethnic identity linking perceived social support and mental health. Methods. Participants were indigenous adults in Taiwan (n=200; mean age=29.51; Female=31%, Male=61%, Others=8%). A cross-sectional quantitative design was implemented using data collected in the year 2020. Respondent-driven sampling was used. Standardised measurements were: Ethnic Identity Scale(6-item); Social Support Questionnaire-SF(6 items); Patient Health Questionnaire(9-item); and Generalised Anxiety Disorder(7-item). Covariates were age, gender and economic satisfaction. A four-stage structural equation modelling (SEM) with robust maximin likelihood estimation was employed using Mplus8.0. Step 1: A measurement model was built and tested using confirmatory factor analysis (CFA). Step 2: Factor covariates were re-specified as direct effects in the SEM. Covariates were added. The direct effects of (1) ethnic identity and social support on depression and anxiety and (2) social support on ethnic identity were tested. The indirect effect of ethnic identity was examined with the bootstrapping technique. Results. The CFA model showed satisfactory fit statistics: x^2(df)=869.69(608), p<.05; Comparative ft index (CFI)/ Tucker-Lewis fit index (TLI)=0.95/0.94; root mean square error of approximation (RMSEA)=0.05; Standardized Root Mean Squared Residual (SRMR)=0.05. Ethnic identity is represented by two latent factors: ethnic identity-commitment and ethnic identity-exploration. Depression, anxiety and social support are single-factor latent variables. For the SEM, model fit statistics were: x^2(df)=779.26(527), p<.05; CFI/TLI=0.94/0.93; RMSEA=0.05; SRMR=0.05. Ethnic identity-commitment (b=-0.30) and social support (b=-0.33) had direct negative effects on depression, but ethnic identity-exploration did not. Ethnic identity-commitment (b=-0.43) and social support (b=-0.31) had direct negative effects on anxiety, while identity-exploration (b=0.24) demonstrated a positive effect. Social support had direct positive effects on ethnic identity-exploration (b=0.26) and ethnic identity-commitment (b=0.31). Mediation analysis demonstrated the indirect effect of ethnic identity-commitment linking social support and depression (b=0.22). Implications: Results underscore the role of social support in preventing depression via ethnic identity commitment among indigenous adults in Taiwan. Adopting the strength-based approach, mental health practitioners can mobilise indigenous peoples’ commitment to their group to promote their well-being.

Keywords: ethnic identity, indigenous population, mental health, perceived social support

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Authors: Sandra Carrillo Hoyos

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Mining activities in South America have significantly grown during the last decades, given the abundance of natural resources, the implemented governmental policies to incentivize foreign investment as well as the boom in international prices for metals and oil between 2002 and 2008. While this context allowed the region to occupy a leading position between the top producers of minerals around the world, it has also meant an increase in socio-environmental conflicts which have generated costs and negative impacts not only for the companies but especially for the governments and local communities.During the latest decade, the mining sector in Peru has faced with the social resistance of a large number of communities, which began organizing actions against the implementation of high investing projects. The dissatisfaction has derived in the prevalence of socio-environmental conflicts associated with mining activities, some of them never solved into an agreement. In order to prevent those socio-environmental conflicts and obtain the social license from local communities, most of the mining companies have developed diverse initiatives within the framework of policies and practices of corporate social responsibility (CSR). This paper has assessed the mining sector’s contribution toward the local development management along the last decade, as part of CSR strategies as well as the policies promoted by the Peruvian State. This assessment found that, in the beginning, these initiatives have been based on a philanthropic approach and were reacting to pressures from local stakeholders to maintain the consent to operate from the surrounding communities as well as to create, as a result, a harmonious atmosphere for operations. Due to the weak State presence, such practices have increased the expectations of communities related to the participation of mining companies in solving structural development problems, especially those related to primary needs, infrastructure, education, health, among others. In other words, this paper was focused on analyze in what extent these initiatives have promoted local empowerment for development planning and integrated management of natural resources from a territorial approach. From this perspective, the analysis demonstrates that, while the design and planning of social investment initiatives have improved due to the sector´s sustainability approach, many companies have developed actions beyond their competence during this process. In some cases, the referenced actions have generated dependency with communities, even though this relationship has not exempted the companies of conflict situations with unfortunate consequences. Furthermore, the social programs developed have not necessarily generated a significant impact in improving the quality of life of affected populations. In fact, it is possible to identify that those regions with high mining resources and investment are facing with a situation of poverty and high dependency on mining production. In spite of the revenues derived from mining industry, local governments have not been able to translate the royalties into sustainable development opportunities. For this reason, the proposed paper suggests some challenges for the mining sector contribution to local development based on the best practices and lessons learnt from a benchmarking for the leading mining companies.

Keywords: corporate social responsibility, local development, mining, socio-environmental conflict

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Authors: O. Squillace, R. L. Thompson

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Migration of small molecules to, and across the surface of polymer matrices is a little-studied problem with important industrial applications. Tackifiers in adhesives, flavors in foods and binding agents in paints all present situations where the function of a product depends on the ability of small molecules to migrate through a polymer matrix to achieve the desired properties such as softness, dispersion of fillers, and to deliver an effect that is felt (or tasted) on a surface. It’s been shown that the chemical and molecular structure, surface free energies, phase behavior, close environment and compatibility of the system, influence the migrants’ motion. When differences in behavior, such as occurrence of segregation to the surface or not, are observed it is then of crucial importance to identify and get a better understanding of the driving forces involved in the process of molecular migration. In this aim, experience is meant to be allied with theory in order to deliver a validated theoretical and computational toolkit to describe and predict these phenomena. The systems that have been chosen for this study aim to address the effect of polarity mismatch between the migrants and the polymer matrix and that of a second migrant over the first one. As a non-polar resin polymer, polyvinyl acetate is used as the material to which more or less polar migrants (sorbitol, carvone, octanoic acid (OA), triacetin) are to be added. Through contact angle measurement a surface excess is seen for sorbitol (polar) mixed with PVAc as the surface energy is lowered compare to the one of pure PVAc. This effect is increased upon the addition of carvon or triacetin (non-polars). Surface micro-structures are also evidenced by atomic force microscopy (AFM). Ion beam analysis (Nuclear Reaction Analysis), supplemented by neutron reflectometry can accurately characterize the self-organization of surfactants, oligomers, aromatic molecules in polymer films in order to relate the macroscopic behavior to the length scales that are amenable to simulation. The nuclear reaction analysis (NRA) data for deuterated OA 20% shows the evidence of a surface excess which is enhanced after annealing. The addition of 10% triacetin, as a second migrant, results in the formation of an underlying layer enriched in triacetin below the surface excess of OA. The results show that molecules in polarity mismatch with the matrix tend to segregate to the surface, and this is favored by the addition of a second migrant of the same polarity than the matrix. As studies have been restricted to materials that are model supported films under static conditions in a first step, it is also wished to address the more challenging conditions of materials under controlled stress or strain. To achieve this, a simple rig and PDMS cell have been designed to stretch the material to a defined strain and to probe these mechanical effects by ion beam analysis and atomic force microscopy. This will make a significant step towards exploring the influence of extensional strain on surface segregation, flavor release in cross-linked rubbers.

Keywords: polymers, surface segregation, thin films, molecular migration

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